CN1560624A - Automatic analyzing instrument for trace metal element in sea water, river water - Google Patents
Automatic analyzing instrument for trace metal element in sea water, river water Download PDFInfo
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Abstract
The invention is an automatic analysis method for trace element in sea water and river water; it is mainly made up of online processing device and testing device. The testing device is the low pressure ion chromatogram device, the working pressure is 2-3X10 to the power 5 Pa. the sample online processing device has two structures, one is the direct processing type, and the other is the complexation type. The direction processing type includes condensing pile, low pressure pump, converting valve, sample container, rinsing liquid container and desorbing container; the complexation type includes condensing pile, low pressure pump, converting valve, sample container, rinsing container, desorbing liquid container, complexation agent container and the reactor. The instrument can upgrade the analysis precision, and the instrument is very small.
Description
Technical field
The invention belongs to the analytical instrument of trace metal element, particularly the automatic analyzer of seawater, river mouth underwater trace metallic element.
Background technology
Because activity of human beings, content of beary metal increases year by year in ocean, the river, and constantly accumulation directly influences the normal breeding of organism in water, and human health is worked the mischief.In order to study the relation of seawater, the contained trace metal element of river mouth water and ecologic environment and mankind's activity, need provide necessary data and the information of studying by analysis to these trace metal elements.About the analytical instrument of seawater, river mouth underwater trace metallic element, be complementary with certain analytical approach.Existing analytical approach comprises the mensuration of the separation and concentration and the trace-metal of sample, the separation and concentration of sample adopts solvent extraction, ion exchange process and coprecipitation usually, the mensuration of trace-metal adopts spectrophotometric method, atomic absorption spectrophotometry, x ray fluorescence spectrometry, ICP-emission spectrometry, anodic stripping voltammetry and neutron activation analysis method usually, pairing instrument of above-mentioned separation and concentration and assay method or volume are big or cost an arm and a leg or poor anti jamming capability, are difficult to adapt to on-the-spot on-line analysis.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide the automatic analyzer of a kind of seawater, river mouth underwater trace metallic element, to satisfy the needs of on-the-spot on-line analysis.
Inventing described automatic analyzer mainly is made of sample online treatment device and proving installation.Proving installation is the low pressure ion chromatography analyser, and working pressure is 2～3 * 10
5Pa.Sample online treatment device has two kinds of versions, and a kind of is direct processing type, and another kind of is complexing processing type.Directly the processing type comprises evaporating column, low-lift pump, cross-over valve, sample receiver, soda liquor container and stripping liquid container; The delivery outlet of low-lift pump is connected with the input port of evaporating column by pipe fitting, and the input port of low-lift pump is connected with the delivery outlet of cross-over valve by pipe fitting, and each input port of cross-over valve is connected with sample receiver, soda liquor container and stripping liquid container respectively by pipe fitting.That the job step of the sample online treatment device of this kind version is followed successively by is concentrated, cleaning and desorb, concentrating is that tested sample is pumped into evaporating column, trace metal element in the tested sample is adsorbed on the evaporating column, cleaning is to pump into cleaning fluid in evaporating column and relevant stream, interfering materials such as the remaining sodium chloride in removal evaporating column and the relevant stream thereof, magnesium, calcium, desorb is to pump into stripping liquid in evaporating column, makes the trace metal element that is adsorbed on the evaporating column break away from the low pressure ion chromatography analytic system that evaporating column enters instrument.Complexing processing type comprises evaporating column, low-lift pump, cross-over valve, sample receiver, soda liquor container, stripping liquid container, complexing agent container and reactor; Low-lift pump is two, a low-lift pump connects between evaporating column and the cross-over valve, its delivery outlet is connected with the input port of evaporating column by pipe fitting, its input port is connected with the delivery outlet of cross-over valve by pipe fitting, another low-lift pump is connected between reactor and sample receiver and the complexing agent container, its input port is by pipe fitting and sample receiver and the connection of complexing agent container, and its delivery outlet is connected with reactor by pipe fitting; Each input port of cross-over valve is connected with soda liquor container, stripping liquid container and reactor respectively by pipe fitting.The job step of the sample online treatment device of this kind version is followed successively by complexing, concentrate, clean and desorb, complexing is that tested sample and complexing agent are pumped into reactor, make trace metal element in the tested sample and the complexing agent generation metal complex that reacts, concentrate is that mixed liquor with the containing metal complex compound pumps into evaporating column, metal complex in the mixed liquor is adsorbed on the evaporating column, cleaning is to pump into cleaning fluid in evaporating column and relevant stream, remove the remaining sodium chloride in evaporating column and the relevant stream thereof, magnesium, interfering materials such as calcium, desorb is to pump into stripping liquid in evaporating column, makes the metal complex that is adsorbed on the evaporating column break away from the low pressure ion chromatography analytic system that evaporating column enters instrument.The outlet of evaporating column in the sample online treatment device is connected with sampling valve in the low pressure ion chromatography analyser by pipe fitting.
Directly the column packing of the evaporating column in the processing type online treatment device is imido oxalic acid class macroporous absorbent resin or ball shaped cellulose metal absorbent.Imido oxalic acid class macroporous absorbent resin belongs to the commercial goods, and the preparation method of ball shaped cellulose metal absorbent is as follows:
(1) preparation of viscose glue is pressed lixiviating liquid with 16～18%NaOH solution with cotton behind 50～60 ℃ of dipping 30～40min, with the cotton of pressing lixiviating liquid in 20～25 ℃ place 12%NaOH solution to flood 20～25min and suction filtration once more, squeezing is done near, the dipping bath of twice dipping is 1: 20 than (ratio of the oven dry weight of pulp and alkali lye), will through twice dipping, the cotton that press dry pulverize the back in 20～25 ℃ aging 48～50 hours, press cellulose (cotton): CS then
2=2: 1 ratio adds CS
2Vibrated 2～2.5 hours, and added the dissolving of 4%NaOH solution and surfactant lauryl sodium sulfate again and make viscose glue, the consumption of lauryl sodium sulfate is 0.10～0.20% of a cellulose;
(2) preparation of cellulose bead body is with transformer oil or 200
#Gasoline is disperse phase, disperse phase and viscose glue be in a ratio of 4: 1, with the sodium oleate is spreading agent, the consumption of spreading agent is 0.3～0.4% of a viscose glue weight, under agitation disperse phase, viscose glue and spreading agent being added in the container is uniformly dispersed it, be heated to 65～70 ℃ and constant temperature 1.0～1.5 hours with 2～3 ℃/min then, upper oil phase is reclaimed in the cooling back, and the solution suction filtration and the water of the plain pearl body of lower floor's fibre-bearing cleaned up the spherical cellulose bead that promptly obtains white;
(3) graft reaction adds the spherical cellulose bead and the water of water cut 75.3% in the container that stirrer, reflux condensing tube and thermometer are housed, the weight ratio of spherical cellulose bead and water is 1: 1.5～2, it is fine to add propylene after stirring 10～15min under 20～25 ℃, fine and the cellulosic mol ratio of propylene is 2～3: 1, react after 1.0～1.5 hours, filter, wash, be drying to obtain cyanethyl cellulose pearl body;
(4) crosslinked, saponification is being equipped with stirrer, tap funnel, temperature is taken into account cyanethyl cellulose pearl body and the water that adds water cut 30.0% in the container that has reflux condensing tube, the weight ratio of cyanethyl cellulose pearl body and water is 1: 1.5～2, add epichlorokydrin then, the volume ratio of epichlorokydrin and water is 1: 10～15, stir, slowly add 8～12%NaOH solution through tap funnel, the volume ratio of NaOH solution and water is 2～2.5: 1, be warming up to 70～80 ℃ with 2～3 ℃/min in 20～25 ℃ of stirrings after 1.5～2.0 hours, continue reaction 1.5～2.0 hours, cold filtration is transferred pH to 6.5 with 0.6～1.0mol/LHCl solution after reclaiming alkali lye, refilter, clean, drying promptly gets the ball shaped cellulose metal absorbent.
After testing, the pore structure specific surface area of ball shaped cellulose metal absorbent can reach 189.12m
2/ g; 65 ℃ of following oxidations 24 hours, the loss in weight only was 0.11%; After 120 days, the loss in weight is still less than 0.8% through microbial degradation; Heat decomposition temperature is about 270 ℃; 20 ℃ down with the acid soak of 2.0mol/L 24 hours, the loss in weight is 0.59%, 20 ℃ down with the dipping by lye of 2.0mol/L 24 hours, the loss in weight is 1.31%; Pressure drop values during beginning deformation is 4.2mmHg/cm, has bigger specific surface area, excellent chemical stability and stronger anti-mechanically deform ability.
The column packing of the evaporating column in the complexing processing type online treatment device is C
18Chemically bonded stationary phase belongs to the commercial goods.
The present invention has following beneficial effect:
1, is the sample online treatment device of core and the analytical instrument that the low pressure ion chromatography analyser constitutes with the evaporating column, can eliminates to disturb and improve analysis precision, can reduce manufacturing cost again, and can make the analytical instrument miniaturization.
2, can carry out on-line automatic analysis to the trace metal element in seawater, the river mouth water easily, lowest detectable limit reaches or is better than national standard, and analysis precision is better than 4%.
3, the ball shaped cellulose metal absorbent not only has bigger specific surface area, excellent chemical stability and stronger anti-mechanically deform ability, and productive rate height, cost are low, as the column packing of evaporating column, can guarantee the quality that sample is handled effectively, cost that again can lowering apparatus.
Description of drawings
Fig. 1 is a kind of structure diagram of the automatic analyzer of seawater of the present invention, river mouth underwater trace metallic element, and instrument is in the sample introduction state;
Fig. 2 is the synoptic diagram that the automatic analyzer among Fig. 1 is in analysis state;
Fig. 3 is a kind of structural drawing of sample online treatment device;
Fig. 4 is the another kind of structural drawing of sample online treatment device;
Fig. 5 is a kind of structural drawing of evaporating column.
Among the figure, 1-sample online treatment device, 2-sampling valve, 3-low-lift pump, 4-eluent container, 5-low-pressure chromatography separating column, 6-low-lift pump, 7-past column reaction liquid container, 8-reactor, 9-optical flow cell, 10-fluorescence detector, 11-chromatographic work station, 12-evaporating column, 13-low-lift pump, 14-cross-over valve, 15-sample receiver, 16-soda liquor container, 17-stripping liquid container, 19-low-lift pump, 20-reactor, 21-import, 22-cylinder, 23-column packing, 24-filter plate, 25-outlet.
Embodiment
Embodiment 1
In the present embodiment, structure such as Fig. 1, Fig. 2, shown in Figure 3 of the automatic analyzer of seawater, river mouth underwater trace metallic element are made of sample online treatment device 1 and low pressure ion chromatography analyser.
Sample online treatment device 1 comprises evaporating column 12, low-lift pump 13, cross-over valve 14, sample receiver 15, soda liquor container 16 and stripping liquid container 17; Low-lift pump 13 is selected commercially available electronic peristaltic pump (claiming electronic micropump again) for use, output maximum pressure 0～5 * 10
5Pa, cross-over valve 14 is selected four way solenoid valve for use, the structure of evaporating column 12 as shown in Figure 5, mainly by cylinder 22 and be installed in the filter plate 24 of cylinder liquid outlet end inner chamber and column packing 23 that cylinder intracavity is filled constitutes, cylinder is the shell container, its two ends are provided with liquid-inlet 21 and liquid outlet 25, column packing 23 is imido oxalic acid class macroporous absorbent resin or ball shaped cellulose metal absorbent, imido oxalic acid class macroporous absorbent resin belongs to the commercial goods, the preparation method of ball shaped cellulose metal absorbent is as follows: the preparation of (1) viscose glue is pressed lixiviating liquid with 18%NaOH solution with the cotton of moisture 10% behind 50 ℃ of dipping 30min, to press the cotton of lixiviating liquid to place 12%NaOH solution to flood 20min and suction filtration once more in 20～25 ℃, squeezing is done near, and the dipping bath of twice dipping is 1: 20 than (ratio of the oven dry weight of pulp and alkali lye); Will through twice dipping, the cotton that press dry pulverize the back in 20～25 ℃ aging 48 hours, press cellulose (cotton): CS then
2=2: 1 ratio adds CS
2Vibrated 2.5 hours, and added the dissolving of 4%NaOH solution and surfactant lauryl sodium sulfate again and make viscose glue, the consumption of lauryl sodium sulfate is 0.1% of a cellulose; (2) preparation of cellulose bead body is disperse phase with the transformer oil, disperse phase and viscose glue be in a ratio of 4: 1, with the sodium oleate is spreading agent, the consumption of spreading agent is 0.4% of a viscose glue weight, under agitation disperse phase, viscose glue and spreading agent being added in the container is uniformly dispersed it, be heated to 70 ℃ and constant temperature 1.5 hours with 2 ℃/min then, upper oil phase is reclaimed in cooling back, the solution of the plain pearl body of lower floor's fibre-bearing is placed in the Buchner funnel suction filtration and water cleans up the spherical cellulose bead that promptly obtains white; (3) graft reaction adds the spherical cellulose bead and the water (weight ratio of spherical cellulose bead and water is 1: 1.5) of water cut 75.3% in the container that stirrer, reflux condensing tube and thermometer are housed, it is fine to add propylene after stirring 10min under 20～25 ℃, fine and the cellulosic mol ratio of propylene is 2.4: 1, react after 1.0 hours, filter, wash, be drying to obtain cyanethyl cellulose pearl body; (4) crosslinked, saponification is being equipped with stirrer, tap funnel, temperature is taken into account cyanethyl cellulose pearl body and the water (weight ratio of cyanethyl cellulose pearl body and water is 1: 2) that adds water cut 30.0% in the container that has reflux condensing tube, add epichlorokydrin (volume ratio of epichlorokydrin and water is 1: 12) then, stir, slowly add 12%NaOH solution (volume ratio of NaOH solution and water is 2: 1) through tap funnel, be warming up to 75 ℃ with 2 ℃/min in 20～25 ℃ of stirrings after 2.0 hours, continue reaction 2.0 hours, cold filtration is transferred pH to 6.5 with 0.6mol/L HCl solution after reclaiming alkali lye, refilter, clean, drying promptly gets the ball shaped cellulose metal absorbent.When the column packing of evaporating column is the ball shaped cellulose metal absorbent, column section diameter phi 5mm, column length 80mm; When the column packing of evaporating column is imido oxalic acid class macroporous absorbent resin, diameter of section φ 5mm, column length 60mm.
The assembling mode of sample online treatment device 1 each member: the delivery outlet of low-lift pump 13 is connected with the liquid inlet 21 of evaporating column 12 by pipe fitting, the input port of low-lift pump 13 is connected by the delivery outlet of pipe fitting with cross-over valve 14, and each input port of cross-over valve 14 is connected with sample receiver 15, soda liquor container 16 and stripping liquid container 17 respectively by pipe fitting.
The working pressure of low pressure ion chromatography analyser is 2～3 * 10
5Pa comprises sampling valve 2, low-lift pump 3, eluent container 4, low-pressure chromatography separating column 5, low-lift pump 6, past column reaction liquid container 7, reactor 8, optical flow cell 9, fluorescence detector 10 and chromatographic work station 11; Sampling valve 2 is selected six logical auto injection valves for use, and low-lift pump 3 and low-lift pump 6 are selected commercially available electronic peristaltic pump (claiming electronic micropump again) for use, output maximum pressure 0～5 * 10
5Pa, low-pressure chromatography separating column 5 diameter of section φ 5mm, column length 60mm, column packing is by styrene-divinylbenzene high molecular polymer and the concentrated sulphuric acid or chlorosulfonic acid sulfonation and make, exchange capacity 0.04mmol/g, reactor 8 is the spiral type tube type structure, polyfluortetraethylene pipe coiling by internal diameter 0.3～0.5mm forms, optical flow cell 9 is made by hard glass, fluorescence detector 10 is made up of light source, photoelectric cell, amplifier, logarithmic amplifier, digital display gauge outfit, and chromatographic work station 11 is made up of the computer interface circuit and the software kit of routine.The assembling mode of each member of low pressure ion chromatography analyser and with the assembling mode of sample online treatment device 1: the inlet of sampling valve 2 is connected with evaporating column liquid outlet 25 in the sample online treatment device 1 by pipe fitting; The outlet of low-lift pump 3 is connected by the inlet of pipe fitting with sampling valve 2, and the inlet of low-lift pump 3 is communicated with eluent container 4 by pipe fitting; The inlet of low-pressure chromatography separating column 5 is connected by the outlet of pipe fitting with sampling valve 2, and the liquid outlet of low-pressure chromatography separating column 5 is connected by the inlet of pipe fitting with reactor 8; The liquid outlet of reactor 8 is connected with optical flow cell 9 by pipe fitting; The outlet of low-lift pump 6 is connected by the inlet of pipe fitting with reactor 8, and the import of low-lift pump 6 is communicated with past column reaction liquid container 7 by pipe fitting; Fluorescence detector 10 changes the light signal that receives into electric signal and sends chromatographic work station 11 to, and chromatographic work station 11 handles and draw out spectrogram with the electrical signal transfer that receives to computing machine.
When the column packing of evaporating column is the ball shaped cellulose metal absorbent, the workflow of instrument is: 1, operating instrument, by low-lift pump 13 tested seawater or river mouth water are pumped into evaporating column 12, the trace metal element in the tested river mouth water is adsorbed on the evaporating column 12; 2, by low-lift pump 13 cleaning fluid is pumped in evaporating column 12 and the relevant stream, remove interfering materials such as remaining sodium chloride in evaporating column and the relevant stream thereof, magnesium, calcium; 3, by low-lift pump 13 stripping liquid is pumped in the evaporating column 12, make the trace metal element that is adsorbed on the evaporating column 12 break away from evaporating column and enter the low pressure ion chromatography analytical equipment and test, can obtain Cu by sampling valve 2
2+, Ni
2+, Zn
2+, Pb
2+, Cd
2+Chromatogram Deng trace metal element.
When the column packing of evaporating column is imido oxalic acid class macroporous absorbent resin, the workflow of instrument is: 1, operating instrument, by low-lift pump 13 tested seawater or river mouth water are pumped into evaporating column 12, the trace metal element in the tested river mouth water is adsorbed on the evaporating column 12; 2, by low-lift pump 13 with cleaning fluid---ammonium acetate solution pumps in evaporating column 12 and the relevant stream, removes magnesium, calcium, pumps into cleaning fluid then---deionized water is removed other chaff interference; 3, by low-lift pump 13 stripping liquid is pumped in the evaporating column 12, make the trace metal element that is adsorbed on the evaporating column 12 break away from evaporating column and enter the low pressure ion chromatography analytical equipment and test, can obtain Cu by sampling valve 2
2+, Ni
2+, Zn
2+, pb
2+, Cd
2+Chromatogram Deng trace metal element.
Embodiment 2
In the present embodiment, structure such as Fig. 1, Fig. 2, shown in Figure 4 of the automatic analyzer of seawater, river mouth underwater trace metallic element are made of sample online treatment device 1 and low pressure ion chromatography analyser.
The working pressure of low pressure ion chromatography analyser is identical with embodiment 1 with structure.
Sample online treatment device 1 comprises evaporating column 12, low-lift pump 13, cross-over valve 14, sample receiver 15, soda liquor container 16, stripping liquid container 17, complexing agent container 18, low-lift pump 19 and reactor 20; The assembling mode of above-mentioned member: the delivery outlet of low-lift pump 13 is connected with the liquid inlet 21 of evaporating column 12 by pipe fitting, and the input port of low-lift pump 13 is connected by the delivery outlet of pipe fitting with cross-over valve 14; Each input port of cross-over valve 14 is connected with soda liquor container 16, stripping liquid container 17 and reactor 20 respectively by pipe fitting; The input port of low-lift pump 19 is by pipe fitting and sample receiver 15 and 18 connections of complexing agent container, and the delivery outlet of low-lift pump 19 is connected with reactor 20 by pipe fitting.Low-lift pump 13 and low-lift pump 19 are selected commercially available electronic peristaltic pump (claiming electronic micropump again) for use, output maximum pressure 0～5 * 10
5Pa, low-lift pump 19 both can adopt a binary channels pump, can adopt two single channel pumps again; The structure of evaporating column 12 as shown in Figure 5, mainly by cylinder 22 and be installed in the filter plate 24 of cylinder liquid outlet end inner chamber and column packing 23 that cylinder intracavity is filled constitutes, cylinder is the shell container, and its two ends are provided with liquid-inlet 21 and liquid outlet 25, and the column packing of column packing 23 (23) is C
18Chemically bonded stationary phase (genus commercial goods), column section diameter phi 5mm, column length 50mm; Cross-over valve 14 is a four way solenoid valve; Reactor 20 is for being the spiral type tube type structure, formed by the polyfluortetraethylene pipe coiling of internal diameter 0.3～0.5mm.
The workflow of instrument is: 1, operating instrument, at first tested seawater or river mouth water and complexing agent are pumped into reactor 20 by low-lift pump 19, make trace metal element in the tested seawater and the complexing agent generation metal complex that reacts, form the sea water mixing liquid of 1%8-hydroxyquinoline, by low-lift pump 13 mixed liquor of containing metal complex compound is pumped into evaporating column 12 then, the metal complex in the mixed liquor is adsorbed on the evaporating column 12; 2, by low-lift pump 13 cleaning fluid is pumped in evaporating column 12 and the relevant stream, remove interfering materials such as remaining sodium chloride in evaporating column and the relevant stream thereof, magnesium, calcium; 3, by low-lift pump 13 stripping liquid is pumped in the evaporating column 12, make the metal complex that is adsorbed on the evaporating column 12 break away from evaporating column and enter the low pressure ion chromatography analytical equipment and test, can obtain Cu by sampling valve 2
2+, Ni
2+, Zn
2+, Pb
2+, Cd
2+Chromatogram Deng trace metal element.
Claims (5)
1, the automatic analyzer of a kind of seawater, river mouth underwater trace metallic element mainly is made of sample online treatment device (1) and proving installation, it is characterized in that:
Sample online treatment device (1) comprises evaporating column (12), low-lift pump (13), cross-over valve (14), sample receiver (15), soda liquor container (16) and stripping liquid container (17), the delivery outlet of low-lift pump (13) is connected with the liquid inlet (21) of evaporating column (12) by pipe fitting, the input port of low-lift pump (13) is connected by the delivery outlet of pipe fitting with cross-over valve (14), each input port of cross-over valve (14) by pipe fitting respectively with sample receiver (15), soda liquor container (16) and stripping liquid container (17) are connected
Proving installation is the low pressure ion chromatography analyser, and working pressure is 2～3 * 10
5Pa, its sampling valve (2) is connected by the liquid outlet (25) of the evaporating column (12) in pipe fitting and the sample online treatment device (1).
2, the automatic analyzer of seawater according to claim 1, river mouth underwater trace metallic element, it is characterized in that evaporating column (12) mainly by cylinder (22) and be installed in the filter plate (24) of cylinder liquid outlet end inner chamber and column packing (23) that cylinder intracavity is filled constitutes, column packing is the ball shaped cellulose metal absorbent of following method preparation:
(1) preparation of viscose glue is pressed lixiviating liquid with 16～18%NaOH solution with cotton behind 50～60 ℃ of dipping 30～40min, with the cotton of pressing lixiviating liquid in 20～25 ℃ place 12%NaOH solution to flood 20～25min and suction filtration once more, squeezing is done near, the dipping bath of twice dipping is 1: 20 than (ratio of the oven dry weight of pulp and alkali lye), will through twice dipping, the cotton that press dry pulverize the back in 20～25 ℃ aging 48～50 hours, press cellulose (cotton): CS then
2=2: 1 ratio adds CS
2Vibrated 2～2.5 hours, and added the dissolving of 4%NaOH solution and surfactant lauryl sodium sulfate again and make viscose glue, the consumption of lauryl sodium sulfate is 0.10～0.20% of a cellulose,
(2) preparation of cellulose bead body is with transformer oil or 200
#Gasoline is disperse phase, disperse phase and viscose glue be in a ratio of 4: 1, with the sodium oleate is spreading agent, the consumption of spreading agent is 0.3～0.4% of a viscose glue weight, under agitation will disperse phase, viscose glue and spreading agent add in the container that it is uniformly dispersed, and are heated to 65～70 ℃ and constant temperature 1.0～1.5 hours with 2～3 ℃/min then, upper oil phase is reclaimed in the cooling back, the solution suction filtration and the water of the plain pearl body of lower floor's fibre-bearing are cleaned up the spherical cellulose bead that promptly obtains white
(3) graft reaction adds the spherical cellulose bead and the water of water cut 75.3% in the container that stirrer, reflux condensing tube and thermometer are housed, the weight ratio of spherical cellulose bead and water is 1: 1.5～2, it is fine to add propylene after stirring 10～15min under 20～25 ℃, fine and the cellulosic mol ratio of propylene is 2～3: 1, react after 1.0～1.5 hours, filter, wash, be drying to obtain cyanethyl cellulose pearl body
(4) crosslinked, saponification is being equipped with stirrer, tap funnel, temperature is taken into account cyanethyl cellulose pearl body and the water that adds water cut 30.0% in the container that has reflux condensing tube, the weight ratio of cyanethyl cellulose pearl body and water is 1: 1.5～2, add epichlorokydrin then, the volume ratio of epichlorokydrin and water is 1: 10～15, stir, slowly add 8～12%NaOH solution through tap funnel, the volume ratio of NaOH solution and water is 2～2.5: 1, be warming up to 70～80 ℃ with 2～3 ℃/min in 20～25 ℃ of stirrings after 1.5～2.0 hours, continue reaction 1.5～2.0 hours, cold filtration is transferred pH to 6.5 with 0.6～1.0mol/LHCl solution after reclaiming alkali lye, refilter, clean, drying promptly gets the ball shaped cellulose metal absorbent.
3, the automatic analyzer of seawater according to claim 1, river mouth underwater trace metallic element, it is characterized in that evaporating column (12) mainly by cylinder (22) and be installed in the filter plate (24) of cylinder liquid outlet end inner chamber and column packing (23) that cylinder intracavity is filled constitutes, the column packing (23) of evaporating column (12) is an imido oxalic acid class macroporous absorbent resin.
4, the automatic analyzer of a kind of seawater, river mouth underwater trace metallic element mainly is made of sample online treatment device (1) and proving installation, it is characterized in that:
Sample online treatment device (1) comprises evaporating column (12), low-lift pump (13), cross-over valve (14), sample receiver (15), soda liquor container (16), stripping liquid container (17), complexing agent container (18), low-lift pump (19) and reactor (20), the delivery outlet of low-lift pump (13) is connected with the liquid inlet (21) of evaporating column (12) by pipe fitting, the input port of low-lift pump (13) is connected by the delivery outlet of pipe fitting with cross-over valve (14), each input port of cross-over valve (14) by pipe fitting respectively with soda liquor container (16), stripping liquid container (17) and reactor (20) are connected, the input port of low-lift pump (19) is by pipe fitting and sample receiver (15) and complexing agent container (18) connection, the delivery outlet of low-lift pump (19) is connected with reactor (20) by pipe fitting
Proving installation is the low pressure ion chromatography analyser, and working pressure is 2～3 * 10
5Pa, its sampling valve (2) is connected by the liquid outlet (25) of the evaporating column (12) in pipe fitting and the sample online treatment device (1).
5, the automatic analyzer of seawater according to claim 4, river mouth underwater trace metallic element, it is characterized in that evaporating column (12) mainly by cylinder (22) and be installed in the filter plate (24) of cylinder liquid outlet end inner chamber and column packing (23) that cylinder intracavity is filled constitutes, the column packing (23) of evaporating column (12) is C
18Chemically bonded stationary phase.
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| CN 200410021965 CN1270181C (en) | 2004-03-05 | 2004-03-05 | Automatic analyzing instrument for trace metal element in sea water, river water |
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| WO2007017841A1 (en) * | 2005-08-09 | 2007-02-15 | The Procter & Gamble Company | Low pressure anion chromatographic apparatus and method having two or more eluents |
| US8105837B2 (en) * | 2008-03-11 | 2012-01-31 | Sichuan University | Method for automatic assay of anionic detergents in seawater |
| CN108535377A (en) * | 2018-04-11 | 2018-09-14 | 大连依利特分析仪器有限公司 | It is a kind of to automate quick detection device and rapid detection method |
| CN108548879A (en) * | 2018-04-11 | 2018-09-18 | 大连依利特分析仪器有限公司 | A kind of quick detection device of automation |
| CN108627375A (en) * | 2018-04-26 | 2018-10-09 | 南京新循环保科技有限公司 | The method that heavy metal ion quickly detects |
| CN108871915A (en) * | 2018-04-26 | 2018-11-23 | 南京新循环保科技有限公司 | Heavy metal ion device for fast detecting |
-
2004
- 2004-03-05 CN CN 200410021965 patent/CN1270181C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007017841A1 (en) * | 2005-08-09 | 2007-02-15 | The Procter & Gamble Company | Low pressure anion chromatographic apparatus and method having two or more eluents |
| US8105837B2 (en) * | 2008-03-11 | 2012-01-31 | Sichuan University | Method for automatic assay of anionic detergents in seawater |
| CN108535377A (en) * | 2018-04-11 | 2018-09-14 | 大连依利特分析仪器有限公司 | It is a kind of to automate quick detection device and rapid detection method |
| CN108548879A (en) * | 2018-04-11 | 2018-09-18 | 大连依利特分析仪器有限公司 | A kind of quick detection device of automation |
| CN108548879B (en) * | 2018-04-11 | 2024-07-09 | 大连依利特分析仪器有限公司 | Automatic change rapid detection equipment |
| CN108627375A (en) * | 2018-04-26 | 2018-10-09 | 南京新循环保科技有限公司 | The method that heavy metal ion quickly detects |
| CN108871915A (en) * | 2018-04-26 | 2018-11-23 | 南京新循环保科技有限公司 | Heavy metal ion device for fast detecting |
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| CN1270181C (en) | 2006-08-16 |
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