CN102305835B - Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology - Google Patents
Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology Download PDFInfo
- Publication number
- CN102305835B CN102305835B CN 201110136837 CN201110136837A CN102305835B CN 102305835 B CN102305835 B CN 102305835B CN 201110136837 CN201110136837 CN 201110136837 CN 201110136837 A CN201110136837 A CN 201110136837A CN 102305835 B CN102305835 B CN 102305835B
- Authority
- CN
- China
- Prior art keywords
- formic acid
- flame ionization
- catalytic reduction
- reduction technology
- chromatographic column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides a method for detecting formic acid by using a hydrogen flame ionization detector based on a catalytic reduction technology. A trace amount of formic acid is reduced into methane in the presence of hydrogen by using a nickel hydrogenation reduction catalyst, and the generated methane is detected by the hydrogen flame ionization detector. The trace amount of the formic acid is indirectly detected by the hydrogen flame ionization detector by the catalytic reduction technology. The method has the advantages that: 1, the trace amount of formic acid can be detected under the condition that the structure of the conventional gas chromatograph of the hydrogen flame ionization detector is not needed to be changed greatly, and the method is high in repeatability and measurement linearity; and 2, catalysts which are used in the method, such as platinum, palladium and other noble metal are not needed, so the price is low.
Description
Technical field
What the present invention relates to is a kind of detection method of formic acid.Specifically a kind ofly realize indirectly that by the catalytic reduction technology flame ionization ditector detects the method for the formic acid of trace or trace.
Background technology
Formic acid is a kind of volatile organic contaminant common in the atmosphere, and it mainly is derived from the rough burning, organic rough burning or the incomplete oxidation that contain alcohol and mix oil plant, the decarboxylation procedure in the organic synthesis, the physiological metabolism of ant class.Formic acid is the metabolic product of human body methanol poisoning, is the foundation of forensic identification methanol poisoning.
The operable method of the quantitative test of formic acid has: acid base titration, chromatography, infra-red sepectrometry.The instrument and equipment that acid base titration is used is comparatively simple, but the running time is long, and amount of samples is large, and detectability is higher.Infra-red sepectrometry (tractor and agricultural transportation vehicle, 2009,36 volumes, 80-82) be measure intensity corresponding to the infrared absorption peak of formic acid realize to formic acid quantitatively, can obtain fast the result for noiseless matter sample, if when having other organic acids in the sample then can interference be arranged to measurement result.
Chromatography quantitative test formic acid is the present comparatively method of widespread use, and chromatography can specifically be divided into the chromatography of ions (metallurgical analysis, 2009,29,13-18 again; Development fields of environmental monitoring in china, 2004,23-24), high performance liquid chromatography (Atmospheric Environment, 34,3921-3929; Chromatographia, 50,150-154), vapor-phase chromatography.The chromatography of ions is based on formate ion and other negative ion differently from the acting force between the chromatographic column is separated, quantitatively, uses the chromatography of ions sample alkalization need to be generated formate anion, and chromatography of ions equipment and consumptive material are comparatively expensive simultaneously.The formic acid of liquid chromatography in can well separating mixture, in order to reduce detectability, formic acid need to be derived turns to the material that UV-detector is had response.
Gas chromatography also can be carried out quantitative test to formic acid, but the detectability of formic acid and employed detecting device have much relations.When using thermal conductivity cell detector, because the sensitivity of thermal conductivity cell detector self is lower, so can only be used for quantitative test (the mensuration GB/T 1628.5-2000 of industrial acetic formic acid content of micro-formic acid; Physical and chemical inspection: chemical fascicle, 2008,960-961).Use helium ionization detector (helium ionization detector, gas-chromatography detection method, Chemical Industry Press, 2000) time, can detect the formic acid of ppb rank concentration, but helium ionization detector requires height to the purity of working gas and the impermeability of system, so there is very large difficulty in practical application, so the practical application of helium ionization detector is not very wide.Electron capture detector (chromatogram, 2006,418) can realize easily that ppm level concentration formic acid ground detects, but service condition is comparatively harsh.
Flame ionization ditector is the most frequently used detecting device of gas chromatographic analysis, but formic acid can't generate the methane species in the hydrogen flame of burning, so the response of formic acid on flame ionization ditector almost is per mille (the Journal of chromatography of methane, 1961,312-323; The gas chromatography application manual, Inst. of Jilin Chemical Industry Co is compiled).In order to use flame ionization ditector to carry out the analysis of formic acid, usually formic acid need to be derived turns to material (Gas Chromatographic Method of formic acid in the workshop air, the GB/T17068-1997 that signal response is arranged at flame ionization ditector; Hubei Polytichnic College's journal, 2000,15,40-41), for example methyl formate, ethyl formate.The specific practice of formic acid derivatization is that testing sample is mixed with certain alcohol, add certain sulfuric acid as the catalyzer of esterification, potpourri is placed certain hour 50-60 degree centigrade of sealing, adopt the method for headspace sampling that the potpourri introducing gas chromatography that contains formic ether in the enclosed system gas phase is analyzed.
It is the technology of a comparative maturity that the insensitive material of flame ionization ditector (for example carbon monoxide, carbon dioxide, formaldehyde) is created on methyl alcohol or methane that signal response is arranged on the flame ionization ditector by the hydrogenation catalyst reduction, can detect carbon monoxide, the carbon dioxide of ppm level concentration by the method, but by hydrogenation catalyst also orthoformic acid realize that the method that trace formic acid detects has no open report.
Summary of the invention
The object of the present invention is to provide a kind of simple and easy to do, method of need not the pretreated flame ionization ditector based on the catalytic reduction technology of analyte derivativeization is detected formic acid.
The object of the present invention is achieved like this:
Use nickel hydrogenating reduction catalyzer that the formic acid of trace or trace is reduced to methane under the condition that hydrogen exists, detect the methane that generates by flame ionization ditector.
The present invention can also comprise:
1, described nickel hydrogenation catalyst is made of carrier and active component, described carrier is the BET specific surface area greater than 300 square metres of every grams, the average pore size macro porous silica gel greater than 10 nanometers, described active component is the potpourri of metallic nickel and aluminium oxide, active component accounts for 10%～40% of total weight of carrier, and nickel is 9: 1～1: 9 with the quality of aluminium oxide than scope.
2, described nickel hydrogenation catalyst is loaded in the reaction tube, and reaction tube places between chromatographic column outlet and the flame ionization ditector import.
3, the temperature of described reaction tube is controlled between 310～380 degrees centigrade.
4, the working gas that flows out of described gas chromatographic column is inert gas, hydrogen make-up between chromatographic column outlet and the reaction tube that contains nickel hydrogenation catalyst, and hydrogen flow rate is 0.2～10 times of working gas of gas chromatographic column outflow.
The invention provides a kind of simple and easy to do, need not the analyte derivative pre-service, available conventional flame ionization ditector detects the method for trace or trace formic acid.
The present invention uses nickel hydrogenation catalyst more than 300 degrees centigrade the formic acid Efficient Conversion being methane.Described nickel hydrogenation catalyst is made of carrier and active component, carrier is business-like, BET specific surface area greater than 300 square metres of every grams, the average pore size macro porous silica gel greater than 10 nanometers, active component is metallic nickel and the aluminium oxide of high dispersive, active component accounts for 10%～40% of total weight of carrier, and the quality of nickel, aluminium oxide is 9: 1～1: 9 than scope.Volume ratio is reduced to methane as the formic acid of 1099ppm-5480ppm in can be with hydrogen when catalyzer uses between 310-380 ℃, and conversion ratio is greater than 99.5%.
The entrance point that contains a certain amount of hydrogenation catalyst recited above, chemical inertness, heat-resisting reaction tube is connected in the endpiece of chromatographic column, and the endpiece of this reaction tube is connected in the inlet end of flame ionization ditector.Carry blending ingredients when carrier gas and pass certain chromatographic column, formic acid is separated with other components.If carrier gas is inert gas (for example nitrogen, periodic table the 8th main group rare gas), connect a branch road on the entrance needs side of reaction tube, provide hydrogen as reducing gas.If carrier gas is hydrogen, then the entrance of reaction tube does not need the other branch road that connects.Reaction tube places in the constant temperature heating device, and it is 300～400 degrees centigrade that constant temperature heating device makes the temperature in the reaction tube.When containing the carrier gas process reaction tube of formic acid, hydrogen, formic acid is methane and water by hydrogenating reduction.Methane enters flame ionization ditector with after-combustion, and flame ionization ditector provides signal response.
Flame ionization ditector physical construction need not to change; The mode of operation of hydrogen flame ionization detector is according to normal mode, but required amounts of hydrogen need to be deducted the amounts of hydrogen that the reaction pipe end flows out, and the temperature of detecting device will guarantee that the water of analyzing component and the generation of hydrogen flame combustion does not condense at detecting device.
Advantage of the present invention is mainly reflected in:
1, it just can be the detection that realizes trace or trace formic acid that the structure that possesses the conventional gas chromatograph of flame ionization ditector need not larger change, has simultaneously preferably repeatability and measure linear.
2, the method catalyzer of relating to use need to noble metals such as platinum, palladium, low price.
Description of drawings
Fig. 1 is testing process synoptic diagram of the present invention.
Fig. 2 is the representative chromatogram of embodiment 1.
Fig. 3 is extension concentration～chromatographic peak area relation curve.
Embodiment
The invention will be further described below by embodiment, but claim scope of the present invention is not subjected to the restriction of these embodiment.Such as, all can realize purpose of the present invention as long as satisfy the various conditions of narrating in the summary of the invention, this is that appearance is intelligible to those skilled in the art.For brevity, present embodiment has only provided partial condition, but and does not mean that the condition that does not provide among the embodiment is just infeasible.
Embodiment 1: catalyst support is the BET specific surface area greater than 300 square metres of every grams, the average pore size macro porous silica gel greater than 10 nanometers, active component is metallic nickel and the aluminium oxide of high dispersive, active component accounts for 20% of total weight of carrier, wherein nickel accounts for 10% of total weight of carrier, aluminium oxide accounts for 10% of total weight of carrier, catalyst amount 0.3 gram, 340 degrees centigrade of catalyzer working temperatures.Carrier gas is that purity is better than 99.99% hydrogen, 30 milliliters of per minutes of flow velocity, not extra hydrogen make-up.The combustion-supporting gas of flame ionization ditector is the natural air that discolour silica gel purifies, and the moisture content dew point is lower than subzero 15 degrees centigrade, and hydrocarbons content is lower than 10ppm, 300 milliliters of per minutes of flow velocity.Flame ionization ditector producer normal sensibility is 5 * 10-11g/s (benzene).2 millimeters of chromatographic column internal diameters, 2000 millimeters of column lengths, filler are GDX-502,140 degrees centigrade of chromatographic column temperatures.Sample is that the formic acid volume content is the nitrogen of 5480ppm, 0.3 milliliter of sample size.8680623 microvolt seconds of chromatographic peak area, relative deviation is less than 0.1%, and in fact the instrument of these parameters and use, chromatographic column have very large relation, and these data only possess reference significance.Representative chromatogram as shown in Figure 2, the 3.157min place is formic acid.
Embodiment 2: catalyst support is the BET specific surface area greater than 300 square metres of every grams, the average pore size macro porous silica gel greater than 10 nanometers, active component is metallic nickel and the aluminium oxide of high dispersive, active component accounts for 40% of total weight of carrier, wherein nickel accounts for 4% of total weight of carrier, aluminium oxide accounts for 36% of total weight of carrier, catalyst amount 0.3 gram, 380 degrees centigrade of catalyzer working temperatures.Carrier gas is that purity is better than 99.99% hydrogen, 30 milliliters of per minutes of flow velocity, not extra hydrogen make-up.The combustion-supporting gas of flame ionization ditector is the natural air that discolour silica gel purifies, and the moisture content dew point is lower than subzero 15 degrees centigrade, and hydrocarbons content is lower than 10ppm, 300 milliliters of per minutes of flow velocity.Flame ionization ditector producer normal sensibility is 5 * 10-11g/s (benzene).2 millimeters of chromatographic column internal diameters, 2000 millimeters of column lengths, filler are GDX-502,140 degrees centigrade of chromatographic column temperatures.Sample is that the formic acid volume content is the nitrogen of 5480ppm, 0.3 milliliter of sample size.8591542 microvolt seconds of chromatographic peak area, relative deviation is less than 0.15%, and in fact the instrument of these parameters and use, chromatographic column have very large relation, and these data only possess reference significance.
Embodiment 3: catalyst support is the BET specific surface area greater than 300 square metres of every grams, the average pore size macro porous silica gel greater than 10 nanometers, active component is metallic nickel and the aluminium oxide of high dispersive, active component accounts for 10% of total weight of carrier, wherein nickel accounts for 9% of total weight of carrier, aluminium oxide accounts for 1% of total weight of carrier, catalyst amount 0.3 gram, 310 degrees centigrade of catalyzer working temperatures.Carrier gas is that purity is better than 99.99% nitrogen, 30 milliliters of per minutes of flow velocity, extra 35 milliliters of per minutes of hydrogen make-up.The combustion-supporting gas of flame ionization ditector is the natural air that discolour silica gel purifies, and the moisture content dew point is lower than subzero 15 degrees centigrade, and hydrocarbons content is lower than 10ppm, 300 milliliters of per minutes of flow velocity.Flame ionization ditector producer normal sensibility is 5 * 10-11g/s (benzene).2 millimeters of chromatographic column internal diameters, 2000 millimeters of column lengths, filler are GDX-502,140 degrees centigrade of chromatographic column temperatures.Sample is that the formic acid volume content is the nitrogen of 5480ppm, 0.3 milliliter of sample size.7642334 microvolt seconds of chromatographic peak area, relative deviation is less than 0.2%, and in fact the instrument of these parameters and use, chromatographic column have very large relation, and these data only possess reference significance.
Embodiment 4: catalyst support is the BET specific surface area greater than 300 square metres of every grams, the average pore size macro porous silica gel greater than 10 nanometers, active component is metallic nickel and the aluminium oxide of high dispersive, active component accounts for 20% of total weight of carrier, wherein nickel accounts for 10% of total weight of carrier, aluminium oxide accounts for 10% of total weight of carrier, catalyst amount 0.3 gram, 340 degrees centigrade of catalyzer working temperatures.Carrier gas is that purity is better than 99.99% hydrogen, 30 milliliters of per minutes of flow velocity, not extra hydrogen make-up.The combustion-supporting gas of flame ionization ditector is the natural air that discolour silica gel purifies, and the moisture content dew point is lower than subzero 15 degrees centigrade, and hydrocarbons content is lower than 10ppm, 300 milliliters of per minutes of flow velocity.Flame ionization ditector producer normal sensibility is 5 * 10-11g/s (benzene).2 millimeters of chromatographic column internal diameters, 2000 millimeters of column lengths, filler are GDX-502,140 degrees centigrade of chromatographic column temperatures.Sample size is 0.3 milliliter, and analytic sample is that the formic acid volume content is the nitrogen between 1099～5480ppm, linearly dependent coefficient 0.99961, and extension concentration～chromatographic peak area relation curve can detect and be limited to 149ppm, referring to accompanying drawing 3.In fact the instrument of these results and use, chromatographic column have very large relation, and these data only possess reference significance.
Claims (4)
1. method that detects formic acid based on the flame ionization ditector of catalytic reduction technology, it is characterized in that: use nickel hydrogenating reduction catalyzer that the formic acid of trace or trace is reduced to methane under the condition that hydrogen exists, detect the methane that generates by flame ionization ditector; Described nickel hydrogenation catalyst is made of carrier and active component, described carrier is the BET specific surface area greater than 300 square metres of every grams, the average pore size macro porous silica gel greater than 10 nanometers, described active component is the potpourri of metallic nickel and aluminium oxide, active component accounts for 10%～40% of total weight of carrier, and nickel is 9:1～1:9 with the quality of aluminium oxide than scope.
2. the flame ionization ditector based on the catalytic reduction technology according to claim 1 detects the method for formic acid, it is characterized in that: described nickel hydrogenation catalyst is loaded in the reaction tube, and reaction tube places between chromatographic column outlet and the flame ionization ditector import.
3. the flame ionization ditector based on the catalytic reduction technology according to claim 2 detects the method for formic acid, and it is characterized in that: the temperature of described reaction tube is controlled between 310～380 degrees centigrade.
According to claim 2 or 3 described flame ionization ditectors based on the catalytic reduction technology detect the methods of formic acid, it is characterized in that: the working gas that gas chromatographic column flows out is inert gas, hydrogen make-up between chromatographic column outlet and the reaction tube that contains nickel hydrogenation catalyst, hydrogen flow rate are 0.2～10 times of working gas of gas chromatographic column outflow.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110136837 CN102305835B (en) | 2011-05-24 | 2011-05-24 | Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110136837 CN102305835B (en) | 2011-05-24 | 2011-05-24 | Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102305835A CN102305835A (en) | 2012-01-04 |
| CN102305835B true CN102305835B (en) | 2013-01-16 |
Family
ID=45379716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110136837 Expired - Fee Related CN102305835B (en) | 2011-05-24 | 2011-05-24 | Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102305835B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108333284B (en) * | 2018-02-08 | 2020-08-04 | 北京雪迪龙科技股份有限公司 | Method and system for detecting carbon-containing compound based on catalytic conversion technology |
| CN114324708A (en) * | 2021-12-20 | 2022-04-12 | 杭州谱育科技发展有限公司 | FID detector and method based on catalytic ignition technology |
-
2011
- 2011-05-24 CN CN 201110136837 patent/CN102305835B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Analysis of methanol or formic acid in body fluids by headspace solid-phase microextraction and capillary gas chromatography;Xiao-Pen Lee etal;《Journal of Chromatography B》;19991231;第734卷;155-162 * |
| Xiao-Pen Lee etal.Analysis of methanol or formic acid in body fluids by headspace solid-phase microextraction and capillary gas chromatography.《Journal of Chromatography B》.1999,第734卷155-162. |
| 武峰等.气相色谱法分析一氧化碳中微量二氧化碳.《分析仪器》.2005,(第4期),58-59. |
| 气相色谱法分析一氧化碳中微量二氧化碳;武峰等;《分析仪器》;20051231(第4期);参见58页第2节，图1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102305835A (en) | 2012-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN203870077U (en) | Secondary cold trap enrichment device and GC-FID (Gas Chromatography-Flame Ionization Detector) combined device for detecting trace phosphine | |
| CN105181853A (en) | Method for determining ethanol and isopropyl benzene contents of air and waste gas | |
| Possanzini et al. | Determination of low boiling aldehydes in air and exhaust gases by using annular denuders combined with HPLC techniques | |
| CN102305835B (en) | Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology | |
| CN102230917B (en) | Analyzing device using gas phase chromatography and inverse gas phase chromatography together | |
| CN104007196A (en) | Secondary cold trap enrichment and GC-FID (Gas Chromatography-Flame Ionization Detector) combining device and method for detecting trace hydrogen phosphide | |
| CN103197019A (en) | Capillary gas chromatography analysis method for N-methyldiethanolamine decarbonizer component | |
| Wang et al. | Influence of sampling methods and storage condition on volatile methyl siloxanes quantification in biogas | |
| CN102539556A (en) | Method for detecting pollutants in air by using ionic liquid headspace sampling | |
| CN108414637B (en) | Method for detecting volatile disinfection byproducts in water by utilizing solid phase microextraction-gas chromatography-mass spectrometry combined technology | |
| CN110895266B (en) | Analysis device and method for measuring content of hydrogen sulfide and phosphine | |
| Patil et al. | Determination of benzene, aniline and nitrobenzene in workplace air: a comparison of active and passive sampling | |
| Jonsson et al. | Formation of methyl nitrite in engines fueled with gasoline/methanol and methanol/diesel | |
| Wang et al. | The influence of indoor environmental factors on toluene uptake rate of a tube-type diffusive sampler | |
| Matz et al. | On-line gas chromatography–mass spectrometry for process monitoring using solvent-free sample preparation | |
| CN101614669B (en) | Method and detector for detecting methanol and methyl tertiary butyl ether in gasoline by nano cataluminescence | |
| CN103776931B (en) | The assay method of the ethamine in workplace air | |
| CN204833816U (en) | Educational chromatograph | |
| CN110658265A (en) | Method for simultaneously measuring contents of benzene, toluene, xylene and naphthalene in coal gas | |
| Kaiser | Ultra Trace Analysis of Volatile Substances With GC Methods in the Sub ppm and ppb Range Down to 10− 10% | |
| CN211348073U (en) | Analysis device for measuring contents of hydrogen sulfide and phosphine | |
| CN210720291U (en) | Gas chromatograph for measuring oxygen concentration by hydrogen flame ionization detector | |
| CN110411973A (en) | A kind of method of non-methane total hydrocarbons concentration in detection gas | |
| JP2005265810A (en) | Quantitative analysis method for formaldehyde or the like | |
| CN107345948B (en) | Method for measuring content of unsaturated aldehyde in liquid-phase mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130116 Termination date: 20180524 |