CN102706949B - Method for determination of inorganic element in fuel gas - Google Patents
Method for determination of inorganic element in fuel gas Download PDFInfo
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- CN102706949B CN102706949B CN201210165613.1A CN201210165613A CN102706949B CN 102706949 B CN102706949 B CN 102706949B CN 201210165613 A CN201210165613 A CN 201210165613A CN 102706949 B CN102706949 B CN 102706949B
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- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a method for determination of inorganic element in fuel gas, comprising the following steps: sample collection: the fuel gas is divided into two parts so as to flow through cation absorption liquid and anion absorption liquid respectively after the fuel gas flows through a filter membrance; sample handling: the filter membrance is equally divided into two parts, one part of the filter membrance is dispelled by acid liquor, then the cation absorption liquid is added, and through metered volume and filtering, filtrate for cation analysis is obtained, and the other part of the filter membrance is extracted with water, then the anion absorption liquid is added into the extract liquor, and through metered volume and filtering, filtrate for anion analysis is obtained; sample analysis: above filtrates are respectively subsjected to capillary electrophoresis test, and then data is treated. According to the method and the device provided by the invention, the defects of low efficiency, long consuming time, higher analytical cost and difficult in popularizing in traditional method are overcame. The aim to quick test multiple inorganic elements is realized, the operation cost is lower, the operation is simple, and the method is convenient to popularize.
Description
Technical field
The invention belongs to chemical analysis test field, be specifically related to the rapid assay methods of inorganic elements in a kind of combustion gas.
Background technology
Owing to being subject to the impact of formation and environment of living in, in combustion gas, tend to the inorganic elements that contains variable concentrations.These inorganic elements are with solid granule, and the form of mist and gas exists.When these inorganic elements generation sedimentations, thereby when adhering to or permeating the various device that uses and element, material surface in gas industry, can cause the harm such as metal erosion and material aging.Yet, there is no so far the ripe harvester for inorganic elements in combustion gas and assay method.
At present, in collection combustion gas, the method for inorganic elements can be divided into gas-solid adsorption method and gas-liquid absorption process.Uddin etc. (Energy Fuels, 2009,23,4710-4716) and Ozaki etc. (Fuel, 2008,87,3610-3615) reported respectively and adopted the inorganic mercury of synthetic adsorbent based in combustion gas processed of gas-solid adsorption method enrichment coal quantitatively detection.But the collecting efficiency of these classic methods is not high, object is all for individual other inorganic elements, in addition, also needs to consume a large amount of samples and reagent.Conventional detection inorganic elements method has atomic absorption method (Anal.Chem., 2008,80,9369-9374; Anal.Chim.Acta, 2010,659,60-67), inductively coupled plasma-atomic emission spectrometry (J.Pharm.Biomed.Anal., 2010,52,652-655; Anal.Chim.Acta, 2007,584,204-209), inductively coupled plasma mass spectrometry method (Anal.Chem., 2004,76,2910-2915; J.Agric.Food Chem., 2005,53,5138-5143) and the chromatography of ions (Anal.Chem., 2003,75,6789-6798).These methods have been brought into play important reusing in analyzing inorganic elements, but some shortcomings that they exist have also hindered the application and development of himself.Atomic absorption method can not detect inorganic elements simultaneously, and a kind of element of every detection, all needs to change light source, complex operation.Inductively coupled plasma-atomic emission spectrometry is not high to some nonmetalloid detection sensitivities.Inductively coupled plasma mass spectrometry method, instrument is expensive, and analysis cost is high, is unfavorable for promoting, and is not suitable for the detection of part nonmetalloid.Although chromatography of ions contribution aspect detection nonmetalloid is remarkable, its analysis time is longer, and sensitivity does not often reach the requirement detecting under trace condition yet, and needs complicated sample preconcentration step.In addition, and Rupp etc. (Anal.Chem., 2010,82,6315-6317) adopt gas chromatography-mass spectrography to the micro-Hg in simulation combustion gas, AsH
3, PH
3and H
2se analyzes, but the method is only applicable to the detection of some volatile inorganic elements, to most of inorganic elements, particularly metallic element, cannot detect.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of method of measuring inorganic elements in combustion gas, not only can effectively gather various inorganic elements the Fast Measurement of realization to it in combustion gas, and efficiency is high, cost is low.
According to an aspect of the present invention, provide a kind of method of measuring inorganic elements in combustion gas, comprised the following steps:
Sample collection, gas-flow is after filter membrane, and minute two parts flow through kation absorption liquid and negative ion absorption liquid;
Sample preparation, filter membrane is divided into two parts, and a part of filter membrane is cleared up by acid solution, then adds after kation absorption liquid, and constant volume, filtration, obtain the filtrate for cation analysis; By after another part filter membrane water extraction, extract adds constant volume and filtration after negative ion absorption liquid, obtains the filtrate for anion analysis;
Sample analysis, carries out respectively Capillary Electrophoresis test by described filtrate, then data is processed.
In said method, described filter membrane is for gathering the inorganic elements of combustion gas.Described filter membrane is selected the filtering membrane of macromolecule polymer material.Wherein, described filter membrane preferably polytetrafluoroethylene film.
In said method, described kation absorption liquid is acid solution, for absorbing the kation of combustion gas.Wherein said kation absorption liquid is preferably BAS.In a specific embodiment, the concentration of described BAS is 10 ~ 50mmol/L.
In said method, described negative ion absorption liquid is alkali lye, for absorbing the negative ion of combustion gas.Wherein said negative ion absorption liquid is preferably sodium hydroxide solution.In a specific embodiment, the concentration of described sodium hydroxide solution is 10 ~ 50mmol/L.
In said method, described acid solution is strong acid, for clearing up filter membrane.Described acid solution is preferably pure nitric acid.In a specific embodiment, in the step of sample preparation, for accelerating to clear up and extract, the mode such as can take that microwave is assisted.
In a specific embodiment of said method, in described sample preparation step, described filtration step can adopt membrane filtration, as adopts the membrane filtration of 0.45 μ m.
In said method, in sample analysis step, input mode during Capillary Electrophoresis test is styletable electrical field magnified injection, and ultraviolet source detects.In a specific embodiment, when kation is detected, input mode is styletable electrical field magnified injection mode, first under 0.5psi pressure, intake 5s, then sample introduction 10s under 10kV voltage.In another specific embodiment, when negative ion is detected, input mode is styletable electrical field magnified injection mode, the 10s of first intaking under 0.5psi pressure, then sample introduction 10s under-5kV voltage.
In a specific embodiment of said method, in described step 3), when kation is detected, separation voltage is 20kV, and it is 214nm, wherein mobile phase that ultraviolet detects wavelength: 10mmol/L imidazoles, 1mmol/L 18-crown ether-6,10%(v/v) methyl alcohol, it is 3.5 that acetic acid is adjusted pH.
In another specific embodiment of said method, in described step 3), when negative ion is detected, separation voltage is-10kV, it is 254nm, wherein mobile phase that ultraviolet detects wavelength: 40mmol/L potassium chromate, 0.5mmol/L cetyl trimethyl ammonium bromide, 20mmol/L trishydroxymethylaminomethane, it is 9.1 that acetic acid is adjusted pH.
Said method also comprises the drafting of blank test and typical curve, by data processing, obtains the concentration of contained inorganic elements in combustion gas.
The test of described blank, refers to that zwitterion absorption liquid is placed the time identical with actual samples by collected specimens not, and then zwitterion absorption liquid is respectively after constant volume, filtration, and gained filtrate is carried out Capillary Electrophoresis test, obtains the data of blank sample.
Described typical curve comprises the drafting of kation typical curve and the drafting of negative ion typical curve.Adopt capillary electrophoresis apparatus to analyze the sample solution of handling well, the composition detecting can be divided into kation and the large class of negative ion two.Kation comprises, as ammonium radical ion, potassium ion, calcium ion, sodion, manganese ion, zinc ion, barium ion, aluminium ion and lead ion etc.Negative ion is as chlorion, nitrite ion, nitrate ion, sulfate ion and phosphoric acid one hydrogen radical ion etc.
The drafting of typical curve comprises: the drafting of the drafting of negative ion typical curve and kation typical curve.Configuration comprises respectively the series standard mixed liquor of contained zwitterion in combustion gas, then uses Capillary Electrophoretic Determination, with concentration to peak area drawing standard curve.In a specific embodiment, the drafting of described kation typical curve comprises: preparation contains that ammonium radical ion, potassium ion, calcium ion, sodion, manganese ion, zinc ion, barium ion, aluminium ion and plumbum ion concentration are 10,25,50,75,100,200,500,750, the standard series mixed liquor of 1000ng/mL, then according to instrumentation condition bioassay standard series, each concentration replication 3 times, with concentration to peak area drawing standard curve.In another specific embodiment, the drafting of described negative ion typical curve comprises: preparation contains that chlorion, nitrite ion, nitrate ion, sulfate ion and phosphoric acid one hydrogen radical ion concentration are 10,25,50,75,150,250, the standard series mixed liquor of 400ng/mL.According to instrumentation condition bioassay standard series, each concentration replication 3 times, with concentration to peak area drawing standard curve.
In said method, the actual sample of handling well by mensuration and blank sample, the sample peak area recording deducts after blank peak area, in corresponding typical curve, obtain each concentration of element value, thereby realize, the inorganic elements in combustion gas is carried out to quantitative test, obtain the content of various inorganic elements in combustion gas.Wherein computing formula is as follows:
Sampling volume is converted into standard sample volume:
In formula:
V
0-standard sample volume, unit is L;
V-sampling volume, unit is L;
T-sampled point temperature, unit is ℃;
P-sampled point pressure, unit is kPa.
Calculate inorganic element content in combustion gas:
In formula:
Inorganic element content in C-combustion gas, unit is μ g/m
3;
C
i-sample concentration value, unit is ng/mL;
C
0-blank sample concentration value, unit is ng/mL;
V
i-sample solution constant volume, unit is mL;
V
0-standard sample volume, unit is L;
According to a further aspect in the invention, provide a kind of device of measuring inorganic elements in combustion gas, comprised dual flow path Gas-Liquid Absorption device and capillary electrophoresis apparatus, wherein dual flow path Gas-Liquid Absorption device comprises: containing the filtration unit of filter membrane; The negative ion absorption bottle being connected with filtration unit; The kation absorption bottle being connected with filtration unit.
In said apparatus, the described filtration unit containing filter membrane is for gathering the inorganic elements of combustion gas.In a specific embodiment, the filtering head of poly tetrafluoroethylene is housed in described membrane filtration device.
In said apparatus, the gas feed of described zwitterion absorption bottle has quartzy sieve plate.In a specific embodiment, the thickness of the quartzy sieve plate in zwitterion absorption bottle is 5mm.At described zwitterion absorption bottle, also can be connected with gas flow meter, to control the flow with mensurated gas composition.
According to method and apparatus provided by the invention, overcome low, the consuming time length of traditional sampling method efficiency, analysis cost is higher, is difficult to universal shortcoming, has realized the target of the multiple inorganic elements of fast detecting.According to method and apparatus provided by the invention, operating cost is lower, simple to operate, be convenient to promote, effective collection and fast detecting for inorganic elements in combustion gas, a kind of reliable and new method of being convenient to implement is provided, can have met inorganic elements in combustion gas is detected and the needs of research, also can be used for the content of inorganic elements in Real-Time Monitoring combustion gas simultaneously.
Accompanying drawing explanation
Fig. 1 has shown schematic diagram according to an embodiment of the invention;
Fig. 2 has shown standard cation capillary electrophoresis separation chromatogram according to an embodiment of the invention;
Fig. 3 has shown Plays negative ion capillary electrophoresis separation chromatogram according to one embodiment of present invention.
Embodiment
Below in conjunction with instantiation, the present invention will be further described.
Fig. 1 has shown schematic diagram according to an embodiment of the invention.From fuel gas transportation pipeline 1 combustion gas out, after flange 2 and reduction valve, after 3, enter dual flow path Gas-Liquid Absorption device, then from absorption plant, discharge.Described dual flow path Gas-Liquid Absorption device mainly comprises filtering head 4, kation absorption bottle 6, negative ion absorption bottle 7 and the flowmeter 11 containing poly tetrafluoroethylene 5.After the filtering head 4 of the gas-flow that enters dual flow path Gas-Liquid Absorption device through comprising poly tetrafluoroethylene 5, be divided into two strands, one combustion gas is by kation absorption bottle 6 and the rear discharge of flowmeter 11, and another burst of combustion gas is by negative ion absorption bottle 7 and the rear discharge of flowmeter 11.Kation absorption bottle 6 bottoms are covered with quartzy sieve plate 8, and combustion gas enters from the bottom of kation absorption bottle 6, and flow out on the top from kation absorption bottle 6 after kation absorption liquid 9.Negative ion absorption bottle 7 bottoms are also covered with quartzy sieve plate 8, and combustion gas enters from the bottom of negative ion absorption bottle 7, after negative ion absorption liquid 10 absorbs, from the top of negative ion absorption bottle 7, flow out.
Embodiment 1
1. sample collection:
Use dual flow path Gas-Liquid Absorption device to gather combustion gas, the diameter of filter membrane is 45mm.With 400mL/min flow velocity, gather 90min.In kation absorption bottle, fill the 50mmol/L BAS (for absorbing combustion gas soluble cation) of 6mL.In negative ion absorption bottle, fill the 50mmol/L sodium hydroxide solution (for absorbing combustion gas Soluble Anions) of 6mL.
2. sample preparation: the sample filter membrane of collection is equally divided into two halves, after half shreds, adds 6mL to analyze pure nitric acid, put into microwave instrument and carry out Microwave _ assisted digestion.Solution after clearing up is poured in teflon bottle, and adds the sample filling in 50mmol/L boric acid absorption liquid, mixes constant volume (12ml), after 0.45 μ m membrane filtration for inorganic cation analysis; After second half shreds, add 6mL redistilled water, put into microwave instrument and carry out microwave auxiliary extraction.Solution after extraction is poured in teflon bottle, and adds the sample filling in 50mmol/L NaOH absorption liquid, mixes constant volume (12ml), after 0.45 μ m membrane filtration for inorganic anion analysis.
3. sample analysis:
The drafting of 3.1 typical curves
Standard cation curve: preparation contains that ammonium radical ion, potassium ion, calcium ion, sodion, manganese ion, zinc ion, barium ion, aluminium ion and plumbum ion concentration are 10,25,50,75,100,200,500,750, the standard series mixed liquor of 1000ng/mL.Analytical instrument adopts the U.S. P/ACE MDQ of Beckman company type capillary electrophoresis apparatus, and chromatographic condition is: use the uncoated quartz capillary of inside surface of melting, long 60cm(is effective length 50cm wherein), internal diameter 75 μ m; Mobile phase is 10mmol/L imidazoles, 1mmol/L 18-crown ether-6, and 10%(v/v) methyl alcohol, it is 3.5 that acetic acid is adjusted pH; Separation voltage adopts 20kV; Column temperature is 25 ℃; Ultraviolet detects wavelength and uses 214nm; Adopt styletable electrical field magnified injection mode, first under 0.5psi pressure, intake 5s, then sample introduction 10s under 10kV voltage.Each concentration replication 3 times.With concentration to peak area drawing standard curve.Table 1 is standard cation solution testing result.Concentration is that the Capillary Electrophoresis chromatogram of the standard mixed liquor of 200ng/mL is shown in Fig. 2.
Table 1 kation standard solution linear equation and detectability
Negative ion typical curve: preparation contains that chlorion, nitrite ion, nitrate ion, sulfate ion and phosphoric acid one hydrogen radical ion concentration are 10,25,50,75,150,250, the standard series mixed solution of 400ng/mL.Analytical instrument adopts the U.S. P/ACE MDQ of Beckman company type capillary electrophoresis apparatus, and chromatographic condition is: use the uncoated quartz capillary of inside surface of melting, long 60cm(is effective length 50cm wherein), internal diameter 75 μ m; Mobile phase is 40mmol/L potassium chromate, 0.5mmol/L cetyl trimethyl ammonium bromide, and 20mmol/L trishydroxymethylaminomethane, it is 9.1 that acetic acid is adjusted pH; Separation voltage employing-10kV; Column temperature is 25 ℃; Ultraviolet detects wavelength 254nm; Adopt styletable electrical field magnified injection mode, the 10s of first intaking, then sample introduction 10s under-5kV voltage under 0.5psi pressure.Each concentration replication 3 times, with concentration to peak area drawing standard curve.Table 2 is standard anion solutions testing result.Concentration is that the Capillary Electrophoresis chromatogram of the standard mixed liquor of 200ng/mL is shown in Fig. 3.
Table 2 negative ion standard solution linear equation and detectability
3.2 blank experiments
The dual flow path Gas-Liquid Absorption device that does not contain filter membrane is positioned in air, places 90min.Wherein, in kation absorption bottle, fill the 50mmol/L BAS of 6mL, in negative ion absorption bottle, fill the 50mmol/L sodium hydroxide solution of 6mL.Liquid in zwitterion absorption bottle respectively constant volume (12ml), after 0.45 μ m membrane filtration, carry out respectively Capillary Electrophoresis test, the test condition of test condition during respectively with drawing standard zwitterion curve.The zwitterion blank sample of blank experiment is all measured 3 times.
The mensuration of 3.3 samples
Kation is measured: the test condition of test condition during with drawing standard kation curve, replication 3 times.Negative ion is measured: the test condition of test condition during with drawing standard negative ion curve, replication 3 times.
3.4 data processing
The zwitterion sample peak area recording deducts after corresponding blank zwitterion peak area, in corresponding typical curve, obtain each sample in concentration of element value, then according to formula (1) and (2), calculate the content of each inorganic elements in combustion gas.Table 3 and table 4 are inorganic elements test result in actual sample.The recovery of standard addition of each inorganic ions, between 89%-106%, meets lab analysis requirement.
Inorganic elements measurement result (1) in the actual combustion gas sample of table 3
-represent not detect.
Inorganic elements measurement result (2) in the actual combustion gas sample of table 4
From table 3 and table 4, can find out, according to method and apparatus provided by the invention, can effectively measure the content of contained multiple inorganic elements in combustion gas.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, but should be understood to word wherein used, be descriptive and explanatory vocabulary, rather than limited vocabulary.Can in the scope of the claims in the present invention, to the present invention, modify in accordance with regulations, and within not deviating from scope and spirit of the present invention, the present invention be revised.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Claims (10)
1. a method of measuring inorganic elements in combustion gas, comprises the following steps:
Sample collection, gas-flow is after filter membrane, and minute two parts flow through kation absorption liquid and negative ion absorption liquid;
Sample preparation, filter membrane is divided into two parts, and a part of filter membrane is cleared up by acid solution, then adds after kation absorption liquid, and constant volume, filtration, obtain the filtrate for cation analysis; By after another part filter membrane water extraction, extract adds constant volume and filtration after negative ion absorption liquid, obtains the filtrate for anion analysis;
Sample analysis, carries out respectively Capillary Electrophoresis test by described filtrate, then data is processed;
Wherein, the filtering membrane that described filter membrane is macromolecular material, described kation absorption liquid is acid solution, and described negative ion absorption liquid is alkali lye, and the acid solution that described filter membrane is cleared up use is strong acid.
2. method according to claim 1, is characterized in that, described filter membrane is poly tetrafluoroethylene.
3. method according to claim 1, is characterized in that, described kation absorption liquid is BAS, and the concentration of described BAS is 10～50mmol/L.
4. method according to claim 1, is characterized in that, described negative ion absorption liquid is sodium hydroxide solution, and the concentration of described sodium hydroxide solution is 10～50mmol/L.
5. method according to claim 1, is characterized in that, the acid solution that described filter membrane is cleared up use is pure nitric acid.
6. method according to claim 1, is characterized in that, input mode during described Capillary Electrophoresis test is styletable electrical field magnified injection, and ultraviolet source detects.
7. according to the method described in any one in claim 1～6, it is characterized in that, in described sample analysis step, when kation is detected, separation voltage is 20kV, and it is 214nm that ultraviolet detects wavelength, mobile phase wherein: 10mmol/L imidazoles, 1mmol/L18-crown ether-6,10%(v/v) methyl alcohol, it is 3.5 that acetic acid is adjusted pH.
8. according to the method described in any one in claim 1～6, it is characterized in that, in described sample analysis step, when negative ion is detected, separation voltage is-10kV that it is 254nm that ultraviolet detects wavelength, mobile phase wherein: 40mmol/L potassium chromate, 0.5mmol/L cetyl trimethyl ammonium bromide, 20mmol/L trishydroxymethylaminomethane, it is 9.1 that acetic acid is adjusted pH.
9. utilize in claim 1-8 method described in any one to measure a device for inorganic elements in combustion gas, comprise dual flow path Gas-Liquid Absorption device and capillary electrophoresis apparatus, wherein dual flow path Gas-Liquid Absorption device comprises: filtration unit; The negative ion absorption bottle being connected with filtration unit; The kation absorption bottle being connected with filtration unit.
10. device according to claim 9, is characterized in that, the gas feed of described negative ion absorption bottle and kation absorption bottle has quartzy sieve plate.
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| "气溶胶水溶性无机物及有机物的离子色谱测定";余雪春等;《环境化学》;20040331;第23卷(第2期);第218-222页 * |
| 余雪春等."气溶胶水溶性无机物及有机物的离子色谱测定".《环境化学》.2004,第23卷(第2期),第218-222页. |
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