CN111595932A - Method for separating and analyzing trace metalloporphyrin in condensate oil - Google Patents
Method for separating and analyzing trace metalloporphyrin in condensate oil Download PDFInfo
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- CN111595932A CN111595932A CN202010354003.0A CN202010354003A CN111595932A CN 111595932 A CN111595932 A CN 111595932A CN 202010354003 A CN202010354003 A CN 202010354003A CN 111595932 A CN111595932 A CN 111595932A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
Abstract
The invention discloses a method for separating and analyzing trace metalloporphyrin in condensate oil. The method comprises the following steps: 1) mixing the condensate oil and dioxane or N-methyl pyrrolidone in proportion, and mixing for a preset time under a heating condition; 2) separating the upper layer dioxane or methyl pyrrolidone solution, and concentrating to obtain metal-containing porphyrin solution; 3) mixing the concentrated solution with an equal volume of an electron transfer matrix solution; 4) sampling the mixed solution obtained in the step 3) and analyzing the metalloporphyrin by using a Fourier transform ion cyclotron resonance mass spectrometer provided with a matrix-assisted laser desorption ionization source.
Description
Technical Field
The invention relates to the field of condensate oil analysis, in particular to a method for separating and analyzing trace metal porphyrin in condensate oil.
Background
Most condensate oils contain metalloporphyrin compounds, which are known as condensate oils. The metalloporphyrin in the condensate oil can be used for identifying the source of the condensate oil and the oxidation-reduction property of the deposition environment, and has very important localization significance. Normally, the condensate has a very low metalloporphyrin content (< 10ppm), and since the condensate is an organism with a very complex composition, direct analysis of the metalloporphyrins is difficult to achieve. Therefore, effective separation and analysis are of great importance in determining the structure of metalloporphyrins in gas condensate and their localization.
Therefore, the development of a method for separating and analyzing trace amounts of metalloporphyrins in condensate oil has become a technical problem to be solved in the art.
Disclosure of Invention
The invention aims to provide a method for separating and analyzing trace metalloporphyrin in condensate oil, which can effectively separate and analyze trace metalloporphyrin in condensate oil.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for separating and analyzing trace amounts of metalloporphyrins in condensate, comprising the steps of:
1) mixing the condensate oil and dioxane or N-methyl pyrrolidone in proportion, and mixing for a preset time under a heating condition;
2) separating the upper layer dioxane or methyl pyrrolidone solution, and concentrating to obtain metal-containing porphyrin solution;
3) mixing the concentrated solution with an equal volume of an electron transfer matrix solution;
4) sampling the mixed solution obtained in the step 3) and analyzing the metalloporphyrin by using a Fourier transform ion cyclotron resonance mass spectrometer provided with a matrix-assisted laser desorption ionization source.
The matrix-assisted ionization laser desorption ionization source needs to be matched with an electron transfer matrix, and the electron transfer matrix has the most key function of promoting the electron transfer of a porphyrin compound to further ionize, so that the ionization of trace (< 10ppm) content metalloporphyrin can be realized. Other ionization sources such as electrospray ionization source and atmospheric pressure photoionization source can not realize ionization of metalloporphyrin with trace (< 10ppm) content without the coordination of electron transfer matrix due to different ionization mechanisms. The Fourier transform ion cyclotron resonance mass spectrometer has ultrahigh resolution and detection precision, and can measure the mass-to-charge ratio of the ionized ions of the compound to the 4 th position of a decimal point, so that the molecular formula of the compound can be judged. Therefore, a Fourier transform ion cyclotron resonance mass spectrometer of a matrix-assisted laser desorption ionization source is selected to be matched with a proper electron transfer matrix.
Preferably, in step 1), 1 to 5g of condensate is mixed with 5 to 10mL of dioxane or N-methylpyrrolidone.
Preferably, in step 1), the heating temperature is 40-60 ℃.
Preferably, in the step 1), the mixing is performed by magnetic stirring, and the predetermined time is 30-60 minutes.
Preferably, in step 2), the solution is concentrated to a volume of 200-.
Preferably, the electron transfer matrix is (2Z,2'Z) -2,2' - (1, 4-phenylene) bis (3- (p-tolyl) acrylonitrile) or 4,4'- ((1E,1' E) -1, 4-phenylenebis (ethylene-2, 1-diyl)) dibenzyl cyanide, which promotes ionization of the porphyrin, both with ionization energies of 7.8-8.4 eV.
Preferably, the concentration of the electron transfer matrix solution is 5 to 10 mmol/L.
Preferably, the solute of the electron transfer matrix solution is tetrahydrofuran.
Preferably, in the step 4), 2 to 5 μ L of the mixed solution obtained in the step 3) is sampled and placed on a steel target of a matrix-assisted laser desorption ionization (MALDI) source; analyzing the metalloporphyrin by using a Fourier transform ion cyclotron resonance mass spectrometer provided with a matrix-assisted laser desorption ionization source; the time for the analysis is typically less than 30 min.
In the method, the metalloporphyrin obtained by analysis in the condensate oil is nickel porphyrin and vanadium porphyrin.
In a preferred embodiment of the present invention, the method for separating and analyzing trace amounts of metalloporphyrins in gas condensate comprises the steps of:
1) mixing 1-5g of condensate oil and 5-10mL of dioxane or N-methyl pyrrolidone, and magnetically stirring for 30-60 minutes at 40-60 ℃ under heating;
2) separating the upper layer dioxane or methyl pyrrolidone solution and concentrating to 200-500 μ L metal-containing porphyrin solution;
3) mixing 10-20 μ L of the concentrated solution with 5-10mmol/L of an equal volume of tetrahydrofuran solution of electron transfer matrix (2Z,2'Z) -2,2' - (1, 4-phenylene) bis (3- (p-tolyl) acrylonitrile) or 4,4'- ((1E,1' E) -1, 4-phenylene bis (ethylene-2, 1-diyl)) dibenzyl nitrile;
4) taking out 2-5 mu L of the mixed solution obtained in the step 3) and placing the mixed solution on a steel target of a Matrix Assisted Laser Desorption Ionization (MALDI) source;
5) metalloporphyrins were analyzed using a fourier transform ion cyclotron resonance mass spectrometer equipped with a MALDI source.
The invention has the beneficial effects that: the method can detect the metalloporphyrin with trace (< 10ppm) content in the condensate oil; the signal-to-noise ratio is greater than 50, and the detection reliability is improved; the metalloporphyrin is enriched without chromatographic separation; the mass of the used crude oil is less than or equal to 5 g; the whole process time is less than 1 hour.
Drawings
FIG. 1 is a mass spectrum of metalloporphyrin obtained in example 1.
FIG. 2 is a mass spectrum of metalloporphyrin obtained in example 2.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, and the like, including ranges for each) may generally be approximations that vary (+) or (-) in increments of 0.1 or 1.0 as appropriate. All numerical designations should be understood as preceded by the term "about".
Example 1
This example used the method of the present invention to separate and analyze trace amounts of metalloporphyrin in highly exploratory 1-well crude oil, wherein the method comprises the following steps:
1) 1g of high-probe 1-well crude oil (nickel content 2283ppb, vanadium content 4492ppb) and 10mL of dioxane were mixed in proportion and magnetically stirred at 50 ℃ for 30 minutes;
2) separating the upper layer dioxane solution and concentrating to obtain metal-containing porphyrin solution with the volume of 300 mu L;
3) mu.L of the concentrated solution was mixed with an equal volume of a 5mmol/L (2Z,2'Z) -2,2' - (1, 4-phenylene) bis (3- (p-tolyl) acrylonitrile) tetrahydrofuran solution and shaken;
4) 2 mul of the obtained 20 mul of mixed solution was taken out and placed on a steel target of a Matrix Assisted Laser Desorption Ionization (MALDI) source;
5) metalloporphyrins were analyzed using a magnetic field strength 9.4T fourier transform ion cyclotron resonance mass spectrometer produced by Bruker equipped with a MALDI source.
The mass spectrum is shown in FIG. 1, and the analysis results are shown in Table 1.
TABLE 1
| Molecular formula | Signal to noise ratio | |
| 1 | C30H22SN4Ni | 116.1 |
| 2 | C31H24SN4Ni | 26.6 |
| 3 | C32H26SN4Ni | 113.6 |
| 4 | C33H28SN4Ni | 219.9 |
| 5 | C34H30SN4Ni | 223.1 |
| 6 | C35H32SN4Ni | 221.4 |
| 7 | C36H34ON4Ni | 219.7 |
| 8 | C37H36ON4Ni | 215.8 |
| 9 | C30H22SN4VO2 | 216.9 |
| 10 | C31H24SN4VO2 | 215.1 |
| 11 | C32H26SN4VO2 | 117.8 |
| 12 | C33H28SN4VO2 | 114.5 |
| 13 | C34H30N4VO2 | 111.8 |
| 14 | C35H32N4VO2 | 118.7 |
| 15 | C36H34N4VO2 | 119.2 |
| 16 | C37H36N4VO2 | 113.1 |
Example 2
This example used the method of the present invention to separate and analyze trace amounts of metalloporphyrins in mid-autumn 1 well crude oil, wherein the method comprises the steps of:
1) 5g of mid-autumn 1 well crude oil (with a nickel content of 1258ppb and a vanadium content of 2598ppb) and 5mL of dioxane are mixed in proportion and magnetically stirred for 30 minutes under heating at 50 ℃;
2) separating the upper layer of the methyl pyrrolidone solution and concentrating to obtain a metal-containing porphyrin solution with the volume of 300 mu L;
3) 20. mu.L of the concentrated solution was mixed with an equal volume of a 10mmol/L solution of 4,4'- ((1E,1' E) -1, 4-phenylenebis (ethylene-2, 1-diyl)) dibenzyl cyanide in tetrahydrofuran and shaken up;
4) taking out 5 μ L of the obtained 40 μ L of mixed solution and placing on a steel target of a Matrix Assisted Laser Desorption Ionization (MALDI) source;
5) metalloporphyrin was analyzed by a magnetic field strength 9.4T Fourier transform ion cyclotron resonance mass spectrometer (manufactured by Bruker) equipped with a MALDI source, and the mass spectrum and the analysis result are shown in FIG. 2.
TABLE 2
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A method for separating and analyzing trace amounts of metalloporphyrins in condensate, comprising the steps of:
1) mixing the condensate oil and dioxane or N-methyl pyrrolidone in proportion, and mixing for a preset time under a heating condition;
2) separating the upper layer dioxane or methyl pyrrolidone solution, and concentrating to obtain metal-containing porphyrin solution;
3) mixing the concentrated solution with an equal volume of an electron transfer matrix solution;
4) sampling the mixed solution obtained in the step 3) and analyzing the metalloporphyrin by using a Fourier transform ion cyclotron resonance mass spectrometer provided with a matrix-assisted laser desorption ionization source.
2. The method for separating and analyzing trace metalloporphyrins in gas condensate according to claim 1, characterized in that in step 1), 1-5g of gas condensate is mixed with 5-10mL of dioxane or N-methylpyrrolidone.
3. The method for separating and analyzing trace metalloporphyrins in gas condensate according to claim 1, characterized in that in step 1) the temperature of heating is 40-60 ℃.
4. The method for separating and analyzing trace metalloporphyrin in condensate oil according to claim 1, wherein in step 1), said mixing is performed by magnetic stirring, and said predetermined time is 30-60 minutes.
5. The method for separating and analyzing trace amounts of metalloporphyrins in gas condensate as claimed in claim 2, wherein in step 2), the metal-containing porphyrin solution is concentrated to a volume of 200-.
6. The method for separating and analyzing trace metalloporphyrin in condensate oil as claimed in claim 1, wherein in step 3), 10-20 μ L of the concentrated solution is mixed with an equal volume of the electron transfer matrix solution.
7. The method for the separation and analysis of trace metalloporphyrins in gas condensate according to claim 1, characterized in that the electron transfer matrix is (2Z,2'Z) -2,2' - (1, 4-phenylene) bis (3- (p-tolyl) acrylonitrile) or 4,4'- ((1E,1' E) -1, 4-phenylenebis (ethylene-2, 1-diyl)) dibenzylonitrile.
8. The method for the separation and analysis of trace metalloporphyrins in gas condensate according to claim 7, characterized in that the concentration of the electron transfer matrix solution is comprised between 5 and 10 mmol/L.
9. The method for the separation and analysis of trace metalloporphyrins in gas condensate according to claim 8, characterized in that the solute of the electron transfer matrix solution is tetrahydrofuran.
10. The method for separating and analyzing trace metalloporphyrin in condensate oil according to claim 1, wherein in step 4), 2-5 μ L of the mixed solution obtained in step 3) is sampled and placed on a steel target of a matrix-assisted laser desorption ionization source; metalloporphyrins were analyzed using a fourier transform ion cyclotron resonance mass spectrometer equipped with a matrix assisted laser desorption ionization source.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008012630A (en) * | 2006-07-06 | 2008-01-24 | Osaka Univ | Composite body of carbon nanotube and peptide containing porphyrin |
| WO2016142691A1 (en) * | 2015-03-06 | 2016-09-15 | Micromass Uk Limited | Rapid evaporative ionisation mass spectrometry ("reims") and desorption electrospray ionisation mass spectrometry ("desi-ms") analysis of swabs and biopsy samples |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008012630A (en) * | 2006-07-06 | 2008-01-24 | Osaka Univ | Composite body of carbon nanotube and peptide containing porphyrin |
| WO2016142691A1 (en) * | 2015-03-06 | 2016-09-15 | Micromass Uk Limited | Rapid evaporative ionisation mass spectrometry ("reims") and desorption electrospray ionisation mass spectrometry ("desi-ms") analysis of swabs and biopsy samples |
Non-Patent Citations (8)
| Title |
|---|
| DEISY GIRALDO-DÁVILA.ET AL: ""Selective ionization by electron-transfer MALDI-MS of vanadyl porphyrins from crude oils"", FUEL * |
| JUAN S RAMÍREZ-PRADILLA.ET AL: ""Electron Transfer Ionization of Nanoparticles, Polymers, Porphyrins and Fullerenes Using Synthetically-Tunable #-Cyano-Phenylenevinylenes as UV MALDI-MS Matrices"", AMERICAN CHEMICAL SOCIETY * |
| JUAN S. RAMÍREZ-PRADILLA: ""Comprehensive Petroporphyrin Identification in Crude Oils Using Highly Selective Electron Transfer Reactions in MALDI-FTICR-MS"", ENERGY FUELS * |
| LAURA J. CASTELLANOS-GARCÍA: ""Oligo p-Phenylenevinylene Derivatives as Electron Transfer Matrices for UV-MALDI"", J. AM. SOC. MASS SPECTROM * |
| 孟杨: "重油中镍化合物的合成及脱金属助剂研究", 《CNKI工程科技Ⅰ辑》 * |
| 孟杨: "重油中镍化合物的合成及脱金属助剂研究", 《CNKI工程科技Ⅰ辑》, 15 June 2015 (2015-06-15), pages 31 * |
| 马军国: "辽河常渣中镍化合物的分离与鉴定", 《CNKI工程科技Ⅰ辑》 * |
| 马军国: "辽河常渣中镍化合物的分离与鉴定", 《CNKI工程科技Ⅰ辑》, 15 November 2011 (2011-11-15), pages 6 - 11 * |
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