CN103792131A - Curie-point pyrolyser of volatile matter generated by element in element determination - Google Patents
Curie-point pyrolyser of volatile matter generated by element in element determination Download PDFInfo
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- CN103792131A CN103792131A CN201410031985.4A CN201410031985A CN103792131A CN 103792131 A CN103792131 A CN 103792131A CN 201410031985 A CN201410031985 A CN 201410031985A CN 103792131 A CN103792131 A CN 103792131A
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Abstract
The invention discloses a curie-point pyrolyser of a volatile matter generated by an element in element determination. The curie-point pyrolyser adopts a liner tube and a curie-point pyrolysis crucible or curie-point foil filled with samples, with larger volumes than that of a pyrolysis chromatograph part. The pyrolyser comprises a heating coil 1, a quartz reaction liner tube 2, a reaction cavity 3, a reaction tube seal plug and sample support integrated device 4, a carrier gas inlet 5, a carrier gas outlet 6, the sample crucible or foil 7, a support 8 for carrying the sample crucible or foil, and a bracket 9 for carrying the support of the crucible or foil, wherein the bracket 9 for carrying the support of the crucible or foil and a seal plug are connected with a rod. Compared with a conventional tubular furnace pyrolyser, the curie-point pyrolyser has the advantages that heating velocity is high, the time of generating the volatile matter by the element is short, spectrum peak is sharp in element determination, environment temperature is low, operation is safe, and the like, and is beneficial to the accurate element determination.
Description
Technical field
The invention belongs to instrument analysis technology field, especially relate to a kind of Curie point pyrolyzer of Element generation volatile matter during for element determination.
Background technology
Along with developing rapidly of modern instrumental analysis, to the mensuration of element, atomic spectrograph is fast with its finding speed, accuracy is high and detection limit is low etc., and advantage plays more and more significantly effect.The sample that atomic spectrograph the uses system that enters is mainly pneumatic nebulization system at present.The significant drawbacks of pneumatic nebulization method is that sample nebulization efficiency is too low, and only about 3～5% really entered into instrument atom (ion) containing the sample solution of element and change device is restricted to the sensitivity and the detection limit that make instrument.In order to improve the sensitivity of these elements and to reduce detection limit, gaseous state sampling technique has also been widely used in atomic spectrum.Typical gaseous state sample injection method is hydride sampling system, by on-line mixing sample and sodium borohydride solution, make easily to form the element (as arsenic, antimony, bismuth, tin, selenium, tellurium, germanium, lead etc.) of volatile hydride to react with strong reductant sodium borohydride solution, form volatile element hydrogen compound determined.More conventional pneumatic nebulization method, gaseous state sample introduction has higher efficiency, is conventionally considered to 100%, therefore has higher mensuration sensitivity and detection limit.
At present, when atomic absorption spectrometry element, no matter be to use nebulization sampling or use gaseous state sample introduction, all need in most cases testing sample to clear up (pre-treatment), this just makes whole analytical test process time long (time for sample pretreatment conventionally account for whole analysis time 50-75%), during simultaneously due to pre-treatment, use chemical reagent, made the detection limit of solution influenced, strengthened blank value and affect the accuracy of mensuration.Have, sample pre-treatments has caused environmental pollution again, has also increased analytical test cost.
recently, the patent of invention that some the element reaction forming element volatile matter that produces hydrogen while utilizing organic cracking and then make this cracking hydrogen directly and in sample carries out element determination be in the news (CN103411892A) is proposed by the inventor.But, the cracking heating arrangement that this patent is used is tube furnace pyrolyzer, due to the tube furnace pyrolyzer rate of heat addition slow (be raised to the needed time of cracking temperature temperature from room temperature after sample is heated and be greater than 2 seconds), make element evaporation thing on determining instrument, go out peak hangover seriously, the peak type detecting is not sharp-pointed, the measurement result time is lengthened, and accuracy is bad.
Summary of the invention
The deficiency existing in order to overcome above-identified patent, the inventor improves pyrolysis in tubular furnace device above, found that, forms if use large volume Curie point pyrolyzer to carry out the cracking of element evaporation thing, and tool has an unexpected effect.According to the present invention, the large volume Curie point cracker of design carries out element evaporation thing cracking generation, heating rate is fast (be raised to cracking temperature required time from room temperature and only need tens to hundreds of millisecond) more, the peak of element on detecting instrument is more sharp-pointed, and accuracy is better.The invention discloses following technology contents for realizing this object:
A kind of Curie point pyrolyzer of Element generation volatile matter during for element determination, it is characterized in that this cracker comprises load coil 1, quartz reaction bushing pipe 2, reaction chamber 3, reaction tube sealing-plug and sample carrier integrated apparatus 4, carrier gas inlet 5, carrier gas outlet 6, sample crucible or paper tinsel 7, the support 9 of holder 8, crucible or the paper tinsel carrying use of sample crucible or paper tinsel carrying use, wherein support and the sealing-plug connecting link of crucible or paper tinsel carrying use; The sample crucible that Curie point material is made or paper tinsel are subject to the magnetic fields of self-induction coil, produce eddy current and make crucible or the paper tinsel Curie-point temperature (heating-up time is less than 1 second) that is rapidly heated, at this temperature, the element in sample and to release hydrogen reagent reaction generting element volatile matter determined.
Sample crucible of the present invention or paper tinsel are made up of at the Curie point material of 450 ℃-980 ℃ (preferably 500 ℃-800 ℃) Curie-point temperature, and sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 1 second.The preferred needed time is less than 500 milliseconds, is more preferably less than 300 milliseconds.
Curie point material of the present invention refers to: the magnetic metal simple-substance of tool or metallic gold are closed, preferably iron, cobalt, nickel metal simple-substance or alloy.
The Curie point pyrolyzer of Element generation volatile matter during for element determination of the present invention, wherein element sample to be measured is directly or indirectly loaded in Curie-point pyrolysis crucible or wraps up in folding paper tinsel, is indirectly loaded in Curie point cracking crucible.When element sample room tipping to be measured is loaded in Curie point crucible or wraps up in folding paper tinsel, crucible or paper tinsel contact the surface spraying of sample or are lined with one deck high molecular polymer or the nonmetal oxide coating without decomposition to element evaporation thing; The thickness of described crucible or paper tinsel wall is 0.05-1 millimeter.Wherein nonmetal oxide refers to silicon dioxide, titania, alundum (Al2O3) or zirconia.
The Curie point pyrolyzer of Element generation volatile matter during for element determination of the present invention, aperture position first-selection when wherein carrier gas enters bushing pipe and is output from bushing pipe is opened in the side at bushing pipe two ends, and sample inlet sealing-plug is silicone rubber seal plug.This Curie point pyrolyzer is used for the cracking of hydrogenous material, the element reaction to be measured in the hydrogen producing by cracking and sample, and generting element volatile matter is measured by atomic spectrograph.
Detailed description of the present invention below:
Curie point pyrolyzer of the present invention is used for the cracking of hydrogenous material, the element reaction to be measured in the hydrogen producing by cracking and sample, and generting element volatile matter is measured by atomic spectrograph.Typical supply frequency for generation of the radio-frequency coil (load coil 1) in magnetic field is 600kHz, and power is 48W-200W.
Element sample to be measured can directly or indirectly be contained in and in Curie-point pyrolysis crucible or paper tinsel, carry out cracking, wherein directly dress refers to that Curie point cracking crucible or paper tinsel directly contact with sample, between tipping refer to that Curie point crucible or paper tinsel surface are coated with or are lining with one deck inert barriers, by making Curie point material there is no decomposition to the element evaporation thing producing, make element evaporation thing formation efficiency higher like this.Above mentioned crucible or paper tinsel surface are coated with or are lining with one deck inert barriers and refer to:
(1) contact with the direct of Curie point material by isolating sample to the spraying of crucible or paper tinsel inside surface containing the colloidal sol of inertia nonmetallic materials, its inert material refers to the nonmetal oxide that with silicon dioxide, titania, alundum (Al2O3), zirconia etc., element evaporation thing is not produced decomposition;
(2) by add sample in a small sample bag, then the pouch that this is equipped with to sample pack crucible into or the paper tinsel that folds in, remove to carry out Curie point heating pyrolyze, so also can avoid sample directly to contact Curie point material, make the element evaporation thing forming not by Curie point material breakdown.Small sample bag material composition is pure polymer membrane, paper etc., in order to reach extraordinary isolation effect, in high molecular polymer and paper, can evenly add with nonmetal fine powders such as silicon dioxide, titania, alundum (Al2O3), zirconias.
Typical quartz bushing pipe internal diameter size is that length is at 15-40 centimetres at 1 centimetre to 5 centimetres.The opening of bushing pipe can only arrange an end according to actual conditions opening, also can have opening in two ends.Aperture position when carrier gas enters bushing pipe and is output from bushing pipe can have several different methods, and first-selection is opened the side at bushing pipe two ends.Sample inlet sealing-plug should be selected temperature resistant encapsulation plug, first-selected silicone rubber seal plug.
In the present invention, because sample weighting amount is generally at several milligrams to tens milligrams, therefore the crucible that requirement is used and wraparound well rear metal forming have larger volume, therefore will select the Curie point material of Curie-point temperature higher than cracking temperature, the temperature difference can overcome cracking like this time.Therefore the sample crucible that the Curie point material of selecting is made or the Curie-point temperature of paper tinsel should be at 450 ℃ to 980 ℃.
Curie point magnetic material, the preferably Curie point magnetic material of 500 ℃ to 800 ℃, the composition of these Curie point materials can be obtained by related documents.Such as, when the crucible or the paper tinsel that use pure iron to make make, its Curie-point temperature is 770 ℃; And when using iron nickel when being respectively the iron-nickel alloy of 30::70,40:60,49:51, its Curie-point temperature is respectively 610 ℃, 590 ℃, 510 ℃; In the time using the alloy that nickel-to-cobalt ratio is 40:60, its Curie-point temperature is 900 ℃.
In order to make sample have very fast heating rate, therefore, require crucible and metal forming wall thickness as far as possible little.The thickness that the crucible of sample or the wall of paper tinsel are housed is preferably between 0.05 millimeter to 1 millimeter.The size of crucible preferably meets following condition: in the time that 50 milligrams of testing samples are paved with in crucible bottom, now thickness of sample is preferably between 0.05 millimeter to 1 millimeter.Conventionally in this case, the size of crucible is between 0.5 centimetre to 1 centimetre at bottom internal diameter, and height is between 0.2 centimetre to 1 centimetre.The size of the crucible being more suitable for should be determined according to concrete testing sample character.
The instrument docking with the present invention refers to atomic spectrograph, and concrete is atomic fluorescence spectrophotometer, inductively coupled plasma atomic emission spectrum (ICP-AES), inductivity coupled plasma mass spectrometry (ICP-MS), electrothermal quartz tube Atomic absorption.
Curie point pyrolyzer of the present invention preferably will with one or several purification plant coupling, to remove the organism that produces in cracking and the interference of fine particle, the setting of purification plant and size should make chaff interference can be gone out or not disturb the mensuration of element to be measured completely.
Direct injection analysis when Curie point cracker of the present invention is applicable to atomic absorption spectrometry element, testing sample needn't through clearing up become liquid and directly measure.Apparatus of the present invention are compared with current existing tube furnace pyrolyzer technology, and sample intensification heating rate is able to great raising, and it is faster that therefore element goes out peak on instrument, and peak type is more sharp-pointed, makes measurement result more accurate.There is novelty and creativeness.
First preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction (load coil 1) heating, radio-frequency coil power 100W, frequency 600kHz, 3.5 centimetres of coil heights.In coil, insert 1 centimetre of an internal diameter, the quartz ampoule that length is 6 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.5-20 milligram rice meal sample is put into a monkey of being made up of pure iron (0.5 centimetre of internal diameter, high 1 centimetre, 0.2 millimeter of wall and bottom thickness of scale, in order to reduce the decomposition of metal pair element evaporation thing, the silicon dioxide gel of spraying one deck 0.01 millimeters thick in crucible), in order to prevent sample sputter, can on sample, add a cover the paper tinsel (face of contact sample also sprays the silicon dioxide gel of one deck 0.01 millimeters thick) that a pure iron is made.Then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating, and now iron crucible Curie-point temperature is 770 ℃.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser pipe device (condensing temperature-20 ℃) and a silica wool filtering layer purification of three level semiconductor refrigeration, the volatile matter of element arsenic, cadmium, lead, mercury is detected by atomic fluorescence, for further reducing and disturb, an optical filter can also be installed before atomic fluorescence detector.
Second preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 120W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 1.5 centimetres of internal diameters, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.6 milligrams of vegetable samples are put into one, and by iron-nickel alloy, (iron nickel compares 30:70,610 ℃ of Curie-point temperatures) monkey (0.5 centimetre of the internal diameter made, high 0.6 centimetre, 0.05 millimeter of wall and bottom thickness of scale, in order to reduce the decomposition of metal pair element evaporation thing, the polyethylene film of crucible lining one deck salic 50%, sample is placed in polythene film bag), then with pliers, sidewall of crucible folder in crucible top is left to small gap (being convenient to pyrolysis product volatilizes) to being close to both sides simultaneously, make sample better contact Curie point material.Crucible is put into quartz ampoule, open radio-frequency coil power supply and carry out induction heating.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser (condensing temperature-25 ℃) and a silica wool filtering layer purification of three level semiconductor refrigeration, arsenic, mercury, lead, cadmium and chromium element evaporation thing are detected by electrothermal quartz tube Atomic absorption.
The 3rd preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 80W, frequency 600kHz, 2 centimetres of coil heights.In coil, insert 1 centimetre of an internal diameter, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.2 milligrams of coating powder samples are put into above an iron-nickel alloy paper tinsel (Alloy Foil composition is: iron nickel is than 40:60,590 ℃ of Curie-point temperatures, and the length and width of paper tinsel and thickness are respectively 3 centimetres, 1.5 centimetres and 50 microns; In order to reduce the decomposition of metal pair element evaporation thing, the aluminum hydroxide sol that paper tinsel inside surface spraying a layer thickness is 0.02 millimeter), make sample be wrapped (referring to pyrolysis gas chromatograph part) by folding the paper tinsel that sample is housed, then the folding paper tinsel that is surrounded by sample is placed on sample carrier, puts into quartz ampoule.Open radio-frequency coil power supply and carry out induction heating.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after three level semiconductor refrigeration condensing units (condensing temperature-20 ℃) and a silica wool filtering layer purification, the element evaporation thing of cadmium, chromium is detected by ICP-MS.
The 4th preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 100W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 1.5 centimetres of internal diameters, the quartz ampoule that length is 12 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.5-20 milligram active gold-carrying carbon sample is put into one, and by ferro-cobalt, (ferro-cobalt compares 50:50,980 ℃ of Curie-point temperatures) monkey (0.3 centimetre of the internal diameter made, high 0.6 centimetre, 0.6 millimeter of wall and bottom thickness of scale), in order to reduce the decomposition of metal pair element evaporation thing, the silicon dioxide gel of spraying one deck 0.01 millimeters thick in crucible), in order to prevent sample sputter, can on sample, add a cover the paper tinsel (face of contact sample also sprays the silicon dioxide gel of one deck 0.01 millimeters thick) that a pure iron is made.Then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 250 ml/min) carry after the condenser (condensing temperature+2 ℃) and a silica wool filtering layer purification of three level semiconductor refrigerating plant condensations, the volatile matter of element gold is detected by inductively coupled plasma atomic emission spectrum ICP-AES.
The 5th preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 150W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 2 centimetres of internal diameters, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.10 milligrams of pedotheques are put into monkey (0.5 centimetre of an internal diameter of being made up of pure iron (770 ℃ of Curie-point temperatures), high 0.5 centimetre, 1 millimeter of wall and bottom thickness of scale, in order to reduce the decomposition of metal pair element evaporation thing, the silicon dioxide gel that inner surface of crucible spraying a layer thickness is 0.02 millimeter), then in pedotheque, add 0.1 milliliter of 50% sodium formate, 10% 0.1 milliliter of thiocarbamide, mixes.In order to prevent sample sputter, can on sample, add a cover the paper tinsel (inside surface also sprays the silicon dioxide gel of 0.02 millimeter of a layer thickness) that a pure iron makes and compress sample.Then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser (condensing temperature-30 ℃) and a silica wool filtering layer purification of three level semiconductor refrigerating plant condensations, arsenic element volatile matter is detected by atomic fluorescence spectrophotometer.
The 6th preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 150W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 2 centimetres of internal diameters, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in instructions Fig. 1 in detail.The thickness that a slice is made up of simple metal cobalt (or ferro-cobalt content be 50% alloy or nickel cobalt content be respectively 40% and 60% nickel cobalt (alloy)) is that the sheet metal of 1 millimeter is placed on above crucible tray, makes it the sample in silica crucible above indirect heating holder.0.5 centimetre of silica crucible internal diameter is high 1 centimetre.10 milligrams of soil (being mixed with in advance 10% sodium formate and 1 hydrochloric acid) or organic substrate sample are put into silica crucible the inside and tiled evenly, then above sample, compress another iron foil (silicon dioxide gel that iron foil inside surface spraying a layer thickness is 0.02 millimeter).Crucible is put on crucible tray, opened radio-frequency coil power supply and carry out induction heating.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser (condensing temperature+1 ℃) and a silica wool filtering layer purification of three level semiconductor refrigerating plant condensations, the volatile matter of element copper-lead zinc cadmium nickel is detected by ICP-MS.
The advantage that the Curie point pyrolyzer of Element generation volatile matter has compared with current existing pyrolysis in tubular furnace technology during for element determination disclosed by the invention is:
(1) current existing technology (CN103411892A) is used diamond heating, mainly by heat conduction, so the sample rate of heat addition is slow, conventionally while being raised to cracking, needed temperature is between 2-6 seconds, what therefore element evaporation thing formed is slow, duration is longer, and when mensuration, peak type is not sharp-pointed, and quantitative error is large.And the present invention uses induction heating, Curie point material heating rate fast (0.1 second-0.2 second), when element evaporation thing is measured, peak type is sharp-pointed, and quantitative error is little.
(2) current existing pyrolysis in tubular furnace technology, temperature control needs thermopair, and while therefore control, temperature fluctuation range is larger, is not easy accurate control, therefore measures precision bad.And the present invention to use Curie point material be by induction heating, in the time that temperature reaches Curie-point temperature, stop immediately heating, therefore cracking temperature can accurately be controlled, measuring accuracy is high.
(3) tubular furnace intensification cooling is slow, is unfavorable for that quick turn-on is measured and shutdown finishes mensuration, simultaneously relatively power consumption.And the present invention can overcome deficiency above.
Accompanying drawing explanation:
Fig. 1 is cracker schematic diagram of the present invention: wherein:
1. load coil; 2. quartz reaction bushing pipe; 3. reaction chamber; 4. reaction tube sealing-plug and sample carrier integrated apparatus; 5. carrier gas inlet; 6. carrier gas outlet; 7. sample crucible or paper tinsel; 8. the holder of sample crucible or paper tinsel carrying use; 9. the support of crucible or paper tinsel carrying use.
Embodiment:
Be below the detailed description of several most preferred embodiments, set forth the features and advantages of the present invention.Although the present invention only discloses by several forms, but be clear that for those of ordinary skills: to shape, the size of the part in the present invention with arrange relevant modification, increase and decrease and deletion, all belong to the core invention scope of setting forth in the claims in the present invention.Therefore, when attempt by this teach within the scope that other change under content recommendation or implementation method fall within these claims time, all belong to right category of the present invention.Wherein Curie point magnetic material is bought in magnetic metal material market.
embodiment 1:
A kind of Curie point pyrolyzer of Element generation volatile matter during for element determination, comprise load coil 1, quartz reaction bushing pipe 2, reaction chamber 3, reaction tube sealing-plug and sample carrier integrated apparatus 4, carrier gas inlet 5, carrier gas outlet 6, preferably 500 ℃-800 ℃ of sample crucible 7(), sample crucible is carried the holder 8 of use, the support 9 that crucible carries use, wherein support and the sealing-plug connecting link of crucible or paper tinsel carrying use; Sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 500 milliseconds.Element sample to be measured is directly loaded in Curie-point pyrolysis crucible.When element sample room tipping to be measured is loaded in Curie point crucible, surface spraying one deck high molecular polymer of crucible sample; The thickness of described sidewall of crucible is 0.08-1 millimeter.Wherein high molecular polymer refers to tygon, polypropylene fire high-molecular polyvinyl alcohol compound.
Aperture position first-selection when carrier gas enters bushing pipe and is output from bushing pipe is opened in the side at bushing pipe two ends, and sample inlet sealing-plug is silicone rubber seal plug.This Curie point pyrolyzer is used for the cracking of hydrogenous material, the element reaction to be measured in the hydrogen producing by cracking and sample, and generting element volatile matter is measured by atomic spectrograph.
A kind of Curie point pyrolyzer of Element generation volatile matter during for element determination, comprise load coil 1, quartz reaction bushing pipe 2, reaction chamber 3, reaction tube sealing-plug and sample carrier integrated apparatus 4, carrier gas inlet 5, carrier gas outlet 6, paper tinsel 7, the holder 8 of sample paper tinsel carrying use, the support 9 of paper tinsel carrying use.
Sample crucible of the present invention or paper tinsel are made up of at the Curie point material of 980 ℃ Curie-point temperature, and sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 300 milliseconds.
The Curie point pyrolyzer of Element generation volatile matter during for element determination of the present invention, wherein element sample to be measured is directly or indirectly loaded in Curie-point pyrolysis and wraps up in folding paper tinsel, is indirectly loaded in Curie point cracking crucible.Element sample room to be measured tipping is loaded in Curie point while wrapping up in folding paper tinsel, and the surface spraying of paper tinsel contact sample is the nonmetal oxide coating without decomposition to element evaporation thing; The thickness of described paper tinsel wall is 0.1 millimeter.Element evaporation thing is referred to silicon dioxide, titanium dioxide, alundum (Al2O3) or zirconia without the nonmetal oxide coating of decomposition.
The Curie point pyrolyzer of Element generation volatile matter during for element determination of the present invention, aperture position first-selection when wherein carrier gas enters bushing pipe and is output from bushing pipe is opened in the side at bushing pipe two ends, and sample inlet sealing-plug is silicone rubber seal plug.This Curie point pyrolyzer is used for the cracking of hydrogenous material, the element reaction to be measured in the hydrogen producing by cracking and sample, and generting element volatile matter is measured by atomic spectrograph.
trace arsenic in rice kernels content analysis
Use the device described in preferred embodiment one to carry out the mensuration of arsenic content in rice meal.Accurately take 4 milligrams of rice meal samples in iron crucible, then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating, and now iron crucible Curie-point temperature is 770 ℃.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser pipe device (condensing temperature-20 ℃) and a silica wool filtering layer purification of three level semiconductor refrigeration, the volatile matter of the element arsenic in rice meal is detected (atomic fluorescence atomizer is connected with the hydrogen generator of hydrogen generation growing amount 450 ml/min, to provide hydrogen source normally to catch fire for atomizer) by atomic fluorescence.According to the content of external standard method trace arsenic in rice kernels, use another rice standard specimen (GBW (E) 080684) to do external standard typical curve simultaneously, the content of measuring arsenic is 300ppb.And use normal nitric acid-perchloric acid method clear up after sample with the result that the Atomic fluorescence spectrometry that hydride occurs records arsenic in sample be 315ppb, visible this method has well identical with classic method.
embodiment 4:
analysis on amount of lead in vegetables
Use the device described in preferred embodiment two to carry out the mensuration of lead content in vegetables.Accurately take 10 milligrams of vegetable samples in iron-nickel alloy monkey, above sample, compress an iron foil (silicon dioxide gel that paper tinsel inside surface spraying a layer thickness is 0.02 millimeter), then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser pipe device (condensing temperature-20 ℃) and a silica wool filtering layer purification of three level semiconductor refrigeration, the volatile matter of the Element Lead in sample is detected (atomic fluorescence atomizer is connected with the hydrogen generator of hydrogen generation growing amount 450 ml/min, to provide hydrogen source normally to catch fire for atomizer) by atomic fluorescence.According to content plumbous in external standard method vegetables, use another vegetables standard specimen to do external standard typical curve simultaneously, measuring plumbous content is 160ppb.Be 170ppb and use normal nitric acid-perchloric acid method to clear up to record result plumbous in sample with electrothermal quartz tube atomic absorption spectrophotometer (AAS) after sample, visible this method has well identical with classic method.
embodiment 5:
cadmium and Chromium Content Analysis in coating powder
Use the device described in preferred embodiment three to carry out the mensuration of cadmium and chromium content in coating.Use standard addition method to carry out quantitatively, result is respectively 52ppb and 68ppb, and this measurement result is with digestion procedure measurement result is identical in advance, and visible this method and classic method have well coincide.
embodiment 6:
gold content analysis in acticarbon
In the acticarbon of 20 milligrams of ADSORPTION OF GOLD, add and adsorb the sodium formate solution of 0.2 milliliter 10%, then using the Curie point pyrolyzer in preferred embodiment four to carry out golden cracking experiment.The golden volatile matter that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser pipe device (2 ℃ of condensing temperatures) and a silica wool filtering layer purification of three level semiconductor refrigeration, in sample, the volatile matter of element gold is detected (atomic fluorescence atomizer is connected with the hydrogen generator of hydrogen generation growing amount 350 ml/min, to provide hydrogen source normally to catch fire for atomizer) by atomic fluorescence.According to the content of external standard method gold, measuring plumbous content is 10ppb.And use normal chloroazotic acid clear up after sample with the result that ICP-MS method records Gold Samples be 9.2ppb, visible this method has well identical with classic method.
embodiment 7:
the mensuration of arsenic in water
Use the device described in preferred embodiment one to carry out the mensuration of arsenic content in water.Accurately draw 0.1 ml water all in iron crucible (be lined with in advance a polyethylene film containing silicon dioxide 50% in iron crucible, water sample is placed in polythene film bag), then to adding 0.1 milliliter of 50% sodium formate, 10% 0.1 milliliter of thiocarbamide in water sample.Above sample, compress an iron foil (silicon dioxide gel that paper tinsel inside surface spraying a layer thickness is 0.02 millimeter), then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating, and now iron crucible Curie-point temperature is 770 ℃.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser pipe device (condensing temperature-20 ℃) of three level semiconductor refrigeration purifies, the volatile matter of the element arsenic in water is detected (atomic fluorescence atomizer is connected with the hydrogen generator of hydrogen generation growing amount 450 ml/min, to provide hydrogen source normally to catch fire for atomizer) by atomic fluorescence.According to the content of arsenic in external standard method water, the content of measuring arsenic is 70ppb.And the Atomic fluorescence spectrometry that uses normal sodium borohydride hydride sampling system to record the result of arsenic in sample be 72ppb, visible this method has well identical with classic method.
embodiment 8:
the mensuration of the zinc cadmium lead bronze nickel in soil
Use the device described in preferred embodiment six to carry out the mensuration of the content of ZINC IN SOIL cadmium lead bronze nickel.Use standard pedotheque carries out appearance standard measure, result demonstration, and above-mentioned five element determination results are identical with conventional Mixed Acids Digestion method measurement result, and visible this method and classic method have well coincide.
embodiment 9:
contrast test
Take preferred embodiment one as example, use respectively apparatus of the present invention (Curie point pyrolyzer) and the tube furnace pyrolyzer that patent (CN103411892A) proposes to measure same standard substance (rice, GBW (E) 080684) in arsenic content, experimental result is as following table:
Can find out from this contrast experiment, Curie point pyrolyzer of the present invention has better accuracy of measurement, measures precision and linear dependence than tube furnace pyrolyzer; It is more sharp-pointed that this cracker goes out peak, reaches cracking equilibrium temperature faster.There is very significantly advantage.
Claims (8)
1. the Curie point pyrolyzer of the volatile matter of Element generation during for element determination, it is characterized in that this cracker comprises load coil (1), quartz reaction bushing pipe (2), reaction chamber (3), reaction tube sealing-plug and sample carrier integrated apparatus (4), carrier gas inlet (5), carrier gas outlet (6), sample crucible or paper tinsel (7), the holder (8) of sample crucible or paper tinsel carrying use, the support (9) of crucible or paper tinsel carrying use, sample crucible or paper tinsel are subject to the magnetic fields of self-induction coil, produce eddy current and make crucible or the paper tinsel Curie-point temperature that is rapidly heated, at this temperature, element in sample and to release hydrogen reagent reaction generting element volatile matter determined, the wherein support (9) and sealing-plug connecting link of crucible or paper tinsel carrying use.
2. the Curie point pyrolyzer of Element generation volatile matter during for element determination according to claim 1, it is characterized in that sample crucible or paper tinsel (7) are made up of at the Curie point material of 450 ℃-980 ℃ Curie-point temperature, sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 1 second.
3. according to the Curie point pyrolyzer of Element generation volatile matter during for element determination claimed in claim 1, it is characterized in that sample crucible or paper tinsel (7) are made up of the Curie point material of 500 ℃-800 ℃ of Curie-point temperatures, sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 500 milliseconds.
4. the Curie point pyrolyzer of Element generation volatile matter during for element determination according to claim 1, it is characterized in that element sample to be measured is directly or indirectly loaded in Curie-point pyrolysis crucible or wraps up in folding paper tinsel, is loaded in Curie point cracking crucible indirectly.
5. the Curie point pyrolyzer of Element generation volatile matter during for element determination according to claim 3, it is characterized in that, when element sample room tipping to be measured is loaded in Curie point crucible or wraps up in folding paper tinsel, crucible or paper tinsel contact the surface spraying of sample or are lined with one deck high molecular polymer or the nonmetal oxide coating without decomposition to element evaporation thing; Wherein nonmetal oxide coating refers to silicon dioxide, titania, alundum (Al2O3) or zirconia.
6. the Curie point pyrolyzer of Element generation volatile matter during for element determination according to claim 1, is characterized in that described crucible or the thickness of paper tinsel wall are 0.05-1 millimeter.
7. the Curie point pyrolyzer of Element generation volatile matter during for element determination according to claim 1, it is characterized in that aperture position first-selection when carrier gas enters bushing pipe and is output from bushing pipe opens in the side at bushing pipe two ends, sample inlet sealing-plug is silicone rubber seal plug.
8. the Curie point pyrolyzer of Element generation volatile matter during for element determination according to claim 1, it is characterized in that the cracking of this Curie point pyrolyzer for hydrogenous material, element reaction to be measured in the hydrogen producing by cracking and sample, generting element volatile matter is measured by atomic spectrograph.
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