CN102305835A - 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
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- CN102305835A CN102305835A CN201110136837A CN201110136837A CN102305835A CN 102305835 A CN102305835 A CN 102305835A CN 201110136837 A CN201110136837 A CN 201110136837A CN 201110136837 A CN201110136837 A CN 201110136837A CN 102305835 A CN102305835 A CN 102305835A
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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 of method that realizes the formic acid of flame ionization ditector detection trace or trace through the catalytic reduction technology indirectly.
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 that legal medical expert identifies 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 big, 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 the result fast 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; Chinese environmental monitoring, 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 and differently with the acting force between the chromatographic column is able to separate, quantitatively, uses the chromatography of ions sample alkalization need 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 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 glacial acetic acid 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 big 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, formic acid need be derived usually turns to material (the gas Chromatographic Determination method of formic acid in the workshop air, the GB/T17068-1997 that signal response is arranged on 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 the catalyzer of certain sulfuric acid as 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 through the hydrogenation catalyst reduction; Can detect carbon monoxide, the carbon dioxide of ppm level concentration through this method, but through hydrogenation catalyst also orthoformic acid realize that the method that trace formic acid detects do not see public reported.
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 objective of the invention is to realize 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 through flame ionization ditector.
The present invention can also comprise:
1, described nickel hydrogenation catalyst is made up of carrier and active component; Said 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; Said 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, said 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 said reaction tube is controlled between 310～380 degrees centigrade.
4, the working gas that flows out of said gas chromatographic column is an 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 formic acid efficiently being converted into methane.Described nickel hydrogenation catalyst is made up 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 the 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 able to separate with other components.If carrier gas is inert gas (for example nitrogen, periodic table the 8th a main group rare gas), connect a branch road on the inlet needs side of reaction tube, provide hydrogen as reducing gas.If carrier gas is a hydrogen, then the inlet 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 gets into 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 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 on detecting device.
Advantage of the present invention is mainly reflected in:
1, to need not bigger change just can be the detection that realizes trace or trace formic acid to the structure that possesses the conventional gas chromatograph of flame ionization ditector, has better repeatability and measure linear simultaneously.
2, this method relate to the catalyzer of use need be such as noble metals such as platinum, palladiums, low price.
Description of drawings
Fig. 1 is a 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
Through embodiment the present invention is described further below, but claim scope of the present invention is not subjected to the restriction of these embodiment.Such as, all can realize the object of the invention as long as satisfy the various conditions of narrating in the summary of the invention, this is to understand easily 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 the 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 the nitrogen of 5480ppm for the formic acid volume content, 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 big relation, and these data only possess reference significance.Representative chromatogram is shown in accompanying drawing 2, and the 3.157min place is a 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 the 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 the nitrogen of 5480ppm for the formic acid volume content, 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 big 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 the 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 the nitrogen of 5480ppm for the formic acid volume content, 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 big 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 the 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 the nitrogen between 1099～5480ppm for the formic acid volume content, 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 big relation, and these data only possess reference significance.
Claims (6)
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 through flame ionization ditector.
2. the method that detects formic acid based on the flame ionization ditector of catalytic reduction technology according to claim 1; It is characterized in that: described nickel hydrogenation catalyst is made up of carrier and active component; Said 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; Said 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.
3. the method that detects formic acid based on the flame ionization ditector of catalytic reduction technology according to claim 1 and 2; It is characterized in that: said nickel hydrogenation catalyst is loaded in the reaction tube, and reaction tube places between chromatographic column outlet and the flame ionization ditector import.
4. the flame ionization ditector based on the catalytic reduction technology according to claim 3 detects the method for formic acid, and it is characterized in that: the temperature of said reaction tube is controlled between 310～380 degrees centigrade.
5. the method that detects formic acid based on the flame ionization ditector of catalytic reduction technology according to claim 3; It is characterized in that: the working gas that said gas chromatographic column flows out is an 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.
6. the method that detects formic acid based on the flame ionization ditector of catalytic reduction technology according to claim 4; It is characterized in that: the working gas that said gas chromatographic column flows out is an 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.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108333284A (en) * | 2018-02-08 | 2018-07-27 | 北京雪迪龙科技股份有限公司 | The method and its system of carbon compound are detected based on catalytic conversion technique |
| 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 |
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Non-Patent Citations (3)
| Title |
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| 《Journal of Chromatography B》 19991231 Xiao-Pen Lee etal Analysis of methanol or formic acid in body fluids by headspace solid-phase microextraction and capillary gas chromatography 155-162 1-6 第734卷, * |
| 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》 * |
| 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》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108333284A (en) * | 2018-02-08 | 2018-07-27 | 北京雪迪龙科技股份有限公司 | The method and its system of carbon compound are detected based on catalytic conversion technique |
| CN111551643A (en) * | 2018-02-08 | 2020-08-18 | 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 |
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