CN102375068B - Full-automatic nutrient salt analyzer and analysis method thereof - Google Patents

Full-automatic nutrient salt analyzer and analysis method thereof Download PDF

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CN102375068B
CN102375068B CN 201010258430 CN201010258430A CN102375068B CN 102375068 B CN102375068 B CN 102375068B CN 201010258430 CN201010258430 CN 201010258430 CN 201010258430 A CN201010258430 A CN 201010258430A CN 102375068 B CN102375068 B CN 102375068B
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peristaltic pump
threeway
solution
knitting reactor
pump tube
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CN102375068A (en
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赵萍
魏月仙
成耀祖
肖靖泽
顾爱平
赵立晶
常凤翥
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BEIJING JITIAN INSTRUMENT Co Ltd
Beijing Titan Instruments Co Ltd
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BEIJING JITIAN INSTRUMENT Co Ltd
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Abstract

The invention relates to a full-automatic multi-parameter nutrient salt analysis method and an apparatus for implementing the method. The apparatus adopts artificial sea water as carrying current to eliminate the matrix effect in a sea water sample due to the high salinity change, wherein the prepared NaCl concentration of the artificial sea water is the same as the NaCl concentration of the sea water; five nutritional ingredients of nitrate nitrogen NO3<->, nitrite nitrogen NO2<->, ammonia nitrogen NH4<+>, phosphate PO4<3-> and silicate SiO4<2-> can be synchronously analyzed; a unique flow path design is adopted, such that the problem of the mutual interference between the silicate and the phosphate during the determination can be avoided.

Description

Full-automatic nutritive salt is analyzed instrument and analytical approach
Technical field
The present invention relates to a kind of full-automatic nutritive salt and analyze the detection technique of instrument and analytical approach, especially can Fast Measurement sample in enormous quantities, can carry out simultaneously five parametric measurements, relate generally to a kind of automatic analyzer and analytical approach thereof of nutritive salt.
Background technology
Seawater Phosphate (PO 4 3-), silicate (SiO 4 2-) and inorganic nitrogen, comprise nitrate nitrogen (NO 3 -), nitrite nitrogen (NO 2 -), ammonia nitrogen (NH 4 +) can promote the growth of phytoplankton, but excessive concentration can cause seawater to present eutrophication, thus cause serious environmental problem---red tide.The eutrophication of seawater can consume dissolved oxygen of seawater, causes the animals and plants in the seawater to die owing to oxygen is exhausted, and ecologic environment has been caused destruction.To the detection of nutrients in sea water, it is the important component part of marine environmental monitoring.
At present, the analysis of nutritive salt all is to adopt ship to cruise for annual 2-6 time in China's Marine Pollution Survey and monitoring in the seawater, mainly still relies on spot sampling, gets seawater sample and aboard ship stores, and ashore chemical analysis and measurement are carried out in the laboratory.This method has two shortcomings: the one, and cruising is generally every year several times, and interval time is longer; Behind Sample storage, the use spectrophotometric method of regulation is measured the nutritive salt in the seawater in laboratory using " the 4th part of marine monitoring standard GB 17378.4-2007: sea water analysis ", owing to be not on-the site analysis, all the unreliability that unpredictable factor causes measurement result can appear in Sample storage and later stage mensuration.And along with the increasing of country to the environment monitoring dynamics, the sample size of collection in worksite is large, sampling number is frequent, every day a hundreds of sample the mensuration of a plurality of indexs, the analyst in the laboratory be can't bear the heavy load.And nitrate nitrogen (NO 3 -) mensuration need to use poisonous cadmium post, be a potential threat to experimenter's health.Along with the development of society, the exploitation of full automatic nutritive salt analysis technology and on-spot measuring instrument more and more is subject to the extensive attention in the world.
There is in the market the instrument based on Continuous Flow Analysis of import on sale, bubble interval Continuous Flow Analysis, know-why reaches the limitation of measuring after the balance based on physical mixed and chemical reaction, and the efficient of instrument is lower; Use room air as bubble sample and reagent to be carried out the interval, with reach between sample and the reagent even mixing and to the interval between the different samples, therefore this instrument is had relatively high expectations to laboratory environment, instrument based on bubble interval continuous flow principle design, bubble need to be stablized to the size of bubble and evenly can measure after round and smooth on the border, system stability time length (＞2h), be not suitable for on-site measurement.Import instrument is expensive, and use cost is high.
Flow Injection Analysis is under the nonequilibrium condition of thermodynamics, and the sample of certain volume is injected in the current-carrying solution without the continuous flow at bubble interval, guarantees mixed process and the height reappearance in reaction time.Patent CN 2404124 and patent CN 1120987 disturb for fear of the matrix that the high salinity in the seawater causes, and have used the Continuous Flow Analysis technology without the bubble interval, are not the flowing injecting analysis technology of real meaning.Among the patent CN 1176381C, loaded down with trivial details and a large amount of reagent demand of processing in order to improve data, used reagent has been injected into " reverse flow injection analysis technology " in the sample, but measure when the described instrument of this patent can not carry out multiparameter, and do not address the solution of problem way that interferes with each other for the mensuration of silicate and silicate and phosphate determination.Its license date is in 2004, and new national standard GB 17378.4-2007 is issuing and implementation in 2007, do not address the demand whether test index reaches new country in the patent.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of nitrate nitrogen (NO that realizes is provided 3 -), nitrite nitrogen (NO 2 -), ammonia nitrogen (NH 4 +), phosphate (PO 4 3-), silicate (SiO 4 2-) analyze when five kinds of nutritional labelings; The instrument that can avoid measuring the Full automatic multiple parameter nutritive salt autoanalyzer method of the problem that interferes with each other between silicate and the phosphate and implement the method.For realizing goal of the invention, the present invention has adopted following technical scheme:
Full-automatic nutritive salt is analyzed instrument, comprise constant temperature automatic sampler, main frame, main frame comprises peristaltic pump, by the sample fillup valve group that at least 4 sample fillup valves form, chemical analysis template, 4 temperature control equipments, detector set, peristaltic pump comprise 19 peristaltic pump tubes at least, and detector set forms by being at least 4 roads detecting device in parallel and computer control system, the chemical analysis template is divided into four zones, is respectively nitrate nitrogen (NO 3 -) and nitrite nitrogen (NO 2 -) analysis area, ammonia nitrogen (NH 4 +) analysis area, phosphate (PO 4 3-) analysis area, silicate (SiO 4 2-) the analysis area composition, the constant temperature automatic sampler links to each other with peristaltic pump tube by the capillary connecting pipe, peristaltic pump tube links to each other by the capillary connecting pipe successively with flow cell in chemical analysis template, the detecting device, detecting device is connected with computer control system by signal wire, the airborne temperature of the first temperature control equipment main control system, the second temperature control equipment control ammonia nitrogen (NH 4 +) temperature of heating module in the analysis area, the 3rd temperature control equipment control phosphate (PO 4 3-) temperature of heating module in the analysis area, the 4th temperature control equipment control silicate (SiO 4 2-) temperature of heating module in the analysis area.
Full-automatic nutritive salt is analyzed instrument, wherein, and nitrate nitrogen (NO 3 -), nitrite nitrogen (NO 2 -) analysis area comprises two knitting reactor, two threeways, capillary connecting pipe, container bottle, four-way valve, four-way valve has A ', B ', four interfaces of C ', D ', the first sample fillup valve has A1, B1, C1, D1, six interfaces of E1, F1 at least, and interface F1 links to each other with the capillary connecting pipe with the first sample introduction needle of peristaltic pump the first peristaltic pump tube, constant temperature automatic sampler successively; Interface B1 links to each other with the first sampling ring two ends respectively with E1; Interface D1 links to each other with the capillary connecting pipe with the second peristaltic pump tube, the first current-carrying container bottle successively; Interface C1 successively with the first threeway the first entrance, the first threeway outlet, the first knitting reactor, four-way valve D ' interface, four-way valve C ' interface, the second threeway the first entrance, the second threeway outlet, the second knitting reactor, flow cell is communicated with the capillary connecting pipe, the A ' of four-way valve, B ' interface is connected to the two ends of cadmium reduction column with the capillary connecting pipe, the second entrance of the first threeway and the 3rd peristaltic pump tube, the first reagent container bottle that chloride buffer solution is housed links to each other with the capillary connecting pipe, the second entrance of the second threeway and the 4th peristaltic pump tube, the second reagent container bottle that the sulfanilamide (SN) chromogenic reagent solution is housed links to each other by the capillary connecting pipe, the interface A1 of the first sample fillup valve is communicated with waste liquid tank through the first back pressure regulator with the capillary connecting pipe, be provided with the first flow cell in the first detecting device, the first flow cell links to each other with waste liquid tank through the second back pressure regulator with the capillary connecting pipe, and the first detecting device is connected with computer control system by the first signal line.
Full-automatic nutritive salt is analyzed instrument, wherein, and ammonia nitrogen (NH 4 +) analysis area comprises four knitting reactor, four threeways, capillary connecting pipe, container bottle, the second sample fillup valve has A2, B2, C2, D2, six interfaces of E2, F2 at least, and interface F2 links to each other with the capillary connecting pipe with the second sample introduction needle of peristaltic pump the 5th peristaltic pump tube, constant temperature automatic sampler; Interface B2 links to each other with the second sampling ring two ends respectively with E2; Interface D2 links to each other with the capillary connecting pipe with the 6th peristaltic pump tube, the second current-carrying container bottle successively; Interface C2 successively with the 3rd threeway the first entrance, the 3rd threeway outlet, the 3rd knitting reactor, the 4th threeway the first entrance, the 4th threeway outlet, the 4th knitting reactor, the 5th threeway the first entrance, the 5th threeway outlet, the 5th knitting reactor, the 6th threeway the first entrance, the 6th threeway outlet, the 6th knitting reactor, flow cell is communicated with the capillary connecting pipe, the 6th knitting reactor is wrapped on the heating module, the second entrance of the 3rd threeway and the 7th peristaltic pump tube, the buffer solution container bottle is housed to link to each other with the capillary connecting pipe, the second entrance of the 4th threeway and the 8th peristaltic pump tube, salicylate solution container bottle is housed to link to each other by the capillary connecting pipe, the second entrance of the 5th threeway and the 9th peristaltic pump tube, the sodium nitroprusside solution container bottle is housed to link to each other by the capillary connecting pipe, the second entrance of the 6th threeway and the tenth peristaltic pump tube, the container bottle that sodium dichloroisocyanate solution is housed links to each other by the capillary connecting pipe, the interface A2 of the second sample fillup valve is communicated with waste liquid tank through the 3rd back pressure regulator by the capillary connecting pipe, be provided with the second flow cell in the second detecting device, the second flow cell links to each other with waste liquid tank through the 4th back pressure regulator, and the second detecting device is connected with computer control system by the secondary signal line.
Full-automatic nutritive salt is analyzed instrument, wherein, and phosphate (PO 4 3-) analysis area comprises three knitting reactor, two threeways, capillary connecting pipe, container bottle, the 3rd sample fillup valve has A3, B3, C3, D3, six interfaces of E3, F3 at least, and interface F3 links to each other with the usefulness capillary connecting pipes such as the 3rd sample introduction needle of the 11 peristaltic pump tube, constant temperature automatic sampler; Interface B3 links to each other with the 3rd sampling ring two ends respectively with E3; Interface D3 links to each other with the capillary connecting pipe with the 12 peristaltic pump tube, the 3rd current-carrying container bottle successively; Interface C3 successively with the 7th knitting reactor, the 7th threeway the first entrance, the 7th threeway outlet, the 8th knitting reactor, the 8th threeway the first entrance, the 8th threeway outlet, the 9th knitting reactor, the 3rd flow cell is communicated with the capillary connecting pipe, the 9th knitting reactor is wrapped on the heating module, the second entrance and the 13 peristaltic pump tube of the 7th threeway, the container bottle that the first ascorbic acid solution is housed links to each other with the capillary connecting pipe, the second entrance and the 14 peristaltic pump tube of the 8th threeway, the container bottle that the first ammonium molybdate solution is housed links to each other by the capillary connecting pipe, the interface A3 of the 3rd sample fillup valve is communicated with waste liquid tank through the 5th back pressure regulator by the capillary connecting pipe, be provided with the 3rd flow cell in the 3rd detecting device, the 3rd flow cell links to each other with waste liquid tank through the 6th back pressure regulator, and the 3rd detecting device is connected with computer control system by the 3rd signal wire.
Full-automatic nutritive salt is analyzed instrument, wherein, and silicate (SiO 4 2-) analysis area comprises four knitting reactor, three threeways, capillary connecting pipe, container bottle, the 4th sample fillup valve has A4, B4, C4, D4, six interfaces of E4, F4 at least, and interface F4 links to each other with the usefulness capillary connecting pipes such as the 4th sample introduction needle of the 15 peristaltic pump tube, constant temperature automatic sampler; Interface B4 links to each other with the 4th sampling ring two ends respectively with E4; Interface D4 links to each other with the capillary connecting pipe with the 16 peristaltic pump tube, the 4th current-carrying container bottle successively; Interface C4 successively with the tenth knitting reactor, the 9th threeway the first entrance, the 9th threeway outlet, the 11 knitting reactor, the tenth threeway the first entrance, the tenth threeway outlet, the 12 knitting reactor, the 11 threeway the first entrance, the 11 threeway outlet, the 13 knitting reactor, the 4th flow cell is communicated with the capillary connecting pipe, the 13 knitting reactor is wrapped on the heating module, the second entrance and the 17 peristaltic pump tube of the 9th threeway, the second ammonium molybdate solution container bottle links to each other with the capillary connecting pipe, the second entrance and the 18 peristaltic pump tube of the tenth threeway, the oxalic acid solution container bottle is housed to link to each other by the capillary connecting pipe, the second entrance and the 19 peristaltic pump tube of the 11 threeway, the second ascorbic acid solution container bottle links to each other by the capillary connecting pipe, the interface A4 of the 4th sample fillup valve is communicated with waste liquid tank, be provided with the 4th flow cell in the 4th detecting device, the 4th flow cell links to each other with waste liquid tank through the 8th back pressure regulator, and the 4th detecting device is connected with computer control system by the 4th signal wire.
Full-automatic nutritive salt is analyzed instrument, wherein, the peristaltic pump tube internal diameter is 0.38～1.85mm, pump speed is 15～60 rev/mins, the reagent refrigerating storehouse is at least 4 * 6 designs, can put into five kinds of all reagent that substance-measuring is required, and the constant temperature automatic sampler comprises at least four sample introduction needle or comprises a sample introduction needle and at least one minute four X-over, the constant temperature automatic sampler also comprises platter, rinse bath, the test tube more than 5, and sample introduction needle links to each other with peristaltic pump by the capillary connecting pipe.
Full-automatic nutritive salt is analyzed instrument, and wherein, the first to the 5th knitting reactor, the 7th to the 8th knitting reactor, the tenth to the 12 knitting reactor length are 0.5～2m; The 6th knitting reactor length is 3～10m, and temperature is 40-70 ℃; The 9th knitting reactor length is 1～5m, and temperature is 30-60 ℃; The 13 knitting reactor length is 0.5～9m, and temperature is 30-60 ℃; The length of first to fourth sampling ring is 0.5-4m; The length of each capillary connecting pipe is 0.1-1m.
Use full-automatic nutritive salt to analyze instrument and measure seawater Nitrite Nitrogen (NO 2 -) method, wherein, with after filtering sample by the constant temperature automatic sampler under the effect of peristaltic pump through the first peristaltic pump tube, enter the first sampling ring that connects on the first sample fillup valve, first is full of sampling ring by the direct waste discharge of the first back pressure regulator and enters waste liquid bottle, after sampling process finishes, the first sample fillup valve interface F1 and A1, B1 and C1, E1 and D1 UNICOM, peristaltic pump pumps into the current-carrying solution in the first current-carrying container bottle through the second peristaltic pump tube, sample in the first sampling ring is released, enter in the first threeway and converge with the chloride buffer solution that enters through the 3rd peristaltic pump tube, mixed liquor enters the first knitting reactor to be mixed, mixed solution enters four-way valve through four-way valve D ' mouth, wherein as four-way valve A ' and B ', when D ' is connected with C ', mixed solution goes out by four-way valve C ' mouthful, in the second threeway, converge with the sulfanilamide (SN) developer that enters through the 4th peristaltic pump tube, enter the second knitting reactor hybrid reaction, reacted liquid enters the first flow cell again, carry out colorimetric estimation by the second detecting device at the 540nm place, the liquid that flows out directly enters waste liquid bottle through the second back pressure regulator, by absorbance peak height value or peak area value and the typical curve comparing calculation solution Nitrite Nitrogen (NO of computer system with sample 2 -) content.
Use full-automatic nutritive salt to analyze instrument and measure Nitrate Nitrogen in Seawater (NO 3 -), nitrite nitrogen (NO 2 -) method, wherein, with after filtering sample by the constant temperature automatic sampler under the effect of peristaltic pump through the first peristaltic pump tube, enter the first sampling ring that connects on the first sample fillup valve, first is full of sampling ring by the direct waste discharge of the first back pressure regulator and enters waste liquid bottle, after sampling process finishes, the first sample fillup valve interface F1 and A1, B1 and C1, E1 and D1 UNICOM, peristaltic pump pumps into the current-carrying solution in the first current-carrying container bottle through the second peristaltic pump tube, sample in the first sampling ring is released, enter in the first threeway and converge with the chloride buffer solution that enters through the 3rd peristaltic pump tube, mixed liquor enters the first knitting reactor to be mixed, mixed solution enters four-way valve through four-way valve D ' mouth, out enters afterwards the cadmium reduction column by A ' mouth, with the nitrate nitrogen (NO in the sample liquid 3 -) be reduced to nitrite nitrogen (NO 2 -), the solution that exports out through the cadmium reduction column enters four-way valve B ', go out by four-way valve C ' mouthful, in the second threeway, converge with the sulfanilamide (SN) developer that enters through the 4th peristaltic pump tube, enter the second knitting reactor hybrid reaction, reacted liquid enters the first flow cell again, carry out colorimetric estimation by the second detecting device at the 540nm place, the liquid that flows out directly enters waste liquid bottle through the second back pressure regulator, by computer system with nitrate nitrogen (NO in the absorbance peak height value of sample or peak area value and the typical curve comparing calculation solution 3 -) add nitrite nitrogen (NO 2 -) content; Wherein when four-way valve A ' was connected with C ' with B ', D ', the analysis result that the result of acquisition is was nitrite nitrogen (NO 2 -) content, nitrate nitrogen (NO in the solution 3 -) add nitrite nitrogen (NO 2 -) content deduct nitrite nitrogen (NO 2 -) content be nitrate nitrogen (NO 3 -) analysis result.
Use full-automatic nutritive salt to analyze instrument and measure Nitrate Nitrogen in Seawater (NO 3 -), nitrite nitrogen (NO 2 -) method, wherein, current-carrying solution is artificial seawater, artificial seawater consists of: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and to be settled to 1L; The pH value of chloride buffer solution is 8～9; The phosphoric acid of consisting of in the sulfanilamide (SN) chromogenic reagent solution: 50-200ml 85%, 17～67g sulfanilamide (SN) (C 6H 8N 2O 2S), 0.37～2.5g N-(1-naphthyl) ethylenediamine-hydrochloride (C 12H 16Cl 2N 2), the deionized water dissolving mixing is settled to 1L.
Use full-automatic nutritive salt to analyze instrument and measure Ammonia In Sea Water (NH 4 +) content assaying method, wherein, sample after filtering by the constant temperature automatic sampler under the effect of peristaltic pump through the 5th peristaltic pump tube, enter the second sampling ring that connects on the second six-way valve, the second sampling ring is full of by the direct waste discharge of the 3rd back pressure regulator enters waste liquid bottle, after sampling process finishes, the second six-way valve rotates and makes interface F2 and A2, B2 and C2, E2 and D2 UNICOM state, peristaltic pump pumps into current-carrying solution through the 6th peristaltic pump tube, sample in the second sampling ring is released, sample enters in the 3rd threeway and converges with the buffer solution that enters through the 7th peristaltic pump tube, entering the 3rd knitting reactor mixes, mixed solution converges with the salicylate solution that enters through the 8th peristaltic pump tube in the 4th threeway, enter the 4th knitting reactor hybrid reaction, mixed solution converges with the sodium nitroprusside solution that enters through the 9th peristaltic pump tube in the 5th threeway, enter the 5th knitting reactor hybrid reaction, mixed solution converges with the sodium dichloroisocyanate solution that enters through the tenth peristaltic pump tube in the 6th threeway, enter the 6th knitting reactor hybrid reaction, temperature of reaction is set to 60 ℃, the reacted liquid pond that circulates again, carry out colorimetric estimation by detecting device at the 660nm place, the liquid that flows out directly enters waste liquid bottle through the 4th back pressure regulator, by absorbance peak height value or peak area value and the typical curve comparing calculation ammonia nitrogen in solution (NH of computer system with sample 4 +) content.
Use full-automatic nutritive salt to analyze instrument and measure Ammonia In Sea Water (NH 4 +) content assaying method, wherein, current-carrying solution is artificial seawater, artificial seawater consists of: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and to be settled to 1L; The pH value of buffer solution should be 5～6, and it consists of 21～45g sodium potassium tartrate tetrahydrate (C 4H 4O 6KNa4H 2O), 17～36g sodium citrate (C 6H 5O 7Na 32H 2O), the deionized water dissolving mixing is settled to 1L; Salicylate solution consist of 10-40g NaOH (NaOH), add 50-160g sodium salicylate (C 7H 5NaO 3), the deionized water dissolving mixing is settled to 1L; Sodium nitroprussiate (Na 2[Fe (CN) 5NO] 2H 2O) concentration of solution is 2～9g/L; Sodium dichloroisocyanate (C 3N 3O 3Cl 2Na2H 2O) concentration of solution (44) is 1～7g/L.
Use full-automatic nutritive salt to analyze instrument and measure Seawater Phosphate (PO 4 3-) the method for content value, wherein, sample after filtering by the constant temperature automatic sampler under the effect of peristaltic pump through the 11 peristaltic pump tube, enter the 3rd sampling ring that connects on the 3rd six-way valve, the 3rd sampling ring is full of by the direct waste discharge of the 5th back pressure regulator enters waste liquid bottle, after sampling process finishes, the 3rd six-way valve rotates and makes interface F3 and A3, B3 and C3, E3 and D3 UNICOM state, the state shown in the dotted line in the figure, peristaltic pump pumps into current-carrying solution through the 12 peristaltic pump tube, sample in the sampling ring is released, enter in the 7th knitting reactor and mix, then enter in the 7th threeway and converge with the first ascorbic acid solution that in the 13 peristaltic pump tube, pumps into, then entering the 8th knitting reactor mixes, mixed solution converges with the first ammonium molybdate chromogenic reagent solution that pumps into through the 14 peristaltic pump tube in the 8th threeway, enter the 9th knitting reactor hybrid reaction, temperature of reaction is 37 ℃, reacted liquid enters the 3rd flow cell and carries out colorimetric estimation by the 3rd detecting device at the 880nm place, the liquid that flows out directly enters waste liquid bottle through the 6th back pressure regulator, will can obtain phosphate (PO in the solution in the absorbance peak height value of sample or peak area value and the typical curve comparing calculation solution by computer system 4 3-) the phosphorus content value.
Use full-automatic nutritive salt to analyze instrument and measure Seawater Phosphate (PO 4 3-) the method for content value, wherein, current-carrying solution is artificial seawater, artificial seawater consists of: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and are settled to 1L; The concentration of ascorbic acid is 50～100g/L in the first ascorbic acid solution; The concentration of ammonium molybdate is 5～12g/L in the first ammonium molybdate chromogenic reagent solution, and the concentration of potassium antimony tartrate is 0.1～0.4g/L, and the concentration of sulfuric acid is 2-5% (v/v).
Use full-automatic nutritive salt to analyze instrument and measure seawater mesosilicic acid salt (SiO 4 2-) method, wherein, sample after filtering by the constant temperature automatic sampler under the effect of peristaltic pump through the 15 peristaltic pump tube, enter the 4th sampling ring that connects on the 4th six-way valve, the 4th sampling ring is full of by the direct waste discharge of the 7th back pressure regulator enters waste liquid bottle, after sampling process finishes, the 4th six-way valve rotates and makes interface F4 and A4, B4 and C4, E4 and D4 UNICOM state, peristaltic pump pumps into current-carrying solution through the 16 peristaltic pump tube, sample in the 4th sampling ring is released, enter in the tenth knitting reactor and mix, then enter in the 9th threeway and converge with the second ammonium molybdate chromogenic reagent solution that pumps into through the 17 peristaltic pump tube, then entering the 11 knitting reactor mixes, mixed solution converges with the oxalic acid solution that pumps into through the 18 peristaltic pump tube in the tenth threeway, enter the 12 knitting reactor hybrid reaction, reacted solution converges with the second ascorbic acid solution that pumps into through the 19 peristaltic pump tube in the 11 threeway, enter the 13 knitting reactor hybrid reaction, temperature of reaction is 37 ℃, reacted liquid enters the 4th flow cell and carries out colorimetric estimation by the 4th detecting device at the 880nm place, the liquid that flows out directly enters waste liquid bottle through the 8th back pressure regulator, will can obtain can obtain in the solution solution mesosilicic acid salt (SiO in the absorbance peak height value of sample or peak area value and the typical curve comparing calculation solution by computer system (30) 4 2-) SiO 2Content value.
Use full-automatic nutritive salt to analyze instrument and measure seawater mesosilicic acid salt (SiO 4 2-) method, wherein, wherein current-carrying solution is artificial seawater, artificial seawater consists of: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and to be settled to 1L; The second ammonium molybdate chromogenic reagent solution consist of 2～6mL concentrated sulphuric acid, 8～23g, four water ammonium molybdate [(NH 4) 6Mo 7O 244H 2O], the mixing of 2～9g lauryl sodium sulfate deionized water dissolving is settled to 1L; Ascorbic acid solution concentration is 30-70g/L; Oxalic acid solution (95) concentration is 76-108g/L.
Measuring method of the present invention, wherein, the consisting of of artificial seawater: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and are settled to 1L.The present invention uses artificial seawater as the current-carrying leaf, and the high salinity that can eliminate in the seawater sample changes the matrix effect that causes.
Data record processing method is that the sample light intensity is converted into electric signal, and background correction by the automatic record of computer, is drawn absorbance figure, and integration is obtained a result.
Advantage of the present invention is:
1. chemical analysis template of the present invention is divided into four zones, is respectively nitrate nitrogen (NO 3 -), nitrite nitrogen (NO 2 -) analysis area, ammonia nitrogen (NH 4 +) analysis area, phosphate (PO 4 3-) analysis area, silicate (SiO 4 2-) the analysis area composition, can realize nitrate nitrogen (NO 3 -), nitrite nitrogen (NO 2 -), ammonia nitrogen (NH 4 +), phosphate (PO 4 3-), silicate (SiO 4 2-) analyze when five kinds of nutritional labelings;
2. chemical analysis template of the present invention is divided into four zones, and phosphate (PO43-) analysis area and silicate (SiO42-) analysis area are isolated, can avoid measuring between silicate and the phosphate problem that interferes with each other.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the structure diagram that the full-automatic nutritive salt of the present invention is analyzed instrument;
Fig. 2 is the nitrate nitrogen (NO that full-automatic nutritive salt shown in Figure 1 is analyzed instrument 3 -), nitrite nitrogen (NO 2 -) the stream synoptic diagram;
Fig. 3 is the ammonia nitrogen (NH that full-automatic nutritive salt shown in Figure 1 is analyzed instrument 4 +) the stream synoptic diagram;
Fig. 4 is the phosphate (PO that full-automatic nutritive salt shown in Figure 1 is analyzed instrument 4 3-) the stream synoptic diagram;
Fig. 5 is the silicate (SiO that full-automatic nutritive salt shown in Figure 1 is analyzed instrument 4 2-) the stream synoptic diagram;
Fig. 6 is the constant temperature automatic sampler structural representation that full-automatic nutritive salt shown in Figure 1 is analyzed instrument.
Embodiment
Embodiment 1
The full-automatic nutritive salt of the present invention is analyzed instrument, referring to Fig. 1,6, comprise reagent refrigerating storehouse 2, constant temperature automatic sampler 1, main frame 3, main frame 3 comprises peristaltic pump 4,4 sample fillup valve groups 5 that the sample fillup valve forms, chemical analysis template 6, detector set 8, wherein reagent refrigerating storehouse 2 is 4 * 6 designs, can put into five kinds of all reagent that substance-measuring is required, and constant temperature automatic sampler 1 comprises four sample introduction needle 35, platter 33, rinse bath 36,5 test tubes 34, chemical analysis template 6 is divided into four zones, is respectively nitrate nitrogen NO 3 -, nitrite nitrogen NO 2 -Analysis area, ammonia nitrogen NH 4 +Analysis area, phosphate PO 4 3-Analysis area, silicate SiO 4 2-Analysis area, peristaltic pump 4 comprise 19 peristaltic pump tubes, and the peristaltic pump tube internal diameter is 0.38～1.85mm, and pump speed is 15～60 rev/mins, and detector set 8 comprises 4 roads detecting device in parallel and computer control system 30, and the temperature control equipment group comprises four temperature control equipments.Sample introduction needle 35 links to each other by the peristaltic pump tube of capillary connecting pipe and peristaltic pump 4, and peristaltic pump tube links to each other by the capillary connecting pipe successively with flow cell in chemical analysis template 6, the detecting device, and detecting device is connected with computer control system 30 by signal wire.The first temperature control equipment 701 main control systems 3 airborne temperature, temperature control equipment 702 control ammonia nitrogen (NH 4 +) temperature of heating module in the analysis area, temperature control equipment 703 control phosphate (PO 4 3-) temperature of heating module in the analysis area, temperature control equipment 704 control silicate (SiO 4 2-) temperature of heating module in the analysis area.
Referring to Fig. 2, nitrate nitrogen NO 3 -, nitrite nitrogen NO 2 -Analysis area comprises two knitting reactor, two threeways, capillary connecting pipe, container bottle, four-way valve 20 has A ', B ', four interfaces of C ', D ', the first sample fillup valve 17 has A1, B1, C1, D1, six interfaces of E1, F1, and interface F1 links to each other with the first sample introduction needle 9 usefulness capillary connecting pipes of peristaltic pump the first peristaltic pump tube 10, constant temperature automatic sampler 1 successively; Interface B1 links to each other with the first sampling ring 16 two ends respectively with E1; Interface D1 links to each other with the second peristaltic pump tube 11, the first current-carrying container bottle 15 usefulness capillary connecting pipes successively; Interface C1 is communicated with the capillary connecting pipe with the first threeway 18 first entrances, the first threeway 18 outlets, the first knitting reactor 19, four-way valve 20D ' interface successively; Four-way valve 20C ' interface successively with the second threeway 21 first entrances, the second threeway 21 outlets, the second knitting reactor 24, flow cell 27 usefulness capillary connecting pipes are communicated with, the A ' of four-way valve 20, B ' interface is connected to the two ends of cadmium reduction column 23 with the capillary connecting pipe, the second entrance of the first threeway 18 and the 3rd peristaltic pump tube 12, the first reagent container bottle 25 usefulness capillary connecting pipes that chloride buffer solution is housed link to each other, the second entrance of the second threeway 21 and the 4th peristaltic pump tube 13, the second reagent container bottle 26 that the sulfanilamide (SN) chromogenic reagent solution is housed links to each other by the capillary connecting pipe, the interface A1 of the first sample fillup valve 17 is communicated with waste liquid tank 32 through the first back pressure regulator 22 with the capillary connecting pipe, be provided with the first flow cell 27 in the first detecting device, the first flow cell 27 usefulness capillary connecting pipes link to each other with waste liquid tank 32 through the second back pressure regulator 29, and the first detecting device 28 is connected with computer control system 30 by first signal line 31.
Referring to Fig. 3, ammonia nitrogen NH 4 +Analysis area comprises four knitting reactor, four threeways, capillary connecting pipe, container bottle, the second sample fillup valve 52 has A2, B2, C2, D2, six interfaces of E2, F2, and interface F2 links to each other with the second sample introduction needle 38 usefulness capillary connecting pipes of peristaltic pump the 5th peristaltic pump tube 45, constant temperature automatic sampler 1; Interface B2 links to each other with the second sampling ring 51 two ends respectively with E2; Interface D2 links to each other with the 6th peristaltic pump tube 46, the second current-carrying container bottle 40 usefulness capillary connecting pipes successively; Interface C2 successively with the 3rd threeway 53 first entrances, the 3rd threeway 53 outlets, the 3rd knitting reactor 54, the 4th threeway 55 first entrances, the 4th threeway 55 outlets, the 4th knitting reactor 57, the 5th threeway 58 first entrances, the 5th threeway 58 outlets, the 5th knitting reactor 59, the 6th threeway 60 first entrances, the 6th threeway 60 outlets, the 6th knitting reactor 61, flow cell 62 usefulness capillary connecting pipes are communicated with, the 6th knitting reactor 61 is wrapped on the heating module, the second entrance of the 3rd threeway 53 and the 7th peristaltic pump tube 47, buffer solution container bottle 41 usefulness capillary connecting pipes are housed to link to each other, the second entrance of the 4th threeway 55 and the 8th peristaltic pump tube 48, salicylate solution container bottle 42 is housed to link to each other by the capillary connecting pipe, the second entrance of the 5th threeway 58 and the 9th peristaltic pump tube 49, sodium nitroprusside solution container bottle 43 is housed to link to each other by the capillary connecting pipe, the second entrance of the 6th threeway 60 and the tenth peristaltic pump tube 50, the container bottle 44 that sodium dichloroisocyanate solution is housed links to each other by the capillary connecting pipe, the interface A2 of the second sample fillup valve 52 is communicated with waste liquid tank 32 through the 3rd back pressure regulator 56 by the capillary connecting pipe, be provided with the second flow cell 62 in the second detecting device 63, the second flow cell 62 links to each other with waste liquid tank 32 through the 4th back pressure regulator 64, and the second detecting device is connected with computer control system 30 by secondary signal line 65.
Referring to Fig. 4, phosphate PO 4 3-Analysis area comprises three knitting reactor, two threeways, capillary connecting pipe, container bottle, the 3rd sample fillup valve 80 has A3, B3, C3, D3, six interfaces of E3, F3, and interface F3 links to each other with the 3rd sample introduction needle 70 usefulness capillary connecting pipes of the 11 peristaltic pump tube 75, constant temperature automatic sampler 1; Interface B3 links to each other with the 3rd sampling ring 79 two ends respectively with E3; Interface D3 links to each other with the 12 peristaltic pump tube 76, the 3rd current-carrying container bottle 72 usefulness capillary connecting pipes successively; Interface C3 successively with the 7th knitting reactor 81, the 7th threeway 83 first entrances, the 7th threeway 83 outlets, the 8th knitting reactor 84, the 8th threeway 85 first entrances, the 8th threeway 85 outlets, the 9th knitting reactor 86, the 3rd flow cell 88 usefulness capillary connecting pipes are communicated with, the 9th knitting reactor 86 is wrapped on the heating module, the second entrance of the 7th threeway 83 and the 13 peristaltic pump tube 77, the container bottle 73 usefulness capillary connecting pipes that the first ascorbic acid solution is housed link to each other, the second entrance of the 8th threeway 85 and the 14 peristaltic pump tube 78, the container bottle 74 that the first ammonium molybdate solution is housed links to each other by the capillary connecting pipe, the interface A3 of the 3rd sample fillup valve 80 is communicated with waste liquid tank 32 through the 5th back pressure regulator 82 by the capillary connecting pipe, be provided with the 3rd flow cell 88 in the 3rd detecting device 89, the 3rd flow cell 88 links to each other with waste liquid tank 32 through the 6th back pressure regulator 87, and the 3rd detecting device 89 is connected with computer control system 30 by the 3rd signal wire 90.
Referring to Fig. 5, silicate SiO 4 2-Analysis area comprises four knitting reactor, three threeways, capillary connecting pipe, container bottle, the 4th sample fillup valve 103 has A4, B4, C4, D4, six interfaces of E4, F4, and interface F4 links to each other with the usefulness capillary connecting pipes such as the 4th sample introduction needle 91 of the 15 peristaltic pump tube 97, constant temperature automatic sampler 1; Interface B4 links to each other with the 4th sampling ring 102 two ends respectively with E4; Interface D4 links to each other with the 16 peristaltic pump tube 98, the 4th current-carrying container bottle 93 usefulness capillary connecting pipes successively; Interface C4 successively with the tenth knitting reactor 104, the 9th threeway 105 first entrances, the 9th threeway 105 outlets, the 11 knitting reactor 106, the tenth threeway 107 first entrances, the tenth threeway 107 outlets, the 12 knitting reactor 108, the 11 threeway 109 first entrances, the 11 threeway 109 outlets, the 13 knitting reactor 110, the 4th flow cell 111 usefulness capillary connecting pipes are communicated with, the 13 knitting reactor 110 is wrapped on the heating module, the second entrance of the 9th threeway 105 and the 17 peristaltic pump tube 99, the second ammonium molybdate solution container bottle 94 usefulness capillary connecting pipes link to each other, the second entrance of the tenth threeway 107 and the 18 peristaltic pump tube 100, oxalic acid solution container bottle 95 is housed to link to each other by the capillary connecting pipe, the second entrance of the 11 threeway 109 and the 19 peristaltic pump tube 101, the second ascorbic acid solution container bottle 96 links to each other by the capillary connecting pipe, the interface A4 of the 4th sample fillup valve 103 is communicated with waste liquid tank 32 by the 9th back pressure regulator 115, be provided with the 4th flow cell 111 in the 4th detecting device 112, the 4th flow cell 111 links to each other with waste liquid tank 32 through the 8th back pressure regulator 113, and the 4th detecting device 112 is connected with computer control system 30 by the 4th signal wire 114.
The full-automatic nutritive salt of the present invention is analyzed instrument, and wherein the first to the 5th knitting reactor 19, the 24,54,57,59, the 7th to the 8th knitting reactor 81, the 84, the tenth to the 12 knitting reactor 104,106,108 length are 0.5～2m; The 6th knitting reactor 61 length are 3～10m, and temperature is 40-70 ℃; The 9th knitting reactor 86 length are 1～5m, and temperature is 30-60 ℃; The 13 knitting reactor 110 length are 0.5～9m, and temperature is 30-60 ℃; First to fourth sampling ring 16,51,79,102 length are 0.5-4m; The length of each capillary connecting pipe is 0.1-1m.
The course of work that full-automatic nutritive salt is analyzed instrument is:
Open power switch device, under the driving of peristaltic pump 4, sample is drawn by constant temperature automatic sampler 1, enters chemical analysis template 6 and reacts, and reacted solution enters detecting device 8 and detects, and the spectrogram of generation can be surveyed and drawn.Absorbance peak height value or the peak area value of standard solution according to record done typical curve, the content that calculates nutritive salt at typical curve according to absorbance peak height value or the peak area value of sample.
Embodiment 2
The below describes in detail and uses full-automatic nutritive salt analysis instrument of the present invention to the nitrate nitrogen NO in the seawater 3 -, nitrite nitrogen NO 2 -The course of work of analyzing.
One, present embodiment nitrite nitrogen NO 2 -Method of testing
Present embodiment nitrite nitrogen NO 2 -Required reagent in the operation steps of test:
1, current-carrying is artificial seawater, the preparation of artificial seawater: 40g sodium chloride, the mixing of 0.32g sodium bicarbonate deionized water dissolving is settled to 1L.
2, the preparation of standard specimen:
(1) takes by weighing at 60 ℃ of lower 4.926g potassium nitrite (KNO of dry one hour 2) in the 800ml deionized water, be diluted to scale with artificial seawater after the dissolving, shake up.Be mixed with 1000mg N/L in the nitrite nitrogen NO of nitrogen 2 -Storing solution is for subsequent use.
(2) with the nitrite nitrogen NO of 1000mg/L 2 -Storing solution artificial seawater stepwise dilution is mixed with 0.0,20.0,50.0,100.0,200.0,500.0,800.0,1000.0 μ g N/L standard series.
3, the chloride buffer pH value of solution is 8.5.
4, the phosphoric acid of sulfanilamide (SN) developer: 70ml 85%, 24g sulfanilamide (SN) (C 6H 8N 2O 2S), 1.2g N-(1-naphthyl) ethylenediamine-hydrochloride C 12H 16Cl 2N 2, the deionized water dissolving mixing is settled to 1L.
5, current-carrying is artificial seawater, uses artificial seawater to do the matrix interference that current-carrying can be removed the seawater high salinity.Agents useful for same all adopts domestic reagent, and the purity of reagent is minimum pure for analyzing.
Present embodiment nitrite nitrogen NO 2 -The operation steps of test
Referring to Fig. 2, sample 14 after filtering by constant temperature automatic sampler 1 under the effect of peristaltic pump 4 through the first peristaltic pump tube 10, enter on the six-way valve 17 sampling ring 16 that connects, sampling ring 16 is full of by the 22 direct waste discharges of the first back pressure regulator enters waste liquid bottle 32.After sampling process finishes, six-way valve 17 rotates and makes interface F1 and A1, B1 and C1, E1 and D1 UNICOM, peristaltic pump 4 pumps into current-carrying solution 15 through the second peristaltic pump tube 11, sample in the sampling ring 16 is released, enter in the first threeway 18 and converge with the chloride buffer solution 25 that enters through the 3rd peristaltic pump tube 12, entering the first knitting reactor 19 mixes, at this moment, the position of four-way valve is A ' and B ', D ' is connected with C ', mixed solution is without cadmium reduction column 23, directly D ' the interface from four-way valve flows into, enter the second threeway 21 from the outflow of C ' interface, mixed solution converges with the sulfanilamide (SN) developer 26 that enters through the 4th peristaltic pump tube 13 in the second threeway 21, enter the second knitting reactor 24 hybrid reactions, the reacted liquid pond 27 that circulates is again carried out colorimetric estimation by detecting device 28 at the 540nm place, and the liquid that flows out directly enters waste liquid bottle 32 through the second back pressure regulator 29.
Can obtain solution Nitrite Nitrogen NO by computer system 30 2 -Content, this is result 1, sees Table 1, table 2.
The working curve test result of table 1 nitrite nitrogen
Standard specimen concentration Peak height Peak area Return and calculate concentration (μ g/L)
0 0.0001 0.0108 0.4
1 0.0006 0.0763 1.3
2 0.0011 0.1434 2.2
5 0.0025 0.3294 4.9
10 0.0051 0.6687 9.6
20 0.0106 1.3771 19.6
50 0.0269 3.5154 49.7
100 0.0543 7.1043 100.2
The quality-control sample test result of table 2 nitrite nitrogen
The sample title Concentration known (μ g/L) Peak height Peak area Return and calculate concentration (μ g/L)
The Quality Control sample 83.9±3.4 0.0459 5.9785 84.4
The Quality Control sample 83.9±3.4 0.046 6.0049 84.8
By the result of table 1, table 2 as can be known, instrument of the present invention and method can detect solution Nitrite Nitrogen NO accurately 2 -Content.
Two, present embodiment nitrate nitrogen NO 3 -The method of operating of test
Present embodiment nitrate nitrogen NO 3 -Required reagent in the operation steps of test:
1, current-carrying is artificial seawater, the preparation of artificial seawater: 40g sodium chloride, the mixing of 0.32g sodium bicarbonate deionized water dissolving is settled to 1L.
2, the preparation of standard specimen:
(1) takes by weighing at 60 ℃ of lower 7.221g potassium nitrate KNO3 of dry one hour in the 800ml deionized water, be diluted to scale with artificial seawater after the dissolving, shake up.It is for subsequent use in the nitrate nitrogen NO3-storing solution of nitrogen to be mixed with 1000mg N/L.
(2) with the nitrate nitrogen NO3-storing solution artificial seawater stepwise dilution of 1000mg/L, be mixed with 0.0,20.0,50.0,100.0,200.0,500.0,800.0,1000.0 μ g N/L standard series.
3, the chloride buffer pH value of solution is 8.5.
4, the phosphoric acid of sulfanilamide (SN) developer: 70ml 85%, 24g sulfanilamide (SN) (C6H8N2O2S), 1.2g N-(1-naphthyl) ethylenediamine-hydrochloride C12H16Cl2N2, the deionized water dissolving mixing is settled to 1L.
5, agents useful for same all adopts domestic reagent, and the purity of reagent is minimum pure for analyzing.
Nitrate nitrogen NO in the solution 3 -Add nitrite nitrogen NO 2 -The operation steps of content
Referring to Fig. 1, sample 14 after filtering by constant temperature automatic sampler 1 under the effect of peristaltic pump 4 through the first peristaltic pump tube 10, enter on the six-way valve 17 sampling ring 16 that connects, sampling ring 16 is full of by the 22 direct waste discharges of the first back pressure regulator enters waste liquid bottle 32.After sampling process finishes, six-way valve 17 turns to the state shown in the dotted line among the figure, peristaltic pump 4 pumps into current-carrying solution 15 through the second peristaltic pump tube 11, sample in the sampling ring 16 is released, enter in the first threeway 18 and converge with the chloride buffer solution 25 that enters through the 3rd peristaltic pump tube 12, entering the first knitting reactor 19 mixes, the position of four-way valve is that A ' is connected with C ' with D ', B ', mixed solution enters through four-way valve 20D ' mouthful, out enter afterwards cadmium reduction column 23 by A ' mouth, with the nitrate nitrogen NO in the sample liquid 3 -Be reduced to nitrite nitrogen NO 2 -Enter four-way valve B ' through cadmium reduction column 23 outlets solution out, go out by four-way valve C ' mouthful, in the second threeway 21, converge with the sulfanilamide (SN) developer 26 that enters through the 4th peristaltic pump tube 13, enter the second knitting reactor 24 hybrid reactions, the reacted liquid pond 27 that circulates is again carried out colorimetric estimation by detecting device 28 at the 540nm place, and the liquid that flows out directly enters waste liquid bottle 32 through the second back pressure regulator 29.
Can obtain nitrate nitrogen NO in the solution by computer system 30 3 -Add nitrite nitrogen NO 2 -Content, this is result 2, deducts result 1 with result 2, is nitrate nitrogen NO 3 -Content, the results are shown in Table 3, table 4.
Table 3 nitrate nitrogen standard model is analyzed data
Standard specimen concentration (μ g/L) Peak height Peak area Return and calculate concentration (μ g/L)
2 0.0026 0.41 1.7
5 0.0041 0.6699 5.2
10 0.0064 1.0525 10.2
20 0.0111 1.8491 20.7
50 0.0252 4.1552 51.1
100 0.0473 7.8121 99.3
200 0.1007 16.6861 216.2
500 0.2396 39.5567 517.5
1000 0.46 76.3023 1001.6
2000 0.9003 149.9172 1971.5
Table 4 nitrate nitrogen Quality Control sample is analyzed data
The sample title Concentration known (mg/L) Return and calculate concentration (μ g/L) Peak height Peak area
The Quality Control sample 1.5±0.05 1482.2 0.7138 112.7755
The Quality Control sample 1.5±0.05 1479.0 0.7064 112.5365
By the result of table 3, table 4 as can be known, instrument of the present invention and method can detect nitrate nitrogen NO in the solution accurately 3 -Content.
Embodiment 3
The below describes in detail and uses full-automatic nutritive salt analysis instrument of the present invention to Ammonia In Sea Water NH 4 +The course of work of analyzing.
Present embodiment ammonia nitrogen NH 4 +The required reagent of operation steps of test:
1, current-carrying liquid is artificial seawater, the preparation of artificial seawater: 40g sodium chloride, the mixing of 0.32g sodium bicarbonate deionized water dissolving is settled to 1L.
2, the preparation of standard specimen:
(1) takes by weighing at 60 ℃ of lower 3.819g sal-ammoniac NH4Cl of dry one hour, be diluted to scale with artificial seawater after the dissolving, shake up.It is for subsequent use in nitrogen ammonia nitrogen NH4+ storing solution to be mixed with 1000mg N/L.
(2) with the ammonia nitrogen NH4+ storing solution artificial seawater stepwise dilution of 1000mg/L, be mixed with 0.0,20.0,50.0,100.0,200.0,500.0,800.0,1000.0 μ g N/L standard series.
3, the pH value of buffer solution should be 5.3, and it consists of 30g sodium potassium tartrate tetrahydrate C4H4O6KNa4H2O, 20g sodium citrate C6H5O7Na32H2O, and the deionized water dissolving mixing is settled to 1L.
4, salicylate solution consist of 35g NaOH NaOH, add 98g sodium salicylate C7H5NaO3, deionized water dissolving mixes and is settled to 1L.
5, sodium nitroprussiate Na2[Fe (CN) 5NO] concentration of 2H2O solution is 8g/L.
6, the concentration of sodium dichloroisocyanate (C3N3O3Cl2Na2H2O) solution is 3g/L.
Agents useful for same all adopts domestic reagent, and the purity of reagent is minimum pure for analyzing.
Present embodiment ammonia nitrogen NH 4 +The operation steps of test:
Referring to Fig. 3, sample 39 after filtering by constant temperature automatic sampler 1 under the effect of peristaltic pump 4 through the 5th peristaltic pump tube 45, enter on the six-way valve 52 sampling ring 51 that connects, sampling ring 51 is full of by the 56 direct waste discharges of the 3rd back pressure regulator enters waste liquid bottle 32.After sampling process finishes, six-way valve 52 rotates and makes interface F2 and A2, B2 and C2, E2 and D2 UNICOM state, peristaltic pump 4 pumps into current-carrying solution 40 through the 6th peristaltic pump tube 46, sample in the sampling ring 51 is released, enter in the 3rd threeway 53 and converge with the buffer solution 41 that enters through the 7th peristaltic pump tube 47, entering the 3rd knitting reactor 54 mixes, mixed solution converges with the salicylate solution 42 that enters through the 8th peristaltic pump tube 48 in the 4th threeway 55, enter the 4th knitting reactor 57 hybrid reactions, mixed solution converges with the sodium nitroprusside solution 43 that enters through the 9th peristaltic pump tube 49 in the 5th threeway 58, enter the 5th knitting reactor 59 hybrid reactions, mixed solution converges with the sodium dichloroisocyanate solution 44 that enters through the tenth peristaltic pump tube 44 in the 6th threeway 60, enter the 6th knitting reactor 61 hybrid reactions, the 6th knitting reactor 61 is wrapped on temperature control equipment 7 set temperatures are 60 ℃ on-line heating module.The reacted liquid pond 62 that circulates is again carried out colorimetric estimation by detecting device 63 at the 660nm place, and the liquid that flows out directly enters waste liquid bottle 32 through the 4th back pressure regulator 64.
Can obtain ammonia nitrogen in solution NH by computer system 30 4 +Content, the results are shown in Table 5, table 6.
Table 5 ammonia nitrogen method working curve data
Concentration (μ g/L) Peak height Peak area Return and calculate concentration (μ g/L)
0 0.0004 0.036 0
10 0.0035 0.7771 19.6
50 0.0087 1.8931 50.1
100 0.0171 3.602 96.7
200 0.0346 7.2174 195.3
500 0.0878 18.2397 495.9
1000 0.1781 36.8389 1003.1
The mensuration of table 6 ammonia nitrogen method Quality Control sample
The sample title Concentration known (μ g/L) Return and calculate concentration (μ g/L) Peak height Peak area
Quality-control sample 799±36 800.2 0.1426 29.4001
Quality-control sample 799±36 877.8 0.1407 32.2452
By the result of table 5, table 6 as can be known, instrument of the present invention and method can detect ammonia nitrogen in solution NH accurately 4 +Content.
Embodiment 4
Present embodiment phosphate PO 4 3-Reagent required in the operation steps of test is prepared:
1, current-carrying is artificial seawater, the preparation of artificial seawater: 40g sodium chloride, the mixing of 0.32g sodium bicarbonate deionized water dissolving is settled to 1L.
2, the preparation of standard specimen:
(1) take by weighing 4.396g at 110 ℃ of anhydrous potassium dihydrogenphosphate KH2PO4 that descend dry 2h and let cool in exsiccator, be settled to the 1000ml volumetric flask with artificial seawater after the water dissolving, it is for subsequent use in the phosphate PO43-storing solution of phosphorus to be mixed with 1000mg P/L.
(2) with the phosphate PO43-storing solution artificial seawater stepwise dilution of 1000mg/L, be mixed with 0.0,20.0,50.0,100.0,200.0,500.0,800.0,1000.0 μ g P/L standard series.
3, the concentration of ascorbic acid is 85g/L in the first ascorbic acid solution.
4, the concentration of ammonium molybdate is 8g/L in the first ammonium molybdate chromogenic reagent solution, and the concentration of potassium antimony tartrate is 0.23g/L, and the concentration of sulfuric acid is 5%v/v;
Agents useful for same all adopts domestic reagent, and the purity of reagent is minimum pure for analyzing.
Present embodiment phosphate PO 4 3-The operation steps of test
Referring to Fig. 4, sample 71 after filtering by constant temperature automatic sampler 1 under the effect of peristaltic pump 4 through the 11 peristaltic pump tube 75, enter on the six-way valve 80 sampling ring 79 that connects, sampling ring 79 is full of by the 82 direct waste discharges of the 5th back pressure regulator enters waste liquid bottle 32.After sampling process finishes, six-way valve 80 rotates and makes interface F3 and A3, B3 and C3, E3 and D3 UNICOM state, peristaltic pump 4 pumps into current-carrying solution 72 through the 12 peristaltic pump tube 76, sample in the sampling ring 79 is released, enter in the 7th knitting reactor 81 and mix, then enter in the 7th threeway 83 and converge with the first ascorbic acid solution 73 that in the 13 peristaltic pump tube 77, pumps into, then entering the 8th knitting reactor 84 mixes, mixed solution converges with the first ammonium molybdate chromogenic reagent solution 74 that pumps into through the 14 peristaltic pump tube 78 in the 8th threeway 85, enter the 9th knitting reactor 86 hybrid reactions, the 9th knitting reactor 86 is wrapped on temperature control equipment 7 set temperatures are 37 ℃ on-line heating module.The reacted liquid pond 88 that circulates is carried out colorimetric estimation by detecting device 89 at the 880nm place, and the liquid that flows out directly enters waste liquid bottle 32 through the 6th back pressure regulator 87.
Can obtain phosphate PO in the solution by computer system 30 4 3-The phosphorus content value, the results are shown in Table 7, actual water sample is measured and the recovery testu data result, sees Table 8.
Table 7 phosphate working curve data
Concentration known (μ g/L) Peak height Peak area Return and calculate concentration (μ g/L)
0 0.0003 -0.177 1.9
10 0.0008 0.2494 15.3
20 0.0027 0.7239 22.4
50 0.0092 2.4343 48.1
100 0.0212 5.4232 92.9
200 0.0513 12.5361 199.5
400 0.1139 26.0291 401.8
Table 8 actual water sample is measured and the recovery testu data
The sample title Measured value (mg/L) Add scalar (mg/L) Measured value behind the mark-on (mg/L) The recovery
Municipal administration water 0.0010 0.02 0.0213 106.0％
Potable water 0.0086 0.02 0.0271 92.5％
Surface water 0.1404 0.05 0.1452 96.0％
Sewage 0.0615 0.1 0.1702 108.7％
By the result of table 7, table 8 as can be known, instrument of the present invention and method can detect phosphate PO in the solution accurately 4 3-The phosphorus content value.
Embodiment 5
Present embodiment silicate SiO 4 2-Reagent in the operation steps of test:
1, current-carrying is artificial seawater, the preparation of artificial seawater: 40g sodium chloride, the mixing of 0.32g sodium bicarbonate deionized water dissolving is settled to 1L.
2, the preparation of standard specimen:
(1) take by weighing the 0.946g anhydrous sodium metasilicate, be settled to the 1000ml volumetric flask with artificial seawater after the water dissolving, it is for subsequent use in the silicate SiO42-storing solution of SiO2 to be mixed with 1000mg/L.
(2) with the silicate SiO42-storing solution artificial seawater stepwise dilution of 1000mg/L, be mixed with 0.0,20.0,50.0,100.0,200.0,500.0,800.0,1000.0 μ g/L standard series.
3, the concentration of ascorbic acid is 65g/L in the second ascorbic acid solution.
4, oxalic acid solution concentration is 76-108g/L, and the purpose that adds oxalic acid solution is in order to reduce phosphate to the interference of reaction.
5, the second ammonium molybdate solution consist of the 5mL concentrated sulphuric acid, 16g four water ammonium molybdates [(NH4) 6Mo7O244H2O], 5.8g lauryl sodium sulfate deionized water dissolving mixes and is settled to 1L.
Agents useful for same all adopts domestic reagent, and the purity of reagent is minimum pure for analyzing.
Present embodiment silicate SiO 4 2-In the operation steps of test
Referring to Fig. 5, sample 92 after filtering by constant temperature automatic sampler 1 under the effect of peristaltic pump 4 through the 15 peristaltic pump tube 97, enter on the six-way valve 103 sampling ring 102 that connects, sampling ring 102 is full of by the 115 direct waste discharges of the 7th back pressure regulator enters waste liquid bottle 32.After sampling process finishes, six-way valve 103 rotates and makes interface F4 and A4, B4 and C4, E4 and D4 UNICOM state, peristaltic pump 4 pumps into current-carrying solution 93 through the 16 peristaltic pump tube 98, sample in the sampling ring 102 is released, enter in the tenth knitting reactor 104 and mix, then enter in the 9th threeway 105 and converge with the second ammonium molybdate chromogenic reagent solution 94 that pumps into through the 17 peristaltic pump tube 94, then entering the 11 knitting reactor 106 mixes, mixed solution converges with the oxalic acid solution 95 that pumps into through the 18 peristaltic pump tube 100 in the tenth threeway 107, enter the 12 knitting reactor 108 hybrid reactions, reacted solution converges with the second ascorbic acid solution 96 that pumps into through the 19 peristaltic pump tube 101 in the 11 threeway 109, enter the 13 knitting reactor 110 hybrid reactions, the 13 knitting reactor 110 is wrapped on temperature control equipment 7 set temperatures are 37 ℃ on-line heating module.The reacted liquid pond 111 that circulates is carried out colorimetric estimation by detecting device 112 at the 880nm place, and the liquid that flows out directly enters waste liquid bottle 32 through the 8th back pressure regulator 113.
Can obtain solution mesosilicic acid salt SiO by computer system 30 4 2-SiO 2Content value the results are shown in Table 9, and actual water sample is measured and the recovery testu data result sees Table 10.
Table 9 silicate working curve data
Concentration known (μ g/L) Return and calculate concentration (μ g/L) Peak height Peak area
0 0 0 -0.0455
10 9.3 0.0002 0.0456
20 16.2 0.0004 0.0908
50 48.6 0.0013 0.3021
100 96.2 0.0026 0.6127
200 198.8 0.0053 1.2818
400 401.6 0.0109 2.6042
Table 10 actual water sample is measured and the recovery testu data
The sample title Measured value (μ g/L) Add scalar (μ g/L) Measured value behind the mark-on (μ g/L) The recovery
Surface water 125 100 219 94％
Sewage 750 800 1500 93.7
By the result of table 9, table 10 as can be known, instrument of the present invention and method can detect solution mesosilicic acid salt SiO accurately 4 2-SiO 2Content value.
Above embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.

Claims (16)

1. full-automatic nutritive salt is analyzed instrument, it is characterized in that, comprise constant temperature automatic sampler (1), reagent refrigerating storehouse (2), main frame (3), main frame (3) comprises peristaltic pump (4), the sample fillup valve group (5) that is formed by at least 4 sample fillup valves, chemical analysis template (6), 4 temperature control equipments, detector set (8), peristaltic pump (4) comprises 19 peristaltic pump tubes at least, detector set (8) is comprised of at least 4 roads detecting device in parallel and 1 computer control system (30), and chemical analysis template (6) is divided into four zones, respectively by nitrate nitrogen (NO 3 -) and nitrite nitrogen (NO 2 -) analysis area, ammonia nitrogen (NH 4 +) analysis area, phosphate (PO 4 3-) analysis area, silicate (SiO 4 2-) the analysis area composition, constant temperature automatic sampler (1) links to each other by the peristaltic pump tube of capillary connecting pipe and peristaltic pump (4), peristaltic pump tube links to each other by the capillary connecting pipe successively with flow cell in chemical analysis template (6), the detecting device, detecting device is connected with computer control system (30) by signal wire, the airborne temperature of the first temperature control equipment (701) main control system (3), the second temperature control equipment (702) control ammonia nitrogen (NH 4 +) temperature of heating module in the analysis area, the 3rd temperature control equipment (703) control phosphate (PO 4 3-) temperature of heating module in the analysis area, the 4th temperature control equipment (704) control silicate (SiO 4 2-) temperature of heating module in the analysis area.
2. full-automatic nutritive salt according to claim 1 is analyzed instrument, it is characterized in that described nitrate nitrogen (NO 3 -) and nitrite nitrogen (NO 2 -) analysis area comprises two knitting reactor, two threeways, the capillary connecting pipe, container bottle, four-way valve (20), described two knitting reactor are the first knitting reactor (19) and the second knitting reactor (24), described two threeways are the first threeway (18) and the second threeway (21), four-way valve (20) has A ', B ', C ', four interfaces of D ', the first sample fillup valve (17) has A1 at least, B1, C1, D1, E1, six interfaces of F1, interface F1, peristaltic pump the first peristaltic pump tube (10), first sample introduction needle (9) of constant temperature automatic sampler (1) links to each other successively with the capillary connecting pipe; Interface B1 links to each other with the first sampling ring (16) two ends respectively with E1; Interface D1, the second peristaltic pump tube (11), the first current-carrying container bottle (15) link to each other successively with the capillary connecting pipe; Interface C1, the first threeway (18) first entrances, the first threeway (18) outlet, the first knitting reactor (19), four-way valve (20) D ' interface, four-way valve (20) C ' interface, the second threeway (21) first entrances, the second threeway (21) outlet, the second knitting reactor (24), flow cell (27) is communicated with successively with the capillary connecting pipe, the A ' of described four-way valve (20), B ' interface is connected to the two ends of cadmium reduction column (23) with the capillary connecting pipe, the second entrance of the first threeway (18) and the 3rd peristaltic pump tube (12), the first reagent container bottle (25) that chloride buffer solution is housed links to each other successively with the capillary connecting pipe, the second entrance of described the second threeway (21) and the 4th peristaltic pump tube (13), the second reagent container bottle (26) that the sulfanilamide (SN) chromogenic reagent solution is housed links to each other successively by the capillary connecting pipe, the interface A1 of the first sample fillup valve (17) is communicated with waste liquid tank (32) through the first back pressure regulator (22) with the capillary connecting pipe, be provided with the first flow cell (27) in the first detecting device (28), the first flow cell (27) links to each other with waste liquid tank (32) through the second back pressure regulator (29) with the capillary connecting pipe.
3. full-automatic nutritive salt according to claim 2 is analyzed instrument, it is characterized in that described ammonia nitrogen (NH 4 +) analysis area comprises four knitting reactor, four threeways, the capillary connecting pipe, container bottle, described four knitting reactor are the 3rd knitting reactor (54), the 4th knitting reactor (57), the 5th knitting reactor (59) and the 6th knitting reactor (61), described four threeways are the 3rd threeway (53), the 4th threeway (55), the 5th threeway (58) and the 6th threeway (60), the second sample fillup valve (52) has A2 at least, B2, C2, D2, E2, six interfaces of F2, interface F2, peristaltic pump the 5th peristaltic pump tube (45), second sample introduction needle (38) of constant temperature automatic sampler (1) links to each other successively with the capillary connecting pipe; Interface B2 links to each other with the second sampling ring (51) two ends respectively with E2; Interface D2, the 6th peristaltic pump tube (46), the second current-carrying container bottle (40) link to each other successively with the capillary connecting pipe; Interface C2, the 3rd threeway (53) first entrances, the 3rd threeway (53) outlet, the 3rd knitting reactor (54), the 4th threeway (55) first entrances, the 4th threeway (55) outlet, the 4th knitting reactor (57), the 5th threeway (58) first entrances, the 5th threeway (58) outlet, the 5th knitting reactor (59), the 6th threeway (60) first entrances, the 6th threeway (60) outlet, the 6th knitting reactor (61), flow cell (62) is communicated with successively with the capillary connecting pipe, described the 6th knitting reactor (61) is wrapped on the heating module, the second entrance of the 3rd threeway (53), the 7th peristaltic pump tube (47), buffer solution container bottle (41) is housed to link to each other successively with the capillary connecting pipe, the second entrance of described the 4th threeway (55), the 8th peristaltic pump tube (48), salicylate solution container bottle (42) is housed to link to each other successively by the capillary connecting pipe, the second entrance of described the 5th threeway (58), the 9th peristaltic pump tube (49), sodium nitroprusside solution container bottle (43) is housed to link to each other successively by the capillary connecting pipe, the second entrance of described the 6th threeway (60), the tenth peristaltic pump tube (50), the container bottle (44) that sodium dichloroisocyanate solution is housed links to each other successively by the capillary connecting pipe, the interface A2 of the second sample fillup valve (52) is communicated with waste liquid tank (32) through the 3rd back pressure regulator (56) by the capillary connecting pipe, be provided with the second flow cell (62) in the second detecting device (63), the second flow cell (62) links to each other with waste liquid tank (32) through the 4th back pressure regulator (64).
4. full-automatic nutritive salt according to claim 3 is analyzed instrument, it is characterized in that phosphate (PO 4 3-) analysis area comprises three knitting reactor, two threeways, capillary connecting pipe, container bottle, described three knitting reactor are the 7th knitting reactor (81), the 8th knitting reactor (84) and the 9th knitting reactor (86), described two threeways are the 7th threeway (83) and the 8th threeway (85), the 3rd sample fillup valve (80) has A3, B3, C3, D3, six interfaces of E3, F3 at least, and the 3rd sample introduction needle (70) of interface F3, the 11 peristaltic pump tube (75), constant temperature automatic sampler (1) etc. link to each other successively with the capillary connecting pipe; Interface B3 links to each other with the 3rd sampling ring (79) two ends respectively with E3; Interface D3, the 12 peristaltic pump tube (76), the 3rd current-carrying container bottle (72) link to each other successively with the capillary connecting pipe; Interface C3, the 7th knitting reactor (81), the 7th threeway (83) first entrances, the 7th threeway (83) outlet, the 8th knitting reactor (84), the 8th threeway (85) first entrances, the 8th threeway (85) outlet, the 9th knitting reactor (86), the 3rd flow cell (88) is communicated with successively with the capillary connecting pipe, described the 9th knitting reactor (86) is wrapped on the heating module, the second entrance of the 7th threeway (83), the 13 peristaltic pump tube (77), the container bottle (73) that the first ascorbic acid solution is housed links to each other successively with the capillary connecting pipe, the second entrance of described the 8th threeway (85), the 14 peristaltic pump tube (78), the container bottle (74) that the first ammonium molybdate solution is housed links to each other successively by the capillary connecting pipe, the interface A3 of the 3rd sample fillup valve (80) is communicated with waste liquid tank (32) through the 5th back pressure regulator (82) by the capillary connecting pipe, be provided with the 3rd flow cell (88) in the 3rd detecting device (89), the 3rd flow cell (88) links to each other with waste liquid tank (32) through the 6th back pressure regulator (87).
5. full-automatic nutritive salt according to claim 4 is analyzed instrument, it is characterized in that silicate (SiO 4 2-) analysis area comprises four knitting reactor, three threeways, the capillary connecting pipe, container bottle, described four knitting reactor are the tenth knitting reactor (104), the 11 knitting reactor (106), the 12 knitting reactor (108) and the 13 knitting reactor (110), described three threeways are the 9th threeway (105), the tenth threeway (107) and the 11 threeway (109), the 4th sample fillup valve (103) has A4 at least, B4, C4, D4, E4, six interfaces of F4, interface F4, the 15 peristaltic pump tube (97), the 4th sample introduction needle (91) of constant temperature automatic sampler (1) etc. link to each other successively with the capillary connecting pipe; Interface B4 links to each other with the 4th sampling ring (102) two ends respectively with E4; Interface D4, the 16 peristaltic pump tube (98), the 4th current-carrying container bottle (93) link to each other successively with the capillary connecting pipe; Interface C4, the tenth knitting reactor (104), the 9th threeway (105) first entrances, the 9th threeway (105) outlet, the 11 knitting reactor (106), the tenth threeway (107) first entrances, the tenth threeway (107) outlet, the 12 knitting reactor (108), the 11 threeway (109) first entrances, the 11 threeway (109) outlet, the 13 knitting reactor (110), the 4th flow cell (111) is communicated with successively with the capillary connecting pipe, described the 13 knitting reactor (110) is wrapped on the heating module, the second entrance of the 9th threeway (105), the 17 peristaltic pump tube (99), the second ammonium molybdate solution container bottle (94) links to each other successively with the capillary connecting pipe, the second entrance of the described ten threeway (107), the 18 peristaltic pump tube (100), oxalic acid solution container bottle (95) is housed to link to each other successively by the capillary connecting pipe, the second entrance of described the 11 threeway (109), the 19 peristaltic pump tube (101), the second ascorbic acid solution container bottle (96) links to each other successively by the capillary connecting pipe, the interface A4 of the 4th sample fillup valve (103) is communicated with waste liquid tank (32), be provided with the 4th flow cell (111) in the 4th detecting device (112), the 4th flow cell (111) links to each other with waste liquid tank (32) through the 8th back pressure regulator (113).
6. full-automatic nutritive salt according to claim 5 is analyzed instrument, it is characterized in that, described peristaltic pump tube internal diameter is 0.38～1.85mm, the peristaltic pump pump speed is 15～60 rev/mins, described reagent refrigerating storehouse (2) is at least 4 * 6 designs, can put into five kinds of all reagent that substance-measuring is required, constant temperature automatic sampler (1) comprises at least four sample introduction needle (35) or comprises a sample introduction needle and at least one minute four X-over, constant temperature automatic sampler (1) also comprises platter (33), rinse bath (36), test tube more than 5 (34), sample introduction needle (35) links to each other with peristaltic pump (4) by the capillary connecting pipe.
7. full-automatic nutritive salt according to claim 6 is analyzed instrument, it is characterized in that the first to the 5th knitting reactor (19,24,54,57,59), the 7th to the 8th knitting reactor (81,84), the tenth to the 12 knitting reactor (104,106,108) length are 0.5～2m; The 6th knitting reactor (61) length is 3～10m, and temperature is 40-70 ℃; The 9th knitting reactor (86) length is 1～5m, and temperature is 30-60 ℃; The 13 knitting reactor (110) length is 0.5～9m, and temperature is 30-60 ℃; The length of first to fourth sampling ring (16,51,79,102) is 0.5-4m; The length of each capillary connecting pipe is 0.1-1m.
8. use full-automatic nutritive salt as claimed in claim 7 to analyze instrument and measure seawater Nitrite Nitrogen (NO 2 -) method, it is characterized in that, with after filtering sample by constant temperature automatic sampler (1) under the effect of peristaltic pump (4) through the first peristaltic pump tube (10), enter upper the first sampling ring (16) that connects of the first sample fillup valve (17), first with sampling ring (16) be full of by the first back pressure regulator (22) directly waste discharge enter waste liquid bottle (32), after sampling process finishes, the first sample fillup valve (17) interface F1 and A1, B1 and C1, E1 and D1 UNICOM, peristaltic pump (4) pumps into the current-carrying solution in the first current-carrying container bottle (15) through the second peristaltic pump tube (11), sample in the first sampling ring (16) is released, enter in the first threeway (18) and converge with the chloride buffer solution that enters through the 3rd peristaltic pump tube (12), mixed liquor enters the first knitting reactor (19) to be mixed, mixed solution enters four-way valve (20) through four-way valve (20) D ' mouth, wherein as four-way valve (20) A ' and B ', when D ' is connected with C ', mixed solution goes out by four-way valve C ' mouthful, in the second threeway (21), converge with the sulfanilamide (SN) developer that enters through the 4th peristaltic pump tube (13), enter the second knitting reactor (24) hybrid reaction, reacted liquid enters the first flow cell (27) again, carry out colorimetric estimation by the second detecting device (28) at the 540nm place, the liquid that flows out directly enters waste liquid bottle (32) through the second back pressure regulator (29), by absorbance peak height value or peak area value and the typical curve comparing calculation solution Nitrite Nitrogen (NO of computer system (30) with sample 2 -) content.
9. use full-automatic nutritive salt as claimed in claim 7 to analyze instrument and measure Nitrate Nitrogen in Seawater (NO 3 -), nitrite nitrogen (NO 2 -) method, it is characterized in that, with after filtering sample by constant temperature automatic sampler (1) under the effect of peristaltic pump (4) through the first peristaltic pump tube (10), enter upper the first sampling ring (16) that connects of the first sample fillup valve (17), first with sampling ring (16) be full of by the first back pressure regulator (22) directly waste discharge enter waste liquid bottle (32), after sampling process finishes, the first sample fillup valve (17) interface F1 and A1, B1 and C1, E1 and D1 UNICOM, peristaltic pump (4) pumps into the current-carrying solution in the first current-carrying container bottle (15) through the second peristaltic pump tube (11), sample in the first sampling ring (16) is released, enter in the first threeway (18) and converge with the chloride buffer solution that enters through the 3rd peristaltic pump tube (12), mixed liquor enters the first knitting reactor (19) to be mixed, mixed solution enters four-way valve (20) through four-way valve (20) D ' mouth, out enter afterwards cadmium reduction column (23) by A ' mouth, with the nitrate nitrogen (NO in the sample liquid 3 -) be reduced to nitrite nitrogen (NO 2 -), enter four-way valve B ' through cadmium reduction column (23) outlet solution out, go out by four-way valve C ' mouthful, in the second threeway (21), converge with the sulfanilamide (SN) developer that enters through the 4th peristaltic pump tube (13), enter the second knitting reactor (24) hybrid reaction, reacted liquid enters the first flow cell (27) again, carry out colorimetric estimation by the second detecting device (28) at the 540nm place, the liquid that flows out directly enters waste liquid bottle (32) through the second back pressure regulator (29), by computer system (30) with nitrate nitrogen (NO in the absorbance peak height value of sample or peak area value and the typical curve comparing calculation solution 3 -) add nitrite nitrogen (NO 2 -) content; Wherein when four-way valve A ' was connected with C ' with B ', D ', the analysis result that the result of acquisition is was nitrite nitrogen (NO 2 -) content, nitrate nitrogen (NO in the solution 3 -) add nitrite nitrogen (NO 2 -) content deduct nitrite nitrogen (NO 2 -) content be nitrate nitrogen (NO 3 -) analysis result.
10. measurement Nitrate Nitrogen in Seawater (NO according to claim 9 3 -), nitrite nitrogen (NO 2 -) method, it is characterized in that described current-carrying solution is artificial seawater, artificial seawater consists of: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and to be settled to 1L; The pH value of described chloride buffer solution is 8～9; The phosphoric acid of consisting of in the sulfanilamide (SN) chromogenic reagent solution: 50-200ml85%, 17～67g sulfanilamide (SN) (C 6H 8N 2O 2S), 0.37～2.5g N-(1-naphthyl) ethylenediamine-hydrochloride (C 12H 16Cl 2N 2), the deionized water dissolving mixing is settled to 1L.
Measure Ammonia In Sea Water (NH 11. use full-automatic nutritive salt as claimed in claim 7 to analyze instrument 4 +) content assaying method, it is characterized in that, sample after filtering (39) by constant temperature automatic sampler (1) under the effect of peristaltic pump (4) through the 5th peristaltic pump tube (45), enter upper the second sampling ring (51) that connects of the second six-way valve (52), with the second sampling ring (51) be full of by the 3rd back pressure regulator (56) directly waste discharge enter waste liquid bottle (32), after sampling process finishes, the second six-way valve (52) rotates and makes interface F2 and A2, B2 and C2, E2 and D2 UNICOM state, peristaltic pump (4) pumps into current-carrying solution (40) through the 6th peristaltic pump tube (46), sample in the second sampling ring (51) is released, sample enters in the 3rd threeway (53) and converges with the buffer solution that enters through the 7th peristaltic pump tube (47), entering the 3rd knitting reactor (54) mixes, mixed solution converges with the salicylate solution that enters through the 8th peristaltic pump tube (48) in the 4th threeway (55), enter the 4th knitting reactor (57) hybrid reaction, mixed solution converges with the sodium nitroprusside solution (43) that enters through the 9th peristaltic pump tube (49) in the 5th threeway (58), enter the 5th knitting reactor (59) hybrid reaction, mixed solution converges with the sodium dichloroisocyanate solution (44) that enters through the tenth peristaltic pump tube (44) in the 6th threeway (60), enter the 6th knitting reactor (61) hybrid reaction, temperature of reaction is set to 60 ℃, the reacted liquid pond (62) that circulates again, carry out colorimetric estimation by detecting device (63) at the 660nm place, the liquid that flows out directly enters waste liquid bottle (32) through the 4th back pressure regulator (64), by absorbance peak height value or peak area value and the typical curve comparing calculation ammonia nitrogen in solution (NH of computer system (30) with sample 4 +) content.
12. measurement Ammonia In Sea Water (NH according to claim 11 4 +) content assaying method, it is characterized in that described current-carrying solution is artificial seawater, artificial seawater consists of: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and to be settled to 1L; The pH value of buffer solution should be 5～6, and it consists of 21～45g sodium potassium tartrate tetrahydrate (C 4H 4O 6KNa4H 2O), 17～36g sodium citrate (C 6H 5O 7Na 32H 2O), the deionized water dissolving mixing is settled to 1L; Salicylate solution consist of 10-40g NaOH (NaOH), add 50-160g sodium salicylate (C 7H 5NaO 3), the deionized water dissolving mixing is settled to 1L; Sodium nitroprussiate (Na 2[Fe (CN) 5NO] 2H 2O) concentration of solution is 2～9g/L; Sodium dichloroisocyanate (C 3N 3O 3Cl 2Na2H 2O) concentration of solution (44) is 1～7g/L.
Measure Seawater Phosphate (PO 13. use full-automatic nutritive salt as claimed in claim 7 to analyze instrument 4 3-) the method for content value, it is characterized in that, sample after filtering (71) by constant temperature automatic sampler (1) under the effect of peristaltic pump (4) through the 11 peristaltic pump tube (75), enter upper the 3rd sampling ring (79) that connects of the 3rd six-way valve (80), with the 3rd sampling ring (79) be full of by the 5th back pressure regulator (82) directly waste discharge enter waste liquid bottle (32), after sampling process finishes, the 3rd six-way valve (80) rotates and makes interface F3 and A3, B3 and C3, E3 and D3 UNICOM state, the state shown in the dotted line in the figure, peristaltic pump (4) pumps into current-carrying solution (72) through the 12 peristaltic pump tube (76), sample in the sampling ring (79) is released, enter in the 7th knitting reactor (81) and mix, then enter in the 7th threeway (83) and converge with the first ascorbic acid solution (73) that in the 13 peristaltic pump tube (77), pumps into, then entering the 8th knitting reactor (84) mixes, mixed solution converges with the first ammonium molybdate chromogenic reagent solution (74) that pumps into through the 14 peristaltic pump tube (78) in the 8th threeway (85), enter the 9th knitting reactor (86) hybrid reaction, temperature of reaction is 37 ℃, reacted liquid enters the 3rd flow cell (88) and carries out colorimetric estimation by the 3rd detecting device (89) at the 880nm place, the liquid that flows out directly enters waste liquid bottle (32) through the 6th back pressure regulator (87), will can obtain phosphate (PO in the solution in the absorbance peak height value of sample or peak area value and the typical curve comparing calculation solution by computer system (30) 4 3-) the phosphorus content value.
14. instrument according to claim 13 is measured Seawater Phosphate (PO 4 3-) the method for content value, it is characterized in that described current-carrying solution is artificial seawater, artificial seawater consists of: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and are settled to 1L; The concentration of ascorbic acid is 50～100g/L in described the first ascorbic acid solution; The concentration of ammonium molybdate is 5～12g/L in described the first ammonium molybdate chromogenic reagent solution, and the concentration of potassium antimony tartrate is 0.1～0.4g/L, and the concentration of sulfuric acid is 2-5%(v/v).
Measure seawater mesosilicic acid salt (SiO 15. use full-automatic nutritive salt as claimed in claim 7 to analyze instrument 4 2-) method, it is characterized in that, sample after filtering (92) by constant temperature automatic sampler (1) under the effect of peristaltic pump (4) through the 15 peristaltic pump tube (97), enter upper the 4th sampling ring (102) that connects of the 4th six-way valve (103), with the 4th sampling ring (102) be full of by the 7th back pressure regulator (115) directly waste discharge enter waste liquid bottle (32), after sampling process finishes, the 4th six-way valve (103) rotates and makes interface F4 and A4, B4 and C4, E4 and D4 UNICOM state, peristaltic pump (4) pumps into current-carrying solution through the 16 peristaltic pump tube (98), sample in the 4th sampling ring (102) is released, enter in the tenth knitting reactor (104) and mix, then enter in the 9th threeway (105) and converge with the second ammonium molybdate chromogenic reagent solution that pumps into through the 17 peristaltic pump tube (94), then entering the 11 knitting reactor (106) mixes, mixed solution converges with the oxalic acid solution that pumps into through the 18 peristaltic pump tube (100) in the tenth threeway (107), enter the 12 knitting reactor (108) hybrid reaction, reacted solution converges with the second ascorbic acid solution that pumps into through the 19 peristaltic pump tube (101) in the 11 threeway (109), enter the 13 knitting reactor (110) hybrid reaction, temperature of reaction is 37 ℃, reacted liquid enters the 4th flow cell (111) and carries out colorimetric estimation by the 4th detecting device (112) at the 880nm place, the liquid that flows out directly enters waste liquid bottle (32) through the 8th back pressure regulator (113), will can obtain can obtain in the solution solution mesosilicic acid salt (SiO in the absorbance peak height value of sample or peak area value and the typical curve comparing calculation solution by computer system (30) 4 2-) SiO 2Content value.
16. measurement seawater mesosilicic acid salt (SiO according to claim 15 4 2-) method, it is characterized in that wherein current-carrying solution (93) is artificial seawater, artificial seawater consists of: 30～50g sodium chloride, 0.1-0.5g sodium bicarbonate deionized water dissolving mix and to be settled to 1L; The second ammonium molybdate chromogenic reagent solution consist of 2～6mL concentrated sulphuric acid, 8～23g, four water ammonium molybdate [(NH 4) 6Mo 7O 244H 2O], the mixing of 2～9g lauryl sodium sulfate deionized water dissolving is settled to 1L; Ascorbic acid solution concentration is 30-70g/L; Oxalic acid solution (95) concentration is 76-108g/L.
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