CN102253108B - High pressure digestion ICP-MS method for determining rare earth element content in crude oil - Google Patents
High pressure digestion ICP-MS method for determining rare earth element content in crude oil Download PDFInfo
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Abstract
A high pressure digestion ICP-MS (inductively coupled plasma mass spectrometry) method for determining rare earth element contents in crude oil belongs to a chemical detection method for detecting 16 rare earth elements in crude oil, such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, etc. In a sample high pressure digestion process, an ICP-OES (inductively coupled plasma optical emission spectrometry) method is first used to determine a wave spectrum intensity at 193.027nm of a carbonaceous element in a digestion solution, in order to determine a digestion degree; so that problems of apparatus loss and pollution caused by incomplete digestion and large result deviation caused by high matrix interference in a high pressure digestion method are solved. In an ICP-MS apparatus determination of the sample digestion solution, an on-line adding of internal standard solution and a collision reaction cell technology are employed to eliminate interferences and optimize apparatus working conditions. The method has a detection limit reaching 0.01[mu]g/kg-0.7[mu]g/kg and a recovery rate between 80.4%-105.2%, has advantages of low detection limit, rapidness and accuracy, etc., and can satisfy detection requirements of rare earth elements in crude oil.
Description
Technical field
The present invention relates to a kind of chemical detection method of crude oil middle rare earth constituent content, be meant the method for high-pressure digestion ICP-MS method mensuration crude oil middle rare earth constituent content specifically.
Background technology
Rare earth is meant the general name of scandium in the periodic table of elements, yttrium and lanthanide series.REE is a heavy metal element, and in Crude Oil Processing, the REE in the crude oil not only can reduce activity of such catalysts; Make the permanent poisoning of catalyzer; Shorten catalyzer serviceable life, also can reduce purpose product selectivity in the crude oil, very big to petroleum refining technology and product quality influence; Therefore the content of crude oil middle rare earth element is to estimate a good and bad important indicator of crude oil, and it is significant accurately to measure its content.
The analytical approach of crude oil middle rare earth element mainly contains atomic absorption spectrography (AAS), inductively coupled plasma spectrometry method at present; Be methods such as ICP-OES method, these methods respectively have its limitation, and they or sample pre-treatments are complicated; Maybe can not be used for polycomponent, multielement analysis; Time and effort consuming, and instrumental sensitivity or detection limit do not reach index request, and have defectives such as element interference, spectrum interference.So commonly used still is with high-pressure digestion and inductively coupled plasma mass spectrometry; Be that the ICP-MS method is measured; The high-pressure digestion technology is ICP-MS method pre-treatment means commonly used, have that Specimen eliminating is fast, reagent consumption less, low, the no container of blank value adsorbs, digestion process does not have and advantage such as stains.But at present, high-pressure digestion is weighed clear up complete with the clarity of digestion solution and the color and luster of solution, and the result lacks accuracy, influences the mensuration result of ICP-MS method easily.
Summary of the invention
Technical matters to be solved by this invention be to overcome the defective of prior art and provide a kind of have detection limit low, detect the method that quick and accurate high-pressure digestion ICP-MS method is measured crude oil middle rare earth constituent content.
Technical matters of the present invention realizes through following technical scheme:
A kind of high-pressure digestion ICP-MS method is measured the method for crude oil middle rare earth constituent content, comprise at first use in the ICP-OES method working sample digestion solution institute's carbon elements at the 193.027nm place wave spectrum intensity judge clearing up degree; Use the content of each REE in the ICP-MS method working sample digestion solution then;
Wave spectrum intensity is following to the step of clearing up degree and judging at the 193.027nm place for institute's carbon elements in the described ICP-OES method working sample digestion solution:
(1) take by weighing crude oil sample 0.4g～0.5g and place in the 100mL high-pressure digestion jar, add concentration 70% nitric acid, 8～14mL and concentration 30% hydrogen peroxide 1～5mL and process a kind liquid, tighten cover, the high-pressure digestion jar that kind liquid will be housed is then put into air dry oven; Start air dry oven, open program control system, set air dry oven and be warming up to 190 ℃～195 ℃, powered-down behind constant temperature time 1～7h, natural cooling; Open cover after the end, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to 25mL with ultrapure water, obtain Specimen eliminating solution; In another 100mL high-pressure digestion jar, directly add concentration 70% nitric acid, 8～14mL and concentration 30% hydrogen peroxide 1～5mL and process a kind liquid, tighten cover, the high-pressure digestion jar that kind liquid will be housed is then put into air dry oven; Start air dry oven, open program control system, set air dry oven and be warming up to 190 ℃～195 ℃, powered-down behind constant temperature time 1～7h, natural cooling; Open cover after the end, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to 25mL with ultrapure water, obtain blank digestion solution;
The Specimen eliminating solution utilization inductively-coupled plasma spectrometer that (2) will obtain according to step (1), promptly in the ICP-OES Instrument measuring Specimen eliminating solution institute's carbon elements at the 193.027nm place wave spectrum intensity, record the carbon intensity level, and definite Specimen eliminating degree;
The step of each ree content is following in the described ICP-MS method working sample digestion solution:
(3) configuration standard working solution: take by weighing rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb and Lu standard inventory solution that concentration is 1.0mg/mL respectively; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-1 of concentration as 1.0mg/L; The said standard solution mother liquor-1 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-1 respectively with concentration 5% salpeter solution, the content of each element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L respectively in the standard operation solution-1 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL; Take by weighing rare earth element tb standard inventory solution; The Tb standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-2 of concentration as 1.0mg/L; The standard solution mother liquor-2 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-2 respectively with concentration 5% salpeter solution, the content of Tb element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L in the standard operation solution-2 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL;
(4) configuration inner mark solution: taking by weighing concentration respectively is REE Ge and the Tb standard inventory solution of 1.0mg/mL; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-1 of concentration as 1.0mg/L; Taking by weighing concentration is the Rh standard inventory solution of 1.0mg/mL, and the Rh standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-2 of concentration as 1.0mg/L;
The standard operation solution that (5) will obtain according to step (3) and measure: adopt two peristaltic pump sample introduction systems to introduce inner mark solutions-1 and inner mark solution-2 according to the Specimen eliminating solution that step (1) obtains; Pump line with two different inner diameters; Specimen eliminating solution, blank digestion solution that standard operation solution that successively inner mark solution-1 and inner mark solution-2 is obtained with step (3) respectively with same pump speed and step (1) obtain import icp ms; It is the ICP-MS instrument; Before getting into atomizer, mix, select the best isotope of each element to measure; For the first time measure online adding inner mark solution-1, select for use
72Ge be Sc and Y internal standard element,
159Tb is the internal standard element of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, measures online adding inner mark solution-2 for the second time, selects for use
103Rh is as the internal standard element of the Tb in measuring for the first time; Elder generation's metric works solution-1 and standard operation solution-2; Again according to the known content and the icp ms of each element in standard operation solution-1 and the standard operation solution-2; Be the ICP-MS Instrument measuring to each element response draw the standard working curve of each element respectively; The response of working sample digestion solution and blank each element of digestion solution then; Calculate the concentration value of blank each element of digestion solution and the concentration value of each element of Specimen eliminating solution according to standard working curve, calculate the content X of each REE in the crude oil according to following formula
n:
In the formula: C
1The concentration value of-Specimen eliminating solution
C
0The concentration value of-blank digestion solution
V-digestion solution constant volume
The crude oil sample amount that m-takes by weighing
Calculate the content of each rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu and Tb in the crude oil sample.
The high-pressure digestion jar of selecting for use in the described step (1) comprises polytetrafluoroethylliner liner and stainless cylinder of steel overcoat.
Inductively-coupled plasma spectrometer in the described step (2), promptly the ICP-OES instrument is a Varian725-ES type ICP-OES instrument, running parameter is: radio-frequency power 1200W; Atomizer flow 0.6L/min; Secondary air amount 1.50L/min, plasma gas flow rate 15.0L/min, peristaltic pump pump speed 15rpm; Observed altitude 6mm, integral time 10s.
Icp ms in the described step (5), promptly the ICP-MS instrument is an Agilent7500ex type ICP-MS instrument, running parameter is: radio-frequency power 1500W; Sampling depth 7.0mm, torch pipe horizontal level 0.1mm, torch pipe upright position-0.2mm; Carrier gas flux 0.85L/min, complemental air flow 0.3L/min, 2 ℃ of atomization temperatures; Peristaltic pump pump speed 0.1rps, eight grades of bar voltage-18V, level Four bar voltage-16V; Focus voltage-10V, under the crash response pool mode, collision airshed 0.48L/min; Use Full Quant type collection data, be 0.1s the integral time of every kind of element, multiplicity 3 times.
The isotope of selected each element is respectively in the described step (5)
45Sc,
89Y,
139La,
140Ce,
141Pr,
146Nd,
147Sm,
153Eu,
157Gd,
163Dy,
165Ho,
166Er,
169Tm,
172Yb,
175Lu,
159Tb.
The invention has the beneficial effects as follows:
(1) clears up the effect of clearing up that the employed reagent dosage of crude oil sample and digestion time can improve sample through change.
(2) change present high-pressure digestion and weigh clear up complete with the clarity of digestion solution and the color and luster of solution, the result lacks the present situation of accuracy, has realized clearing up the accurate judgement of degree.
(3) quantitative judgement clear up the influence of degree to final mensuration result precision, digestion time is long more, it is just good more to clear up degree, matrix disturbs just more little, the result is just accurate more.
Description of drawings
Fig. 1 is standard working curve figure.
Fig. 2 clears up 1h respectively for crude oil under 195 ℃, 2h, 3h, 4h, 5h, 6h, the carbon spectral intensity figure that records behind the 7h.
Fig. 3 is the influence figure of nitric acid dosage to the carbon response.
Fig. 4 is the influence figure of hydrogen peroxide consumption to the carbon response.
Fig. 5 is the variation of different solutions carbon intensity.
Fig. 6 is that different high-pressure digestions are under the time; Use the inductively coupled plasma spectrometry method respectively; Be that the ICP-OES method is measured carbon intensity and inductively coupled plasma mass spectrometry in the digestion solution, promptly the ICP-MS method is measured the relative ratio of five kinds of constituent contents such as La in the digestion solution.
Fig. 7 is the pattern of imported crude oil middle rare earth element.
Fig. 8 is the pattern of imported crude oil middle rare earth element.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done further explain, but embodiments of the invention are not limited thereto.
High-pressure digestion ICP-MS method is measured the method for crude oil middle rare earth constituent content, and this method comprises that at first using the inductively coupled plasma spectrometry method to measure in the digestion solution institute's carbon elements judges clearing up degree in 193.027 nm place wave spectrum intensity; Use inductively coupled plasma mass spectrometry to measure the content of each REE in the digestion solution then.Inductively coupled plasma spectrometry method, i.e. ICP-OES method; Inductively coupled plasma mass spectrometry, promptly the ICP-MS method below relates to above-mentioned two kinds of methods and all replaces with ICP-OES method and ICP-MS method.
1, used instrument of experiment and equipment
Inductively-coupled plasma spectrometer Varian 725-ES type
Icp ms U.S. Agilent7500ex type
Air dry oven
100mL high-pressure digestion jar: constitute by polytetrafluoroethylliner liner and stainless cylinder of steel overcoat
2, used instrument of experiment and apparatus operating parameters
2.1 inductively-coupled plasma spectrometer, the i.e. running parameter of ICP-OES instrument:
Radio-frequency power: 1200W
Atomizer flow: 0.6L/min
Secondary air amount: 1.50L/min
Plasma gas flow rate: 15.0L/min
Wriggling pump speed: 15rpm
Observed altitude: 6mm
Integral time: 10s
2.2 icp ms, i.e. ICP-MS instrument:
Radio-frequency power: 1500W
Sampling depth: 7.0mm
Torch pipe horizontal level: 0.1mm
Torch pipe upright position :-0.2mm
Carrier gas flux: 0.85L/min
Complemental air flow: 0.3L/min
Atomization temperature: 2 ℃
Peristaltic pump pump speed: 0.1rps
Eight grades of bar voltage :-18V
Level Four bar voltage :-16V
Focus voltage :-10V
Under the crash response pool mode, collision gas (helium) flow: 0.48L/min
Use Full Quant type collection data, be the integral time of every kind of element: 0.1s, multiplicity 3 times
3, experiment agents useful for same
Ultrapure water (self-control)
30% hydrogen peroxide (excellent pure level)
70%, 5% nitric acid (electron level)
The configuration of blank digestion solution: in 100mL high-pressure digestion jar, directly add concentration 70% nitric acid, 8～14mL and concentration 30% hydrogen peroxide 1～5mL and process a kind liquid, tighten cover, the high-pressure digestion jar that kind liquid will be housed is then put into air dry oven; Start air dry oven, open program control system, set air dry oven and be warming up to 190 ℃～195 ℃, powered-down behind constant temperature time 1～7h, natural cooling; Open cover after the end, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to 25mL with ultrapure water, obtain blank digestion solution;
The configuration of standard operation solution-1: take by weighing rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb and Lu standard inventory solution that concentration is 1.0mg/mL respectively; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-1 of concentration as 1.0mg/L; The said standard solution mother liquor-1 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-1 respectively with concentration 5% salpeter solution, the content of each element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L respectively in the standard operation solution-1 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL;
The configuration of standard operation solution-2: take by weighing rare earth element tb standard inventory solution; The Tb standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-2 of concentration as 1.0mg/L; The standard solution mother liquor-2 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-2 respectively with concentration 5% salpeter solution, the content of Tb element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L in the standard operation solution-2 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL;
The configuration of inner mark solution-1: taking by weighing concentration respectively is REE Ge and the Tb standard inventory solution of 1.0mg/mL; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-1 of concentration as 1.0mg/L;
The configuration of inner mark solution-2: taking by weighing concentration is the Rh standard inventory solution of 1.0mg/mL, and the Rh standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-2 of concentration as 1.0mg/L;
Tuning liquid: 1 μ g/L
89Y,
140Ce solution.
4. test procedure
4.1 embodiment 1
Take by weighing DOPA crude oil sample 0.4008g and place in the 100mL high-pressure digestion jar, add concentration 30% hydrogen peroxide 2mL, add concentration 70% nitric acid 12mL then; Tighten cover, put into air dry oven, be warming up to 195 ℃ after constant temperature 3h again; Powered-down then, natural cooling.Clear up and finish to open cover, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to 25mL with ultrapure water, obtain digestion solution.With above-mentioned gained digestion solution utilization inductively-coupled plasma spectrometer, promptly the ICP-OES appearance measure in the digestion solution institute's carbon elements at the 193.027nm place wave spectrum intensity, the carbon intensity level that records is 40235.
The content of each REE in the utilization ICP-MS method fast measuring digestion solution: take by weighing rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb and Lu standard inventory solution that concentration is 1.0mg/mL at first respectively; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-1 of concentration as 1.0mg/L; The said standard solution mother liquor-1 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-1 respectively with concentration 5% salpeter solution, the content of each element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L respectively in the standard operation solution-1 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL; Take by weighing rare earth element tb standard inventory solution; The Tb standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-2 of concentration as 1.0mg/L; The standard solution mother liquor-2 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-2 respectively with concentration 5% salpeter solution, the content of Tb element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L in the standard operation solution-2 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL.
Taking by weighing concentration respectively is REE Ge and the Tb standard inventory solution of 1.0mg/mL, and the standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-1 of concentration as 1.0mg/L; Taking by weighing concentration is the Rh standard inventory solution of 1.0mg/mL, and the Rh standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-2 of concentration as 1.0mg/L.
The utilization icp ms; Be that the ICP-MS instrument is measured standard operation solution and Specimen eliminating solution: adopt two peristaltic pump sample introduction systems to introduce inner mark solution-1 and inner mark solution-2; Pump line with two different inner diameters; Successively inner mark solution-1 and inner mark solution-2 are imported icp ms with standard operation solution, Specimen eliminating solution and blank digestion solution respectively with same pump speed; Be the ICP-MS instrument, before getting into atomizer, mix, select the best isotope of each element to measure; For the first time measure online adding inner mark solution-1, select for use
72Ge be Sc and Y internal standard element,
159Tb is the internal standard element of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, measures online adding inner mark solution-2 for the second time, selects for use
103Rh is as the internal standard element of the Tb in measuring for the first time.
Elder generation's metric works solution-1 and standard operation solution-2; Again according to the known content and the icp ms of each element in standard operation solution-1 and the standard operation solution-2; Be the ICP-MS Instrument measuring to each element response draw the standard working curve of each element respectively; The response of working sample digestion solution and blank each element of digestion solution then; Calculate the concentration value of each element of Specimen eliminating solution and the concentration value of blank each element of digestion solution according to standard working curve, calculate the content X of each REE in the crude oil according to following formula
n:
In the formula: C
1The concentration value of-Specimen eliminating solution
C
0The concentration value of-blank digestion solution
V-digestion solution constant volume
The crude oil sample amount that m-takes by weighing
Record the content of each element of DOPA crude oil digestion solution, calculate the result, see the following form:
Unit: μ g/kg
| Sc | Y | La | Ce | Pr | Nd | Sm | Gd | Tb | Dy | Ho | Er | Tm | Yb | Lu |
| 35.1 | 1654 | 418 | 923 | 121 | 618 | 212 | 2.74 | 0.00 | 0.91 | 39 | 0.73 | 0.07 | 0.23 | 0.1 |
4.2 embodiment 2
Take by weighing DOPA crude oil sample 0.4012g and place in the 100mL high-pressure digestion jar, add concentration 30% hydrogen peroxide 2mL, add concentration 70% nitric acid 12mL then; Tighten cover, put into air dry oven, be warming up to 195 ℃ after constant temperature 5h again; Powered-down then, natural cooling.Clear up and finish to open cover, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to 25mL with ultrapure water, obtain Specimen eliminating solution.With above-mentioned gained digestion solution utilization inductively-coupled plasma spectrometer, promptly the ICP-OES appearance measure in the digestion solution institute's carbon elements at the 193.027nm place wave spectrum intensity, the carbon intensity level that records is 32108.
The content of each REE in the utilization ICP-MS method fast measuring digestion solution: take by weighing rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb and Lu standard inventory solution that concentration is 1.0mg/mL at first respectively; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-1 of concentration as 1.0mg/L; The said standard solution mother liquor-1 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-1 respectively with concentration 5% salpeter solution, the content of each element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L respectively in the standard operation solution-1 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL; Take by weighing rare earth element tb standard inventory solution; The Tb standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-2 of concentration as 1.0mg/L; The standard solution mother liquor-2 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-2 respectively with concentration 5% salpeter solution, the content of Tb element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L in the standard operation solution-2 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL.
Taking by weighing concentration respectively is REE Ge and the Tb standard inventory solution of 1.0mg/mL, and the standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-1 of concentration as 1.0mg/L; Taking by weighing concentration is the Rh standard inventory solution of 1.0mg/mL, and the Rh standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-2 of concentration as 1.0mg/L.
The utilization icp ms; Be that the ICP-MS instrument is measured standard operation solution and Specimen eliminating solution: adopt two peristaltic pump sample introduction systems to introduce inner mark solution-1 and inner mark solution-2; Pump line with two different inner diameters; Successively inner mark solution-1 and inner mark solution-2 are imported icp ms with standard operation solution, Specimen eliminating solution and blank digestion solution respectively with same pump speed; Be the ICP-MS instrument, before getting into atomizer, mix, select the best isotope of each element to measure; For the first time measure online adding inner mark solution-1, select for use
72Ge be Sc and Y internal standard element,
159Tb is the internal standard element of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, measures online adding inner mark solution-2 for the second time, selects for use
103Rh is as the internal standard element of the Tb in measuring for the first time.
Elder generation's metric works solution-1 and standard operation solution-2; Again according to the known content and the icp ms of each element in standard operation solution-1 and the standard operation solution-2; Be the ICP-MS Instrument measuring to each element response draw the standard working curve of each element respectively; The response of working sample digestion solution and blank each element of digestion solution then; Calculate the concentration value of each element of Specimen eliminating solution and the concentration value of blank each element of digestion solution according to standard working curve, calculate the content X of each REE in the crude oil according to following formula
n:
In the formula: C
1The concentration value of-Specimen eliminating solution
C
0The concentration value of-blank digestion solution
V-digestion solution constant volume
The crude oil sample amount that m-takes by weighing
Record the content of each element of DOPA crude oil digestion solution, calculate the result, see the following form:
Unit: μ g/kg
| Sc | Y | La | Ce | Pr | Nd | Sm | Gd | Tb | Dy | Ho | Er | Tm | Yb | Lu |
| 41.1 | 1903 | 602 | 1658 | 178 | 921 | 252 | 417 | 61.4 | 350 | 67.5 | 147 | 14.7 | 73.7 | 6.75 |
4.3 embodiment 3
Take by weighing the blue special crude oil sample 0.4086g of Eschka and place in the 100mL high-pressure digestion jar, add concentration 30% hydrogen peroxide 2mL, add concentration 70% nitric acid 12mL then; Tighten cover, put into air dry oven, be warming up to 195 ℃ after constant temperature 5h again; Powered-down then, natural cooling.Clear up and finish to open cover, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to 25mL with ultrapure water, obtain digestion solution.With above-mentioned gained digestion solution utilization inductively-coupled plasma spectrometer, promptly the ICP-OES appearance measure in the digestion solution institute's carbon elements at the 193.027nm place wave spectrum intensity, the carbon intensity level that records is 33158.
The content of each REE in the utilization ICP-MS method fast measuring digestion solution: take by weighing rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb and Lu standard inventory solution that concentration is 1.0mg/mL at first respectively; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-1 of concentration as 1.0mg/L; The said standard solution mother liquor-1 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-1 respectively with concentration 5% salpeter solution, the content of each element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L respectively in the standard operation solution-1 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL; Take by weighing rare earth element tb standard inventory solution; The Tb standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-2 of concentration as 1.0mg/L; The standard solution mother liquor-2 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-2 respectively with concentration 5% salpeter solution, the content of Tb element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L in the standard operation solution-2 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL.
Taking by weighing concentration respectively is REE Ge and the Tb standard inventory solution of 1.0mg/mL, and the standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-1 of concentration as 1.0mg/L; Taking by weighing concentration is the Rh standard inventory solution of 1.0mg/mL, and the Rh standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-2 of concentration as 1.0mg/L.
The utilization icp ms; Be that the ICP-MS instrument is measured standard operation solution and Specimen eliminating solution: adopt two peristaltic pump sample introduction systems to introduce inner mark solution-1 and inner mark solution-2; Pump line with two different inner diameters; Successively inner mark solution-1 and inner mark solution-2 are imported icp ms with standard operation solution, Specimen eliminating solution and blank digestion solution respectively with same pump speed; Be the ICP-MS instrument, before getting into atomizer, mix, select the best isotope of each element to measure; For the first time measure online adding inner mark solution-1, select for use
72Ge be Sc and Y internal standard element,
159Tb is the internal standard element of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, measures online adding inner mark solution-2 for the second time, selects for use
103Rh is as the internal standard element of the Tb in measuring for the first time.
Elder generation's metric works solution-1 and standard operation solution-2; Again according to the known content and the icp ms of each element in standard operation solution-1 and the standard operation solution-2; Be the ICP-MS Instrument measuring to each element response draw the standard working curve of each element respectively; The response of working sample digestion solution and blank each element of digestion solution then; Calculate the concentration value of each element of Specimen eliminating solution and the concentration value of blank each element of digestion solution according to standard working curve, calculate the content X of each REE in the crude oil according to following formula
n:
In the formula: C
1The concentration value of-Specimen eliminating solution
C
0The concentration value of-blank digestion solution
V-digestion solution constant volume
The crude oil sample amount that m-takes by weighing
Record the content of blue special each element of crude oil digestion solution of Eschka, calculate the result, see the following form:
Unit: μ g/kg
| Sc | Y | La | Ce | Pr | Nd | Sm | Gd | Tb | Dy | Ho | Er | Tm | Yb | Lu |
| 0.38 | 73.8 | 38.4 | 98.3 | 13.8 | 75.7 | 15.7 | 26.6 | 3.34 | 13.8 | 2.65 | 5.51 | 0.38 | 2.06 | 0.26 |
4.4 embodiment 4
Take by weighing Barrow island crude oil sample 0.4118g and place in the 100mL high-pressure digestion jar, add 30% hydrogen peroxide 2mL, add 70% nitric acid 12mL then; Cover lid is packed in the stainless cylinder of steel overcoat, tightens cover; Put into air dry oven; Constant temperature 5h again after being warming up to 195 ℃, powered-down then, natural cooling.Clear up and finish to open cover, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to scale with ultrapure water, obtain digestion solution.With above-mentioned gained digestion solution utilization inductively-coupled plasma spectrometer, promptly the ICP-OES appearance measure in the digestion solution institute's carbon elements at the 193.027nm place wave spectrum intensity, the carbon intensity level that records is 34582.
The content of each REE in the utilization ICP-MS method fast measuring digestion solution: take by weighing rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb and Lu standard inventory solution that concentration is 1.0mg/mL at first respectively; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-1 of concentration as 1.0mg/L; The said standard solution mother liquor-1 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-1 respectively with concentration 5% salpeter solution, the content of each element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L respectively in the standard operation solution-1 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL; Take by weighing rare earth element tb standard inventory solution; The Tb standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-2 of concentration as 1.0mg/L; The standard solution mother liquor-2 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-2 respectively with concentration 5% salpeter solution, the content of Tb element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L in the standard operation solution-2 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL.
Taking by weighing concentration respectively is REE Ge and the Tb standard inventory solution of 1.0mg/mL, and the standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-1 of concentration as 1.0mg/L; Taking by weighing concentration is the Rh standard inventory solution of 1.0mg/mL, and the Rh standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-2 of concentration as 1.0mg/L.
The utilization icp ms; Be that the ICP-MS instrument is measured standard operation solution and Specimen eliminating solution: adopt two peristaltic pump sample introduction systems to introduce inner mark solution-1 and inner mark solution-2; Pump line with two different inner diameters; Successively inner mark solution-1 and inner mark solution-2 are imported icp ms with standard operation solution, Specimen eliminating solution and blank digestion solution respectively with same pump speed; Be the ICP-MS instrument, before getting into atomizer, mix, select the best isotope of each element to measure; For the first time measure online adding inner mark solution-1, select for use
72Ge be Sc and Y internal standard element,
159Tb is the internal standard element of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, measures online adding inner mark solution-2 for the second time, selects for use
103Rh is as the internal standard element of the Tb in measuring for the first time.
Elder generation's metric works solution-1 and standard operation solution-2; Again according to the known content and the icp ms of each element in standard operation solution-1 and the standard operation solution-2; Be the ICP-MS Instrument measuring to each element response draw the standard working curve of each element respectively; The response of working sample digestion solution and blank each element of digestion solution then; Calculate the concentration value of each element of Specimen eliminating solution and the concentration value of blank each element of digestion solution according to standard working curve, calculate the content X of each REE in the crude oil according to following formula
n:
In the formula: C
1The concentration value of-Specimen eliminating solution
C
0The concentration value of-blank digestion solution
V-digestion solution constant volume
The crude oil sample amount that m-takes by weighing
Record the content of Barrow island each element of crude oil digestion solution, calculate the result, see the following form:
Unit: μ g/kg
| Sc | Y | La | Ce | Pr | Nd | Sm | Gd | Tb | Dy | Ho | Er | Tm | Yb | Lu |
| 3.96 | 3.96 | 609 | 79.2 | 4.02 | 7.92 | 2.92 | 2.74 | 0 | 0.91 | 0.24 | 0.73 | 0.07 | 0.23 | 0.1 |
5. the affirmation of intensification temperature and constant temperature time
The digestion condition height is two most important factor that effect is cleared up in influence with time length; 190 ℃～195 ℃ is the preference temperature of oil product being carried out high-pressure digestion, therefore, is chosen under 195 ℃; For clearing up reagent, investigated digestion time with nitric acid-hydrogen peroxide to clearing up the influence of degree.Fig. 2 clears up 1h respectively for crude oil under 195 ℃, 2h, 3h, 4h, 5h, 6h, the carbon spectral intensity figure that records behind the 7h.As can beappreciated from fig. 2, along with the prolongation of digestion time, carbon intensity reduces.Clear up at 195 ℃ when crude oil and to reach 5h when above, carbon signal response value tends towards stability.Explanation is cleared up fully after the clearing up of 5h at 195 ℃ of following crude oil basically.Observe the clarity of digestion solution and the color and luster of solution, crude oil 195 ℃ clear up 4h after, digestion solution is limpid, but still has more foam after acutely shaking, and explain that crude oil is not also thoroughly cleared up at this moment; And crude oil 195 ℃ clear up 5h after, acutely shake back solution clear still, explain that this moment, crude oil was cleared up complete at 195 ℃ after 5h clears up.This phenomenon is consistent through the carbon spectral intensity result of different digestion time gained with crude oil.Thereby the condition of clearing up of this experimental selection crude oil is for to clear up 5h under 195 ℃.Nitric acid is that the first-selection during ICP-MS analyzes is cleared up reagent, and the adding of superoxol helps to reduce the digestion of pressure and promotion sample, and for this reason, this experiment adopts nitric acid-hydrogen peroxide system as clearing up reagent.
6. clearing up the consumption of nitric acid and hydrogen peroxide in the reagent selects
Nitric acid is that the first-selection during ICP-MS analyzes is cleared up reagent, and the adding of hydrogen peroxide helps to reduce the digestion of pressure and promotion sample, and for this reason, this test adopts nitric acid-hydrogen peroxide system as clearing up reagent.
Investigated and cleared up reagent dosage clearing up the influence of degree.Fig. 3 is the influence figure of nitric acid dosage to the carbon response, and visible by Fig. 3, along with the continuous increase of nitric acid amount, the carbon response constantly reduces, and when nitric acid added 12mL, the signal response value tended towards stability.Because the concentration of superoxol is about 30%, too much adding hydrogen peroxide might cause the reduction of nitric acid digestion system concentration, thus influence digestion effect, and when superoxol added 2mL, the signal response value was minimum, sees Fig. 4.Amid all these factors, select in test adding 12mL nitric acid and 2mL hydrogen peroxide that crude oil is carried out high-pressure digestion.
7. carbon is in the affirmation of 193.027nm place wave spectrum intensity
In crude oil high-pressure digestion process, what mainly destroy is the organic hydrocarbon component of crude oil, makes the carbochain fracture.The ICP-OES method can be measured the spectral intensity at C193.027nm place, if crude oil sample is cleared up fully, then the organic hydrocarbon carbochain ruptures fully and is broken in the micromolecule solution acid solution or becomes CO
2And the CO form, C193.027nm place signal analog value reduces.In 5% aqueous solution of nitric acid, add methyl alcohol, ethanol,
propyl alcohol, normal butyl alcohol and corresponding mixture respectively; Making the carbon content in the solution all is that (ratio in the potpourri all is mol ratio to 100mmol/L; Ratio is 1: 1); Observe their carbon response, as shown in Figure 5.Visible by Fig. 5; Be in the solution of 100mmol/L in carbon content; The ICP-OES method records C193.027nm place spectral intensity and constantly increases along with the increase of carbochain, is illustrated under the certain condition of former oil mass, and C193.027nm place spectral intensity can reflect the degree of clearing up of crude oil.Therefore this test judges that through the intensity of spectral lines of ICP-OES method mensuration carbon crude oil clears up degree.
8. the degree of clearing up is to measuring result's influence
The degree of clearing up is to measure the whether accurate key factor of result.Investigated the different degree of clearing up to measuring result's influences, Fig. 6 be different high-pressure digestions under the time, uses the ICP-OES method to measure the relative ratio of five kinds of constituent contents such as La in carbon intensity in the digestion solution and the ICP-MS mensuration digestion solution respectively.The result shows that digestion time is long more, and carbon intensity is low more, and the measured value of five kinds of REEs is high more.Explain that digestion time is long more, it is just good more to clear up degree, and matrix disturbs just more little, and the result is just accurate more.
9. instrument optimization and interference eliminated
Crude oil sample still also has no small matrix effect behind high-pressure digestion, the oxide of LREE such as La formation simultaneously can cause serious disturbance to heavy rare earth element.Based on these factors, in the condition optimizing experiment, investigated parameters such as RF power, sampling depth, gas flow to instrumental sensitivity, stability, optimal condition has been confirmed in the influence of oxide productive rate and double-charge ion productive rate.Instrument condition parameter after the optimization makes
89The count value of Y is greater than 1500,
56The count value of M is less than 1800, and 20 minutes stable RSD are less than 3%, and the oxide productive rate is less than 1.5%, and the double-charge ion productive rate is less than 3%.
Eliminate the matrix interference and take the crash response pool technology to eliminate multi-atomic ion interference such as oxide through mark mixed solution in the online adding simultaneously, use the reaction gas of helium as the crash response pond.
10. the selection of internal standard element
In ICP-MS method analytic process, analytic signal can change in time and drifts about, and matrix effect is obvious, and suppressing or enhancement effect can appear in the measured object signal.Select suitable internal standard element for use, can not only improve precision, and can also compensate interference, can effectively address the above problem with the concentration multiplication.Principle according to the internal standard element selection; Selection Ge is the internal standard element of Sc, Y; Tb is the internal standard element of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, then uses online adding 1mg/L Rh standard solution as the positive solution of interior calibration to the Tb element as internal standard element.
11. method detection limit and linear relationship
Under selected condition, measure by test method, each element linear equation, related coefficient and detection limit result see table 1.Visible by table 1, the equal 1 μ g/kg of the detection limit of each element satisfies the detection of crude oil middle rare earth element.
Each element linear equation of table 1, related coefficient and detection limit
12. accuracy testing
Select Barrow island crude oil and DOPA crude oil to carry out repeatability and investigate, use this law METHOD FOR CONTINUOUS DETERMINATION crude oil sample 7 times, calculate its relative standard deviation, the result sees table 2.Can find out that from table 2 except that the Lu element, the relative standard deviation of all the other elements is equal 8.7%, illustration method has good precision.
Each element essence density experiment (n=7) of table 2
13. recovery test
Select Barrow island crude oil sample that La, Ce, Pr, Nd are carried out recovery test, DOPA crude oil carries out recovery test to Sc, Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the result sees table 3.Visible by table 3, remove Sc, outside Tb and the Lu element, the recovery of standard addition of all the other 13 kinds of elements explains that this method accuracy is higher between 90.0%～105.2%.
Each element recovery rate experiment (n=3) of table 3
14. different crude oils sample middle rare earth element result and analysis
15 kinds of imported crude oils of 14 countries such as Angola, Brazil, Oman have been collected in experiment; 16 kinds of REEs in every kind of crude oil are measured; Result such as Fig. 7, shown in Figure 8, wherein, Yin Baluo island crude oil, DOPA crude oil ree content are higher; For relatively convenient, Barrow island crude oil, DOPA crude oil REE are respectively 1/10 and 1/50 of measured value among the figure.As can beappreciated from fig. 6, the REE distribution curve in the crude oil has parallel relation.This parallel distribution pattern of REE can be distinguished the crude oil of varying environment and separate sources on this basis, and foundation is provided for the origin cause of formation of crude oil.
The present invention adopts the method for high-pressure digestion that crude oil sample is carried out pre-treatment; Measure crude oil C193.027nm wave spectrum intensity through the ICP-OES method and realized judgement that it is cleared up degree, solved crude oil high-pressure digestion method and cleared up the loss that not exclusively causes instrument and pollution or cause the bigger problem of result error greatly because of matrix disturbs.Use the ICP-MS standard measure to measure 16 kinds of REEs in the crude oil, the detection limit of method is between 0.01～0.7 μ g/kg, and accuracy and precision are higher, can satisfy the requirement that trace rare-earth element is analyzed in the crude oil, and matrix disturbs little, and the result is accurate.
Claims (5)
1. a high-pressure digestion ICP-MS method is measured the method for crude oil middle rare earth constituent content, it is characterized in that this method comprise at first use in the ICP-OES method working sample digestion solution institute's carbon elements at the 193.027nm place wave spectrum intensity judge clearing up degree; Use the content of each REE in the ICP-MS method working sample digestion solution then;
Wave spectrum intensity is following to the step of clearing up degree and judging at the 193.027nm place for institute's carbon elements in the described ICP-OES method working sample digestion solution:
(1) take by weighing crude oil sample 0.4g～0.5g and place in the 100mL high-pressure digestion jar, add concentration 70% nitric acid, 8～14mL and concentration 30% hydrogen peroxide 1～5mL and process a kind liquid, tighten cover, the high-pressure digestion jar that kind liquid will be housed is then put into air dry oven; Start air dry oven, open program control system, set air dry oven and be warming up to 190 ℃～195 ℃, powered-down behind constant temperature time 1～7h, natural cooling; Open cover after the end, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to 25mL with ultrapure water, obtain Specimen eliminating solution; In another 100mL high-pressure digestion jar, directly add concentration 70% nitric acid, 8～14mL and concentration 30% hydrogen peroxide 1～5mL and process a kind liquid, tighten cover, the high-pressure digestion jar that kind liquid will be housed is then put into air dry oven; Start air dry oven, open program control system, set air dry oven and be warming up to 190 ℃～195 ℃, powered-down behind constant temperature time 1～7h, natural cooling; Open cover after the end, appearance liquid is placed fuming cupboard leave standstill, limpid to appearance liquid, transfer to then in the 25mL plastics volumetric flask, be settled to 25mL with ultrapure water, obtain blank digestion solution;
The Specimen eliminating solution utilization inductively-coupled plasma spectrometer that (2) will obtain according to step (1), promptly in the ICP-OES Instrument measuring Specimen eliminating solution institute's carbon elements at the 193.027nm place wave spectrum intensity, record the carbon intensity level, and definite Specimen eliminating degree;
The step of each ree content is following in the described ICP-MS method working sample digestion solution:
(3) configuration standard working solution: take by weighing rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb and Lu standard inventory solution that concentration is 1.0mg/mL respectively; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-1 of concentration as 1.0mg/L; The said standard solution mother liquor-1 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-1 respectively with concentration 5% salpeter solution, the content of each element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L respectively in the standard operation solution-1 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL; Take by weighing rare earth element tb standard inventory solution; The Tb standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask; Use concentration 5% salpeter solution to be diluted to the standard solution mother liquor-2 of concentration as 1.0mg/L; The standard solution mother liquor-2 that takes out 0uL, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL more respectively places the 10mL volumetric flask respectively; Be diluted to standard operation solution-2 respectively with concentration 5% salpeter solution, the content of Tb element corresponds to 0ug/L, 1ug/L, 2ug/L, 5ug/L, 10ug/L, 20ug/L, 50ug/L in the standard operation solution-2 of the 0uL of acquisition, 10uL, 20uL, 50uL, 100uL, 200uL and 500uL;
(4) configuration inner mark solution: taking by weighing concentration respectively is REE Ge and the Tb standard inventory solution of 1.0mg/mL; The standard inventory solution that therefrom respectively takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-1 of concentration as 1.0mg/L; Taking by weighing concentration is the Rh standard inventory solution of 1.0mg/mL, and the Rh standard inventory solution that therefrom takes out 100uL places the 100mL volumetric flask, uses concentration 5% salpeter solution to be diluted to the inner mark solution-2 of concentration as 1.0mg/L;
The standard operation solution that (5) will obtain according to step (3) and measure: adopt two peristaltic pump sample introduction systems to introduce inner mark solutions-1 and inner mark solution-2 according to the Specimen eliminating solution that step (1) obtains; Pump line with two different inner diameters; Specimen eliminating solution, blank digestion solution that standard operation solution that successively inner mark solution-1 and inner mark solution-2 is obtained with step (3) respectively with same pump speed and step (1) obtain import icp ms; It is the ICP-MS instrument; Before getting into atomizer, mix, select the best isotope of each element to measure; For the first time measure online adding inner mark solution-1, select for use
72Ge be Sc and Y internal standard element,
159Tb is the internal standard element of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, measures online adding inner mark solution-2 for the second time, selects for use
103Rh is as the internal standard element of the Tb in measuring for the first time; Elder generation's metric works solution-1 and standard operation solution-2; Again according to the known content and the icp ms of each element in standard operation solution-1 and the standard operation solution-2; Be the ICP-MS Instrument measuring to each element response draw the standard working curve of each element respectively; The response of working sample digestion solution and blank each element of digestion solution then; Calculate the concentration value of blank each element of digestion solution and the concentration value of each element of Specimen eliminating solution according to standard working curve, calculate the content X of each REE in the crude oil according to following formula
n:
In the formula: C
1The concentration value of-Specimen eliminating solution
C
0The concentration value of-blank digestion solution
V-digestion solution constant volume
The crude oil sample amount that m-takes by weighing
Calculate the content of each rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu and Tb in the crude oil sample.
2. high-pressure digestion ICP-MS method according to claim 1 is measured the method for crude oil middle rare earth constituent content, it is characterized in that the high-pressure digestion jar of selecting for use in the described step (1) comprises polytetrafluoroethylliner liner and stainless cylinder of steel overcoat.
3. high-pressure digestion ICP-MS method according to claim 1 is measured the method for crude oil middle rare earth constituent content, it is characterized in that the inductively-coupled plasma spectrometer in the described step (2), and promptly the ICP-OES instrument is a Varian 725-ES type ICP-OES instrument; Running parameter is: radio-frequency power 1200W, atomizer flow 0.6L/min, secondary air amount 1.50L/min; Plasma gas flow rate 15.0L/min; Peristaltic pump pump speed 15rpm, observed altitude 6mm, integral time 10s.
4. high-pressure digestion ICP-MS method according to claim 1 is measured the method for crude oil middle rare earth constituent content, it is characterized in that the icp ms in the described step (5), and promptly the ICP-MS instrument is an Agilent7500ex type ICP-MS instrument, and running parameter is: radio-frequency power 1500W; Sampling depth 7.0mm, torch pipe horizontal level 0.1mm, torch pipe upright position-0.2mm; Carrier gas flux 0.85L/min, complemental air flow 0.3L/min, 2 ℃ of atomization temperatures; Peristaltic pump pump speed 0.1rps, eight grades of bar voltage-18V, level Four bar voltage-16V; Focus voltage-10V, under the crash response pool mode, collision airshed 0.48L/min; Use Full Quant type collection data, be 0.1s the integral time of every kind of element, multiplicity 3 times.
5. high-pressure digestion ICP-MS method according to claim 1 is measured the method for crude oil middle rare earth constituent content, it is characterized in that the isotope of selected each element in the described step (5) is respectively
45Sc,
89Y,
139La,
140Ce,
141Pr,
146Nd,
147Sm,
153Eu,
157Gd,
163Dy,
165Ho,
166Er,
169Tm,
172Yb,
175Lu,
159Tb.
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| CN101620186B (en) * | 2009-07-27 | 2011-03-16 | 中国科学院上海硅酸盐研究所 | Method for analyzing arsenic content in glass refining agent |
| CN101986155B (en) * | 2010-06-10 | 2013-07-03 | 中国人民解放军63653部队 | Method for quickly analyzing 90Sr in soil |
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