CN103134851A - Direct measuring apparatus and measuring method for hydrogen sulfide content and sulfur isotope in natural gas - Google Patents
Direct measuring apparatus and measuring method for hydrogen sulfide content and sulfur isotope in natural gas Download PDFInfo
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- CN103134851A CN103134851A CN2011103765656A CN201110376565A CN103134851A CN 103134851 A CN103134851 A CN 103134851A CN 2011103765656 A CN2011103765656 A CN 2011103765656A CN 201110376565 A CN201110376565 A CN 201110376565A CN 103134851 A CN103134851 A CN 103134851A
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Abstract
The invention discloses a direct measuring apparatus and a measuring method for hydrogen sulfide content and sulfur isotope in a natural gas. The measuring apparatus comprises an injection port, a U-shaped cold trap and a mass spectrometer, wherein one end of the U-shaped cold trap is connected with the injection port; the other end of the U-shaped cold trap is connected with the mass spectrometer; a vacuum valve A is disposed on a pipeline between the injection port and the U-shaped cold trap; a vacuum valve B is disposed on a pipeline between the U-shaped cold trap and the mass spectrometer, a vacuum pump is communicated with the pipeline between the U-shaped cold trap and the vacuum valve B through the pipeline; a vacuum valve C is disposed on the vacuum pump; and the apparatus is a sealed apparatus. The measuring method comprises that the natural gas is directly introduced to a mass spectrometer for measuring the hydrogen sulfide content and sulfur isotope after being enriched by the U-shaped cold trap. The apparatus and the method can be used for measuring by the mass spectrometer, and have the characteristics of accurate data, simple operations, little sample, rapid analysis speed, etc.
Description
Technical field
The invention belongs to the geochemical analysis field, further, relate to a kind of hydrogen sulfide in natural gas content and the direct measurement mechanism of sulfur isotope and measuring method.
Background technology
The analytical approach of hydrogen sulfide in natural gas content is a lot, and iodimetric titration, methylene blue method, lead acetate method, spectrophotometric method, ultraviolet absorption method, vapor-phase chromatography etc. are arranged, and only having vapor-phase chromatography in these methods is direct analysis, and other is all indirect analysis method.Indirect analysis method is at the scene with the sulfuretted hydrogen in chemical reagent absorption rock gas, use again its content of chemical analysis methods, as iodimetric titration (the mensuration iodimetric titration of GB/T 11060.1-1998 hydrogen sulfide in natural gas content), methylene blue method (the mensuration methylene blue method of GB/T 11060.2-1998 hydrogen sulfide in natural gas content), lead acetate method; Or in the laboratory, sulfuretted hydrogen is converted into the analyzable form of instrument, analyze its content, as spectrophotometric method, ultraviolet absorption method.The indirect analysis method step is more, easily produces error, and the gas chromatography range of linearity is narrower, needs the standard model of preparation different content.
The sulfur isotope analytical approach of hydrogen sulfide in natural gas generally adopts chemical method at the scene with the H in rock gas
2S is converted into sulfide, indoor, sulfide is converted into sulphuric dioxide again, analyze its sulfur isotope with the stable isotope mass spectrograph and form (Chunfang Cai et al., 2003), also sulfide can be converted into sulfur hexafluoride and analyze its sulfur isotope composition (S.Ono et al., 2006).These methods all comprise two steps or two above chemical reactions of step, and in order to prevent isotope fractionation, it is very thorough that the chemical reaction requirement is carried out, and therefore also stricter to the requirement of operation, the factor of corresponding generation error is also more.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of hydrogen sulfide in natural gas content and the direct measurement mechanism of sulfur isotope and measuring method, can adopt mass spectrometer directly to measure, have the characteristics such as data are accurate, easy and simple to handle, few with the sample amount, analysis speed is fast.
One of purpose of the present invention is to provide a kind of hydrogen sulfide in natural gas content and the direct measurement mechanism of sulfur isotope.
Described device comprises: U-shaped cold-trap and mass spectrometer, and U-shaped cold-trap one end connects injection port, and the other end connects mass spectrometer;
Be provided with vacuum valve A on pipeline between injection port and U-shaped cold-trap, be provided with vacuum valve B on the pipeline between U-shaped cold-trap and mass spectrometer, vacuum pump is communicated with pipeline between U-shaped cold-trap and vacuum valve B by pipeline, is provided with vacuum valve C on it;
Described device is packoff;
Described pipeline is the vacuum seal pipeline, and piping material preferably stainless steel material makes;
Connection between above-described each parts is sealed into suitable with assurance, can adopt the connection of guaranteed sealings all in prior art, and in the present invention, preferably cutting ferrule connects; Injection port and pipeline preferably cutting ferrule are connected, and are provided with sealing gasket between injection port and pipeline, are preferably silicone rubber seal gasket.
Described U-shaped cold-trap and pipeline can adopt same material to make.
Two of purpose of the present invention is to provide a kind of hydrogen sulfide in natural gas content and sulfur isotope direct measuring method.
Comprise:
Directly send into mass spectrograph after the U-shaped cold-trap enrichment of natural gas via and measure hydrogen sulfide content and sulfur isotope.
Specifically comprise the following steps:
(1) drive vacuum pump, close vacuum valve B, open vacuum valve A and C, cold-trap and injection port are vacuumized, be evacuated to≤5Pa;
(2) with the liquid nitrogen glass holder on " U " type cold-trap, condenser temperature is closed vacuum valve C lower than-80 ℃, and the rock gas that gathers is injected the cold-trap enrichment fast, sulfuretted hydrogen and carbon dioxide are enriched in cold-trap, freezing 3min～5min;
(3) open vacuum valve C, take out interference gas, after 5min～7min, close vacuum valve A and C, remove the liquid nitrogen cup;
(4) cold-trap of removing after the liquid nitrogen cup is warming up to 20～25 ℃ naturally, opens the pressured difference of vacuum valve B sulfuretted hydrogen and the carbon dioxide of enrichment in cold-trap are sent into mass spectrometer;
(5) directly measure hydrogen sulfide content and sulfur isotope with mass spectrometer.
When measuring hydrogen sulfide content, first utilize the rock gas of hydrogen sulfide content 〉=10%, measure the sulfuretted hydrogen sensitivity data: utilize " U " type cold-trap, enrichment sulfuretted hydrogen and carbon dioxide, and other gas componant content very low (0～0.1%) are due to CO
2Sensitivity known, by measuring CO
2The mass spectrum peak height, can calculate CO
2Amount (μ l), H
2The amount of S (μ l)=sample total amount (μ l)-CO
2Amount (μ l), with the amount (μ l) of sulfuretted hydrogen on sulfuretted hydrogen mass spectrum ratio of peak, namely obtain the sensitivity data of sulfuretted hydrogen.In the situation that sulfuretted hydrogen sensitivity is known, for the rock gas sample of any hydrogen sulfide content (0-100%), no longer need to carry out enrichment by " U " type cold-trap, but can directly enter mass spectrometer, by measuring the mass spectrum peak height of sulfuretted hydrogen, then than upper H
2The sensitivity data of S can calculate the amount (μ l) of hydrogen sulfide in natural gas, and the amount of sulfuretted hydrogen is compared the volumn concentration that can obtain hydrogen sulfide in natural gas with the sample total amount.
And in classic method, the classic method of mass spectrometer sulfuretted hydrogen sensitivity determination needs the Application standard sample, and classic method must customize hydrogen sulfide standard gas, and its term of validity is shorter, and preservation condition is strict.
While measuring sulfur isotope, by mass spectrograph, measured in natural gas
34H
2S and
36H
2The mass spectrum ratio of peak of S; Use the same method and measure H
2The S reference gas
34H
2S and
36H
2The mass spectrum ratio of peak of S; The isotopics computing formula that the two substitution is general, the sulfur isotope that can obtain hydrogen sulfide in natural gas forms.
Can adopt that in prior art, common acquisition method carries out the rock gas collection, generally gather rock gas with high pressure aluminium alloy steel cylinder, sample pressure is greater than 0.1MPa, and what have reaches 8.0MPa.During sampling, reduction valve is installed on steel cylinder, is blocked the reduction valve outlet with rubber gasket, regulate back pressure in the 0.2MPa left and right, plug the syringe needle venting on rubber gasket, by opening and closing the valve of steel cylinder, the air in the displacement reduction valve.Displacement number of times pressure per sample determines, when sample is pressed 5MPa, replaces and gets final product for 3～4 times.If sample pressure less than 1.0MPa, can not fill reduction valve, directly fill a nut with cover on small steel cylinder, cover central authorities and open one
This hole is blocked with rubber gasket in the hole of left and right, by opening and closing the valve of small steel cylinder, the air between displacement lid and valve, general 3～4 times.Displacement is outdoor or carry out in fuming cupboard.Syringe with 1～10ml extracts the 1ml sample, enters fast U-shaped cold-trap, has just completed sampling.In sampling process, reduce the retention time of sample in reduction valve as far as possible.
H
2S and CO
2Be collected in cold-trap, remaining gas is discharged by vacuum system, heats cold-trap, makes the H of enrichment
2S and CO
2Send into mass spectrometer;
Owing to only containing H in the gas that is collected
2S and CO
2, by measuring CO
2Concentration can calculate H
2The concentration of S, thus its sensitivity data obtained.
Mass spectrograph adopts the EI ion gun, magnetic analyzer, and faraday receives cup, selects the molecule of different specific charges by changing magnetic field, by changing in whole specific charge magnetic field position the mass spectra peak that voltage obtains a flat-top, thereby guarantees the accuracy measured.During analysis, gaseous sample enters ion gun from the sample storage device continuously by a micropore, and the molecule that is ionized enters analyzer by acceleration, and selecteed ion arrives Faraday cup, through amplifying and change into digital signal by computer acquisition.Vacuum system continuous working simultaneously, the high vacuum of maintenance dirft tube.Electron energy 86eV, accelerating potential 8kV, transmitter current 40 μ A, when analyzing rock gas, with two measurement passages, mass resolution is respectively 220 and 3000.With resolution be 220 passage scanning m/e=2 to the mass spectrum of m/e=66, obtain H
2, He, CH
4, H
2O, N
2, C
2H
6, O
2, H
2S, Ar, CO
2, C
3H
8, C
4H
10, SO
2Deng the mass spectrum of composition, be the mass spectra peak that the scanning of 3000 passage is disturbed with resolution, as O
+/ CH
4, N
2/ C
2H
4 +, S
+/ O
2, Ar/C
3H
4 +, CO
2/ C
3H
8, it is whole identical in quality, but accurate mass has difference, can separate by high resolving power.
Gas with pure gas or known content is made standard specimen, measures the sensitivity of unimolecule gas.Process by the mass spectrometric data that scanning is obtained, in conjunction with sensitivity data, can calculate the volumetric concentration of every kind of composition, process as ideal gas, be volumetric molar concentration.For C
4The situation that above component content is very little also can normalize to 100% with total volumetric concentration, to reduce error.H
2When S content hanged down, its content data was subjected to
18O
16The impact of O, solution are to utilize " U " type cold-trap enrichment H
2S gets rid of oxygen, then analyzes, according to sample size and H
2H is calculated in the response of S mass spectrum
2The concentration of S.For the error that the human factor of avoiding sample introduction produces, can utilize H
2S and CO
2Content than and the CO that measured
2Cubage H
2The content of S.Both can mutually verify.
To be enriched to H
2The S conductance enters mass spectrograph, directly measures the ratio of m/e=36 and m/e=34; With the FeS of known sulfur isotope composition and enough watery hydrochloric acid reactions, make FeS all be converted into H
2S, then measure the ratio of m/e=36 and m/e=34 by same method calculates and determines H in rock gas with the isotopics defined formula
2The sulfur isotope of S forms.In the sulfuretted hydrogen enrichment process, CO
2And C
3Above hydrocarbon gas also is enriched in cold-trap, CO
2Produce [
18O
16O]
+The impact of ion pair m/e=34 is atomic, does not substantially affect the measurement of sulfur isotope, C
3Above hydrocarbon gas produces the m/e=36 mass spectra peak in mass spectrum, disturb the measurement of sulfur isotope.For high sulfur-containing natural gas, C
2Above component content is very low, and the sulfur isotope test data is not had impact substantially, for low sulfur-containing gas, because the sulfuretted hydrogen amount is few, must carry out enrichment, C with more rock gas
2Above one-tenth branch produces certain impact to the sulfur isotope test data.Hydrogen isotope major effect m/e=35 in sulfuretted hydrogen can ignore the impact of m/e=36.
With FeS and watery hydrochloric acid reaction preparation sulfuretted hydrogen, reaction equation is as follows:
FeS+2HCl＝H
2S↑+FeCl
2
Table 1 is H
2S gas single sample introduction, 6 repetitive measuring experiment data, therefrom the measuring accuracy of sulfur isotope can reach 0.02% as can be known, can satisfy the research work needs.
Table 1H
2S gas (δ
34S
CDT=29.84 ‰) sulfur isotope mass spectrum ratio of peak test result
| m/e | 34(V) | R 35/34(％) | R 36/34(％) |
| 1# | 2.7725 | 2.6415 | 4.4544 |
| 2# | 2.7635 | 2.6413 | 4.4547 |
| 3# | 2.7541 | 2.6422 | 4.4536 |
| 4# | 2.7454 | 2.6425 | 4.4540 |
| 5# | 2.7365 | 2.6441 | 4.4559 |
| 6# | 2.7289 | 2.6431 | 4.4536 |
| Mean value | 2.6425 | 4.4544 | |
| Standard deviation | 0.0010 | 0.0009 | |
| Relative standard deviation (%) | 0.04 | 0.02 |
Wherein, 34 (V) expression mass spectrum peak height or intensity, unit is V;
R
36/34(%) the mass spectrum ratio of peak of expression m/e=36 and m/e=34.
This method directly imports mass spectrograph with sample and analyzes H in rock gas
2The content of S utilizes that the mass spectrograph range of linearity is wide, the characteristics of good reproducibility, only needs one of the sulfuretted hydrogen standard specimen of preparation known content, and the method has the characteristics such as data are accurate, easy and simple to handle, few with the sample amount, analysis speed is fast after primary calibration.
Description of drawings
Fig. 1 measurement mechanism schematic diagram of the present invention
Description of reference numerals:
The 1-injection port; 2-vacuum valve A; 3-vacuum valve B; 4-vacuum valve C;
The 5-vacuum pump; 6-U type cold-trap; The 7-mass spectrometer
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Mass spectrograph model: MAT271
Type ion source: EI source
Electron energy: 86eV
Transmitter current: 40 μ A
Working method: single cup that receives, jump in magnetic field, and high pressure slightly scans
Embodiment:
As shown in Figure 1, a kind of hydrogen sulfide in natural gas content and the direct measurement mechanism of sulfur isotope comprise: injection port 1, U-shaped cold-trap 6 and mass spectrometer 7, and U-shaped cold-trap 6 one ends connect injection port 1, and the other end connects mass spectrometer 7;
Be provided with vacuum valve A2 on pipeline between injection port 1 and U-shaped cold-trap 6, be provided with vacuum valve B3 on the pipeline between U-shaped cold-trap 6 and mass spectrometer 7, vacuum pump 5 is communicated with pipeline between U-shaped cold-trap 6 and vacuum valve B3 by pipeline, is provided with vacuum valve C4 on it;
Described device is packoff, and pipeline is the vacuum seal pipeline, and piping material is that stainless steel material makes; Injection port is that cutting ferrule is connected with pipeline, is provided with silicone rubber seal gasket between injection port and pipeline.
Testing procedure is as follows:
A prepares sample: utilize high pressure aluminium alloy steel cylinder to gather rock gas, sample pressure 5MPa in container.
B sampling: during sampling, on high pressure aluminium alloy steel cylinder, reduction valve is installed, is blocked the reduction valve outlet with rubber gasket, regulate back pressure at 0.2MPa, insert the syringe needle venting on rubber gasket, by opening and closing the valve of high pressure aluminium alloy steel cylinder, the air in the displacement reduction valve.Replace 3 times, displacement is carried out outdoor.
C sample introduction: drive vacuum pump, close vacuum valve B, open vacuum valve A and C, cold-trap and injection port are vacuumized, be evacuated to 5Pa; The liquid nitrogen glass holder on " U " type cold-trap, is closed vacuum valve C, and with the syringe extraction 1ml sample U-shaped cold-trap enrichment of injection fast of 5ml, sulfuretted hydrogen and carbon dioxide are enriched in cold-trap, freezing 3min; Open vacuum valve C, take out interference gas, after 5min, close vacuum valve A and C, remove the liquid nitrogen cup; Naturally rise to room temperature (23 ℃, air-conditioning) etc. U-shaped cold-trap, open vacuum valve B, sulfuretted hydrogen and the carbon dioxide of enrichment in cold-trap are sent into mass spectrometer;
D mass spectrophotometry: after sample enters mass spectrograph, carry out the full scan analysis, record the mass spectrum peak height of sample total amount and each component.
The e data are processed: by measuring CO
2Concentration can calculate H
2The concentration of S, and obtain its sensitivity data, the sensitivity of the sulfuretted hydrogen that sulfuretted hydrogen mass spectrum ratio of peak is known namely obtains the amount of sulfuretted hydrogen, the amount by sulfuretted hydrogen with the sample total amount than the volumn concentration that can obtain hydrogen sulfide in natural gas.
The mass spectrum peak height of f scanning analysis m/e=36 and m/e=34;
G is by FeS and the watery hydrochloric acid reaction preparation sulfuretted hydrogen of known sulfur isotope, and as standard model, reaction equation is as follows:
FeS+2HCl＝H
2S↑+FeCl
2
Record the mass spectrum ratio of peak of its m/e=36 and m/e=34.
With the hydrogen sulfide in natural gas m/e=36 that records and the mass spectrum ratio of peak of m/e=34, with the mass spectrum ratio of peak substitution isotope δ value computing formula of standard model m/e=36 and m/e=34, can calculate the δ of hydrogen sulfide in natural gas
34S
CDT
Comparative Examples:
Utilize high pressure aluminium alloy steel cylinder, gathered at the scene the sulfur-containing gas sample, obtain simultaneously the H of the on-the-spot iodometric determination of these samples
2The S content data.In the laboratory, utilize respectively iodimetric titration and mass spectrum Direct Determination, these rock gas samples are carried out H
2The S assay, wherein the mass spectrum Direct Determination has carried out revision test, and table 1 is test figure.
H in rock gas
2The existing method of testing of S sulfur isotope be at the scene by chemical method with H
2S is converted into solid-state sulfide, then utilizes high-temperature oxidation that solid-state sulfide is converted into gaseous state SO in the laboratory
2, then import isotope mass spectrometer and carry out the sulfur isotope composition analysis.Correlation data sees Table 2.
The H of table 1 mass spectrum direct measuring method and iodometric determination
2The contrast of S content data
Illustrate: in table 1, on-the-spot value refers to, the data that record with iodimetric titration on gasser, iodimetric titration refer to the data that record in the use for laboratory iodimetric titration; Each sample number into spectrum represents a rock gas sample, totally 6 samples; Mass spectroscopy 1 and mass spectroscopy 2 refer to the data of the same rock gas sample of twice measurement gained.
Can find out by contrast, for identical sulfur-containing gas sample, adopt the described mass spectrum Direct Determination of this invention and prior art iodimetric titration, two kinds of H that method of testing obtains
2Have reasonable comparability between the S content data, and from Comparative Examples, same sample H
2The direct determination data of the mass spectrum of S content has good repeatability, and H in the rock gas that the method records is described
2The S content data has higher precision and accuracy, and can disposablely detect other gas composition content of rock gas sample, analyzes data stabilization reliable.With H
2The existing common analysis iodimetric titration of S content is compared, the distinguishing features such as that the described mass spectrum Direct Determination of this invention has is easy and simple to handle, few with the sample amount, standard model is easy to preparation, analysis speed is fast, measuring accuracy is high are suitable for H in sulfur-containing gas
2The on-line system analysis of S gas and other gas composition.
H in table 2 rock gas
2The direct method of testing of S sulfur isotope mass spectrum and CdS high-temperature oxidation test figure
Can find out by contrast, sulfur-containing gas sample for different content, utilize the distribution of the difference of two kinds of resulting test figures of method of testing in 0.1 ‰～1 ‰ scopes, have reasonable consistance, illustrated that method of testing of the present invention and existing method of testing have comparability preferably.
From analysis process, H in existing rock gas
2S sulfur isotope method of testing step more complicated need to prepare at the scene solid-state sulfur isotope analytic sample, then utilize high-temperature oxidation that solid-state sulfide is converted into gaseous state SO in the laboratory
2, its determination is comprising two steps or two above chemical reactions of step, in order to prevent Sulfur Isotope Fractionation, it is very thorough that the requirement chemical reaction carries out, therefore also stricter to the requirement of operation, the factor of corresponding generation error is also more, and needs long analysis time.H in rock gas of the present invention
2S sulfur isotope method of testing has greatly been simplified sample pre-treatments and sulfur isotope testing procedure, have simple to operate, source of error is few, analysis time is short and analyze data and wait accurately and reliably characteristics.
Claims (9)
1. a hydrogen sulfide in natural gas content and the direct measurement mechanism of sulfur isotope is characterized in that:
Described device comprises: injection port, U-shaped cold-trap and mass spectrometer, and U-shaped cold-trap one end connects injection port, and the other end connects mass spectrometer;
Be provided with vacuum valve A on pipeline between injection port and U-shaped cold-trap, be provided with vacuum valve B on the pipeline between U-shaped cold-trap and mass spectrometer, vacuum pump is communicated with pipeline between U-shaped cold-trap and vacuum valve B by pipeline, is provided with vacuum valve C on it;
Described device is packoff.
2. hydrogen sulfide in natural gas content as claimed in claim 1 and the direct measurement mechanism of sulfur isotope is characterized in that:
Described pipeline is the vacuum seal pipeline;
Described injection port is connected with the pipeline cutting ferrule, is provided with sealing gasket between injection port and pipeline.
3. hydrogen sulfide in natural gas content as claimed in claim 2 and the direct measurement mechanism of sulfur isotope is characterized in that:
Described sealing gasket is silicone rubber seal gasket.
4. hydrogen sulfide in natural gas content as claimed in claim 1 and the direct measurement mechanism of sulfur isotope is characterized in that:
Described U-shaped cold-trap and pipeline are that same material makes.
5. adopt the measuring method of hydrogen sulfide in natural gas content as described in one of claim 1～4 and the direct measurement mechanism of sulfur isotope, comprising:
Directly send into mass spectrograph after the U-shaped cold-trap enrichment of natural gas via and measure hydrogen sulfide content and sulfur isotope.
6. measuring method as claimed in claim 5 is characterized in that said method comprising the steps of:
(1) drive vacuum pump, close vacuum valve B, open vacuum valve A and C, cold-trap and injection port are vacuumized, be evacuated to≤5Pa;
(2) with the liquid nitrogen glass holder on " U " type cold-trap, condenser temperature is closed vacuum valve C lower than-80 ℃, and the rock gas that gathers is injected the cold-trap enrichment fast, sulfuretted hydrogen and carbon dioxide are enriched in cold-trap, freezing 3min～5min;
(3) open vacuum valve C, take out interference gas, after 5min～7min, close vacuum valve A and C, remove the liquid nitrogen cup;
(4) cold-trap is warming up to 20～25 ℃, opens vacuum valve B, and pressured difference is sent sulfuretted hydrogen and the carbon dioxide of enrichment in cold-trap into mass spectrometer;
(5) directly measure hydrogen sulfide content and sulfur isotope with mass spectrometer.
7. measuring method as claimed in claim 6 is characterized in that:
In described step (5), by measuring CO
2Concentration can calculate H
2The concentration of S, and obtain its sensitivity data, measure hydrogen sulfide in natural gas content according to sensitivity data.
8. measuring method as claimed in claim 6 is characterized in that:
In described step (5), with mass spectrograph, measure in natural gas
34H
2S and
36H
2The mass spectrum ratio of peak of S; Use the same method and measure H
2The S reference gas
34H
2S and
36H
2The mass spectrum ratio of peak of S; The isotopics computing formula that the two substitution is general, the sulfur isotope that can obtain hydrogen sulfide in natural gas forms.
9. measuring method as claimed in claim 7 is characterized in that:
In described step (5), after recording first sulfuretted hydrogen sensitivity, can directly with the hydrogen sulfide content in mass spectrometer measurement rock gas, need not the cold-trap enrichment.
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