CN201945559U - Device for measuring ammonium nitrogen in fertilizer by cold air distillation method - Google Patents
Device for measuring ammonium nitrogen in fertilizer by cold air distillation method Download PDFInfo
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- CN201945559U CN201945559U CN201120048228XU CN201120048228U CN201945559U CN 201945559 U CN201945559 U CN 201945559U CN 201120048228X U CN201120048228X U CN 201120048228XU CN 201120048228 U CN201120048228 U CN 201120048228U CN 201945559 U CN201945559 U CN 201945559U
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Abstract
The utility model relates to a device for measuring ammonium nitrogen in fertilizer by a cold air distillation method. A gas scrubbing system, a distillation system and an absorption system are connected and compressed air is used for blowing, under a mild alkaline condition, ammonium salt in fertilizer reacts with weak base to generate ammonia, the generated ammonia is brought by the compressed air to boric acid absorption solution to be absorbed, and the absorbed ammonia in the absorption solution is measured to calculate out the content of the ammonium nitrogen in the fertilizer. By use of the device, the traditional method for measuring the content of the nitrogen species in the fertilizer is simplified, and selectivity of the measuring method is improved; the whole device has the advantages of being simple and convenient in mounting, easy in operation, safe and reliable, good in air tightness and the like. During the measuring, reagents applied are all non-toxic and harmless and meet the requirements of environmental protection. The device is capable of measuring and calculating the ammonium nitrogen in coexistence of a plurality of nitrogen species; therefore, the device is advantageous for further research and measurement on various nitrogen species in the fertilizer, and the requirement of measuring the content of the ammonium nitrogen in imported composite fertilizer can be further satisfied.
Description
Technical field
The utility model relates to the diagnostic test device of various form nitrogen contents in the fertilizer, particularly a kind of device that adopts the cold air way of distillation to measure ammonium nitrogen in the fertilizer.
Background technology
Ammonium nitrogen is mainly from ammonium salt in the fertilizer, as ammonium chloride, ammonium sulfate, ammonium bicarbonate, ammonium nitrate, monoammonium phosphate, Diammonium phosphate (DAP) etc., assay method about ammonium nitrogen in the act.std mainly comprises formaldehyde method, the way of distillation, Kjeldahl, wherein the formaldehyde method of GB/T3600-2000 " mensuration-formaldehyde method of ammoniacal nitrogen in the fertilizer " regulation only is applicable to and does not contain urea or derivatives thereof cyanogen aminate and nitrogen-containing organic compound in the sample, and the way of distillation, Kjeldahl only are applicable to and do not contain other form nitrogen in the fertilizer.Therefore existing standard only limits to the mensuration of nitrogen content in the single form nitrogen chemical fertilizer, if there is variform nitrogen in the fertilizer simultaneously, detects the result that the content of ammonium nitrogen wherein must make mistake possibly by existing standard and device.
When coexisting for variform nitrogen at present, need be according to the ammonium nitrogen content in the form comprehensive utilization several different methods indirect determination fertilizer that exists of ammonium nitrogen in the fertilizer, mainly be divided into following several situation: 1, when only having ammonium nitrogen in the fertilizer or only having ammonium nitrogen and nitrate nitrogen, can measure ammonium nitrogen content by Kjeldahl method.2, when having ammonium nitrogen and amidonitrogen in the fertilizer, the method that adopts first sulfuric acid to digest highly basic thermal distillation is again measured total nitrogen content, adopts urease methods to measure amidonitrogen, and both differences are ammonium nitrogen content.3, when having ammonium nitrogen, amidonitrogen and nitrate nitrogen in the fertilizer, adopt the method for metallic reducing, sulfuric acid digestion, highly basic thermal distillation to measure total nitrogen content, adopt the spectrophotometry nitrate nitrogen content, adopt urease methods to measure amidonitrogen content, total nitrogen content deducts nitrate nitrogen content and amidonitrogen content is ammonium nitrogen content.
Existing method is measured the flow process more complicated, has significant limitation in the application, when there is form in nitrogen in unknown fertilizer measurement result is had very big influence.Urease price comparison costliness, the pot-life of using in the acid amides attitude content assaying method in addition, are shorter.Therefore, coexist, when especially ammonium nitrogen and amidonitrogen coexist, also do not have a kind of device that can directly measure ammonium nitrogen in the fertilizer at present for variform nitrogen in the fertilizer.
Summary of the invention
In view of the deficiency that prior art exists, in order to solve the problem that can't directly measure ammonium nitrogen content when various form nitrogen exist simultaneously, the utility model designs a kind of device that adopts the cold air way of distillation to measure ammonium nitrogen in the fertilizer.This device can make ammonium nitrogen and other form nitrogen realize separating in still-process, can directly measure the content of ammonium nitrogen in the fertilizer, and the assay method in conjunction with other form nitrogen reaches the purpose of measuring each form nitrogen in the fertilizer again.By this device can be when variform nitrogen coexists directly to fertilizer in ammonium nitrogen measure and calculate, on the basis that guarantees accuracy of measurement and precision, reduced cost, help the further research and the mensuration of various form nitrogen in the fertilizer, and then satisfy the needs of ammonium nitrogen assay in the import composite fertilizer.
The technical scheme that the utility model is taked for achieving the above object is: a kind of device that adopts the cold air way of distillation to measure ammonium nitrogen in the fertilizer, it is characterized in that: comprise glass rotameter, also comprise the gas washing system, Distallation systm and absorption system, described gas washing system comprises two Drexel bottles at least, be respectively first Drexel bottle and second Drexel bottle, described Distallation systm comprises two cucurbits at least, be respectively first cucurbit, the after-fractionating bottle, described absorption system comprises two groups at least, every group of three absorption bottles, totally six absorption bottles, first group is respectively first absorption bottle, second absorption bottle, the 3rd absorption bottle, second group is respectively the 4th absorption bottle, the 5th absorption bottle, the 6th absorption bottle, two Drexel bottles of gas washing system, the bottleneck of two cucurbits of Distallation systm and six absorption bottles of absorption system fixedly has the frosted mouth bottle stopper of draft tube and escape pipe respectively, draft tube and escape pipe one end stretch out outside the frosted mouth bottle stopper, the other end puts in the bottle, wherein, draft tube in first Drexel bottle is connected with the gas outlet of glass rotameter by connecting pipe, escape pipe in first Drexel bottle is connected with draft tube in second Drexel bottle by connecting pipe, escape pipe in second Drexel bottle is connected with three-way pipe by connecting pipe, three-way pipe by connecting pipe respectively with first cucurbit, draft tube on the after-fractionating bottle connects, first cucurbit, escape pipe on the after-fractionating bottle connects first absorption bottle in two groups of absorption bottles of absorption system respectively by connecting pipe, draft tube on the 4th absorption bottle, first absorption bottle, escape pipe on the 4th absorption bottle is respectively by the connecting pipe and second absorption bottle, draft tube on the 5th absorption bottle connects, second absorption bottle, escape pipe on the 5th absorption bottle is respectively by connecting pipe and the 3rd absorption bottle, draft tube on the 6th absorption bottle connects.
The beneficial effect that the utility model produced is: adopt this device, make the ammonium nitrogen in the fertilizer in still-process, realize separating with other form nitrogen, simplified the assay method of form nitrogen content in the fertilizer, increased the selectivity that adopts assay method, package unit has simple installation, easy operating, safe and reliable, characteristics such as impermeability is good.Agents useful for same is all nontoxic in the mensuration, compliance with environmental protection requirements.The recovery that adopts this device to measure ammonium nitrogen content is 99.39%~100.13%; In conjunction with the conventional determining method of other form nitrogen, the recovery of measuring ammonium nitrogen, nitrate nitrogen, three kinds of form nitrogen of amidonitrogen and total nitrogen content is 99.75%~102.08%.Thereby the assay method in conjunction with other form nitrogen has reached the purpose of measuring each form nitrogen in the fertilizer.
Description of drawings
Fig. 1 is the invention structural representation.
Fig. 2 is the Drexel bottle structural representation.
Fig. 3 is the cucurbit structural representation.
Fig. 4 is the absorption bottle structural representation.
Embodiment
The utility model is described in further detail below in conjunction with drawings and Examples.As Fig. 1,2,3, shown in 4, the device that adopts the cold air way of distillation to measure ammonium nitrogen in the fertilizer comprises that glass rotameter 1(model is LZB) and the gas washing system, Distallation systm, absorption system, the gas washing system comprises two Drexel bottles at least, be respectively the first Drexel bottle 2-1 and the second Drexel bottle 2-2, Distallation systm comprises two cucurbits at least, be respectively the first cucurbit 3-1, after-fractionating bottle 3-2, absorption system comprises two groups at least, every group of three absorption bottles, totally six absorption bottles, first group is respectively the first absorption bottle 4-1, the second absorption bottle 4-2, the 3rd absorption bottle 4-3, second group is respectively the 4th absorption bottle 4-4, the 5th absorption bottle 4-5, the 6th absorption bottle 4-6, two Drexel bottles of gas washing system, the bottleneck of two cucurbits of Distallation systm and six absorption bottles of absorption system spiral-lock respectively fixedly has the frosted mouth bottle stopper 5 of draft tube and escape pipe, draft tube and escape pipe one end stretch out outside the frosted mouth bottle stopper 5, the other end puts in the bottle, wherein, draft tube on the first Drexel bottle 2-1 is connected with the gas outlet of glass rotameter 1 by connecting pipe 6, the air intake opening of glass rotameter 1 connects pressurized air, escape pipe on the first Drexel bottle 2-1 is connected with draft tube on the second Drexel bottle 2-2 by connecting pipe 6, escape pipe on the second Drexel bottle 2-2 is connected with three-way pipe 7 by connecting pipe 6, three-way pipe 7 by connecting pipe 6 respectively with the first cucurbit 3-1, draft tube on the after-fractionating bottle 3-2 connects, the first cucurbit 3-1, escape pipe on the after-fractionating bottle 3-2 connects the first absorption bottle 4-1 in two groups of absorption bottles of absorption system respectively by connecting pipe 6, draft tube on the 4th absorption bottle 4-4, the first absorption bottle 4-1, escape pipe on the 4th absorption bottle 4-4 is respectively by the connecting pipe 6 and the second absorption bottle 4-2, draft tube on the 5th absorption bottle 4-5 connects, the second absorption bottle 4-2, escape pipe on the 5th absorption bottle 4-5 is respectively by connecting pipe 6 and the 3rd absorption bottle 4-3, draft tube on the 6th absorption bottle 4-6 connects.In the bottle gas discharge by the escape pipe mouth of pipe of the 3rd absorption bottle 4-3, the 6th absorption bottle 4-6.
Upper end one side of two cucurbits of Distallation systm is provided with funnel 3-3, and funnel 3-3 and cucurbit are processed as one, and funnel 3-3 is provided with flow rate regulation cock 3-4.Connecting pipe 6 adopts the silicone tube of diameter 8mm, and three-way pipe 7 is a glass tube.
The bottleneck side of two cucurbits of two Drexel bottles of gas washing system, Distallation systm and six absorption bottles of absorption system is arranged with two protruding 234-1, frosted mouth bottle stopper 5 sides also be provided with two symmetries and with two corresponding protruding 5-1 of protruding 234-1, and with two protruding 5-1 colligations of two protruding 234-1 of bottleneck side and frosted mouth bottle stopper 5 sides together by the rubber muscle.
On the escape pipe of two Drexel bottles of gas washing system, on the escape pipe of two cucurbits of Distallation systm, all have globe joint 234-2 on the draft tube of six absorption bottles of absorption system and the escape pipe, globe joint 234-2 and tracheae are processed as one.The bottom of the escape pipe of two Drexel bottles of gas washing system, two cucurbits of Distallation systm all is made as crotch-shaped 23-1.The design of globe joint 234-2 and crotch-shaped 23-1 is in order to prevent that the liquid foam that air-flow will splash from bringing tracheae into.
The lower end of the draft tube of two cucurbits of two Drexel bottles of gas washing system, Distallation systm and six absorption bottles of absorption system connects spray type showerhead 234-3 by connecting pipe 6 respectively.This design be make in the bottle gas fully contact with liquid, to improve reaction efficiency.Spray type showerhead 10 is provided with pore and is about 30, and the aperture is 1mm.
Principle of work of the present utility model: purge by pressurized air, under weak basic condition, ammonium salt in the fertilizer and weak base reaction generate ammonia, and the ammonia of generation is compressed air and brings to the absorption of boric acid absorption liquid, by measuring the content that the ammonia that absorbs in the absorption liquid calculates ammonium nitrogen in the fertilizer.
Embodiment: measure ammonium nitrogen content in the composite fertilizer: preparation sulfuric acid solution, sodium hydroxide solution, solution of potassium carbonate, bromcresol green indicator, methyl red indicator, hydrochloric acid standard titration solution [c (HCl)=0.5 mol/L], hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L] and boric acid absorption liquid are standby earlier.
(1), sulfuric acid solution: the volume ratio according to sulfuric acid and deionized water is that 1:20 prepares sulfuric acid solution, and volume unit is mL;
(2), sodium hydroxide solution: the w/v according to NaOH and deionized water is that 30:1000 prepares sodium hydroxide solution, and unit of weight is g, and volume unit is mL; (3), solution of potassium carbonate: the w/v according to sal tartari and deionized water is that 55:100 prepares solution of potassium carbonate, and unit of weight is g, and volume unit is mL; (4), bromcresol green indicator: the w/v according to bromcresol green and ethanol is that 1:100 prepares the bromcresol green indicator, and unit of weight is g, and volume unit is mL; (5), methyl red indicator: the w/v according to methyl red and ethanol is that 1:100 prepares methyl red indicator, and unit of weight is g, and volume unit is mL; (6), hydrochloric acid standard titration solution [c (HCl)=0.5 mol/L]: by standard GB/T 601 preparations and demarcation concentration is the hydrochloric acid standard titration solution of [c (HCl)=0.5 mol/L]; (7), hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L]: pipette the hydrochloric acid standard titration solution of 100 mL concentration for [c (HCl)=0.5 mol/L], be settled to the hydrochloric acid standard titration solution of 1000 mL concentration with no carbon dioxide distilled water for [c (HCl)=0.05 mol/L], calculate the actual concentrations of hydrochloric acid standard titration solution then, be designated as C
1, concentration unit is mol/L, actual concentrations C
1Be 0.0559mol/L.(8), boric acid absorption liquid: the w/v according to boric acid and deionized water is that 10:1000 prepares BAS earlier, unit of weight is, volume unit is mL, the 100 mL bromcresol green indicator and the 70 mL methyl red indicators that add preparation then, drip the sodium hydroxide solution of preparation, make BAS obvious celadon occur; Before the use, use hydrochloric acid standard titration solution [c (HCl)=0.5 mol/L] titration again to kermesinus.
Connect the ammonium nitrogen determinator according to Fig. 1,200 mL sulfuric acid solutions will be added among the first Drexel bottle 2-1, will be among the second Drexel bottle 2-2 add 200 mL sodium hydroxide solutions, add the boric acid absorption liquid that 50 mL prepare respectively among totally six absorption bottle 4-1~4-6 two groups of absorption system.
Take by weighing a certain amount of testing sample, sample quality is designated as m, and m is 0.2005g, places a cucurbit 3-1 to do sample determination the testing sample that takes by weighing, and second cucurbit 3-2 do not add sample and do blank determination; To cucurbit, add the 60 ml solution of potassium carbonate that prepare respectively from the funnel 3-3 of two cucurbits; With low amounts of water washing bottle wall, the complete soln volume is advisable to be no more than 110 mL; Open pressurized air, the control compressed air require is 3L/min, distillation 8h.
After the 8h distillation finishes, the closes compression air, every absorption bottle with hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L] difference titration absorption system, make boric acid absorption liquid in every absorption bottle to kermesinus, and write down the volume that every absorption bottle consumes hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L], be designated as V
1To V
6V wherein
1Be 15.55mL, V
2Be 0.05 mL, V
3Be 0.00 mL, V
4Be 0.07 mL, V
5Be 0.03 mL, V
6Be 0.00 mL.
Absorption system after the titration is connected with Distallation systm, open pressurized air, the control compressed air require is 3L/min, continue distillation 1h, after 1h distillation finished, with hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L] every absorption bottle of titration absorption system respectively, the boric acid absorption liquid in this moment every absorption bottle was to kermesinus, the hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L] that every absorption bottle titration is consumed does not surpass 0.03 mL, and distillation finishes.Illustrate that ammonium nitrogen content is not more than 25mg in this composite fertilizer's testing sample.If the ammonium nitrogen content in the working sample then needs to reduce sample weighting amount greater than 25mg, continue the operation of repeating step (two) to step (eight).
Three absorption bottles that totally are used for sample determination consume the volume of hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L], with V
1To V
3Cumulative volume consume the cumulative volume of hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L] as sample determination, be designated as V, V is 15.60mL; Three absorption bottles that totally are used for blank determination consume the volume of hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L], with V
4To V
6Cumulative volume consume the cumulative volume of hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L] as blank determination, be designated as V
0, V
0Be 0.10 mL.
V, V with above accumulative total or record
0, C
1, m data substitution formula:
, calculate at last that the ammonium nitrogen percentage composition is 6.05 % (the gained result keeps two-decimal) in the testing sample.
In the formula: ammonium nitrogen content (%) in X-testing sample;
V-sample determination consumes the cumulative volume of hydrochloric acid standard titration solution, Unit;
V
0-blank determination consumes the cumulative volume of hydrochloric acid standard titration solution, Unit;
C
1The actual concentrations of-hydrochloric acid standard titration solution [c (HCl)=0.05 mol/L], the mol/L of unit;
0.014 the quality of 01-suitable with 1.00 mL hydrochloric acid standard titration solutions [c (HCl)=1.000 mol/L] nitrogen with the gram expression;
The quality of m-testing sample, the g of unit.
Abovely measure according to the utility model that ammonium nitrogen content is 6.05% in this composite fertilizer, ammonium nitrogen content is 6.02% in this composite fertilizer's testing sample that records according to the complicated assay method (the third method) of tradition, this shows that two kinds of methods record basically identical as a result.Therefore, adopt this device can substitute the method for ammonium nitrogen in the complicated mensuration fertilizer of tradition fully.
Claims (6)
1. device that adopts the cold air way of distillation to measure ammonium nitrogen in the fertilizer, it is characterized in that: comprise glass rotameter (1), also comprise the gas washing system, Distallation systm and absorption system, described gas washing system comprises two Drexel bottles at least, be respectively first Drexel bottle (2-1) and second Drexel bottle (2-2), described Distallation systm comprises two cucurbits at least, be respectively first cucurbit (3-1), after-fractionating bottle (3-2), described absorption system comprises two groups at least, every group of three absorption bottles, totally six absorption bottles, first group is respectively first absorption bottle (4-1), second absorption bottle (4-2), the 3rd absorption bottle (4-3), second group is respectively the 4th absorption bottle (4-4), the 5th absorption bottle (4-5), the 6th absorption bottle (4-6), two Drexel bottles of gas washing system, the bottleneck of two cucurbits of Distallation systm and six absorption bottles of absorption system fixedly has the frosted mouth bottle stopper (5) of draft tube and escape pipe respectively, draft tube and escape pipe one end stretch out outside the frosted mouth bottle stopper (5), the other end puts in the bottle, wherein, draft tube in first Drexel bottle (2-1) is connected with the gas outlet of glass rotameter (1) by connecting pipe (6), escape pipe in first Drexel bottle (2-1) is connected with draft tube in second Drexel bottle (2-2) by connecting pipe (6), escape pipe in second Drexel bottle (2-2) is connected with three-way pipe (7) by connecting pipe (6), three-way pipe (7) by connecting pipe (6) respectively with first cucurbit (3-1), draft tube on the after-fractionating bottle (3-2) connects, first cucurbit (3-1), escape pipe on the after-fractionating bottle (3-2) connects first absorption bottle (4-1) in two groups of absorption bottles of absorption system respectively by connecting pipe (6), draft tube on the 4th absorption bottle (4-4), first absorption bottle (4-1), escape pipe on the 4th absorption bottle (4-4) is respectively by connecting pipe (6) and second absorption bottle (4-2), draft tube on the 5th absorption bottle (4-5) connects, second absorption bottle (4-2), escape pipe on the 5th absorption bottle (4-5) is respectively by connecting pipe (6) and the 3rd absorption bottle (4-3), draft tube on the 6th absorption bottle (4-6) connects.
2. the employing cold air way of distillation according to claim 1 is measured the device of ammonium nitrogen in the fertilizer, it is characterized in that: upper end one side of two cucurbits of described Distallation systm is provided with funnel (3-3), and funnel (3-3) is provided with flow rate regulation cock (3-4).
3. the employing cold air way of distillation according to claim 1 is measured the device of ammonium nitrogen in the fertilizer, it is characterized in that: the bottleneck side of two cucurbits of two Drexel bottles of described gas washing system, Distallation systm and six absorption bottles of absorption system is arranged with two projectioies (234-1), described frosted mouth bottle stopper (5) side also be provided with two symmetries and with the corresponding projectioies of two projectioies (234-1) (5-1).
4. the employing cold air way of distillation according to claim 1 is measured the device of ammonium nitrogen in the fertilizer, it is characterized in that: on the escape pipe of two Drexel bottles of gas washing system, on the escape pipe of two cucurbits of Distallation systm, all have globe joint (234-2) on the draft tube of six absorption bottles of absorption system and the escape pipe.
5. the employing cold air way of distillation according to claim 1 is measured the device of ammonium nitrogen in the fertilizer, it is characterized in that: the bottom of the escape pipe of two Drexel bottles of described gas washing system, two cucurbits of Distallation systm is crotch-shaped (23-1).
6. the employing cold air way of distillation according to claim 1 is measured the device of ammonium nitrogen in the fertilizer, it is characterized in that: the lower end of the draft tube of two cucurbits of two Drexel bottles of described gas washing system, Distallation systm and six absorption bottles of absorption system connects spray type showerhead (234-3) by connecting pipe (6) respectively.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102095729A (en) * | 2011-02-25 | 2011-06-15 | 天津出入境检验检疫局化矿金属材料检测中心 | Device for detecting ammonium nitrogen in fertilizer with cold air distillation method and method thereof |
CN102590205A (en) * | 2012-02-17 | 2012-07-18 | 贵州兴化化工股份有限公司 | Method and device for determining acetic acid content in acetate cuprammonia |
CN103217394A (en) * | 2013-04-10 | 2013-07-24 | 中国科学院合肥物质科学研究院 | Online detection device of water dissolved-out nitrogen nutrients of chemical fertilizer |
CN111579318A (en) * | 2020-06-09 | 2020-08-25 | 苏州方元智能环保科技有限公司 | Sampling device and sampling method applied to determination of ammonium nitrogen isotope |
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2011
- 2011-02-25 CN CN201120048228XU patent/CN201945559U/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102095729A (en) * | 2011-02-25 | 2011-06-15 | 天津出入境检验检疫局化矿金属材料检测中心 | Device for detecting ammonium nitrogen in fertilizer with cold air distillation method and method thereof |
CN102095729B (en) * | 2011-02-25 | 2012-08-08 | 天津出入境检验检疫局化矿金属材料检测中心 | Device for detecting ammonium nitrogen in fertilizer with cold air distillation method and method thereof |
CN102590205A (en) * | 2012-02-17 | 2012-07-18 | 贵州兴化化工股份有限公司 | Method and device for determining acetic acid content in acetate cuprammonia |
CN103217394A (en) * | 2013-04-10 | 2013-07-24 | 中国科学院合肥物质科学研究院 | Online detection device of water dissolved-out nitrogen nutrients of chemical fertilizer |
CN103217394B (en) * | 2013-04-10 | 2014-11-26 | 中国科学院合肥物质科学研究院 | Online detection device of water dissolved-out nitrogen nutrients of chemical fertilizer |
CN111579318A (en) * | 2020-06-09 | 2020-08-25 | 苏州方元智能环保科技有限公司 | Sampling device and sampling method applied to determination of ammonium nitrogen isotope |
CN111579318B (en) * | 2020-06-09 | 2022-12-23 | 苏州方元智能环保科技有限公司 | Sampling device and sampling method applied to determination of ammonium nitrogen isotope |
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