CN101806744A - Method for rapid analysis of fluoride through flowing injection and device thereof - Google Patents
Method for rapid analysis of fluoride through flowing injection and device thereof Download PDFInfo
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Abstract
The invention discloses a method for rapid analysis of fluoride through flowing injection and device thereof. The method of the invention comprises the following steps: taking sodium acetate-acetic acid buffer solution as a carrier solution, continuously injecting the carrier solution into the pipeline of a capillary pipe through a carrier solution injection pump, injecting a water sample and an indicating agent into the carrier solution through a sample-injection valve to make the water sample spread in the directional flowing carrier solution, mix with the indicating agent and the buffer solution, and enter a colorimetric flow cell along with the carrier solution, and measuring the remaining fluorine in the water through the light abortion with wavelength of 620nm and the photoelectric conversion. The device of the invention comprises a photoelectric flow cell, a pressure sensor, a back pressure pipe, an indicating agent storage bottle, a carrier solution storage bottle, a first peristaltic pump, a carrier solution injection pump, a second peristaltic pump, a carrier solution four-way valve, a first sample injection six-way valve, a second sample injection six-way valve, a capillary pipe, a capillary sampling pipe, a first standard sample source, a second first standard sample source, a first solenoid valve and a second solenoid valve switched with a water sample source. The invention has the advantages of accurate test data and significantly shortened test cycle, and is suitable for rapid detection of fluoride.
Description
Technical field
The present invention relates to a kind of method and device thereof of flow injection spectrophotometric analysis fluoride, be particularly related to and analyze or the flow injection spectrophotometric detecting method of on-line monitoring fluoride in surface water or the solution, belong to chemical analysis and monitoring water environment analysis field.
Background technology
Fluoride (F
-) be one of trace element of needed by human, scarce fluorine is easily suffered from dental caries, and fluorine-containing suitable concentration is 0.5～1.0mg/L (F in the drinking-water
-).When the long-term drinking fluorinated volume is higher than the water of 1～1.5mg/L, then easily suffer from the spot tooth disease, when fluorinated volume is higher than 4mg/L in the water, then can cause fluorosis of bone.
Fluoride extensively is present in the natural water body.Usually all there is fluoride in the waste water of nonferrous metallurgy, iron and steel and aluminium processing, coke, glass, pottery, electronics, plating, chemical fertilizer, insecticide factory and the waste water of fluorine-containing mineral.
The analysis determining method that can be used for fluoride has a lot, can be divided into chemical analysis method and instrument analytical method two big classes.Chemical analysis method mainly refers to methods such as steam distillation, generally is used for the analysis of constant fluoride.Because the accuracy of analysis of these methods often depends on operator's skill level, and expends chemical reagent, therefore along with the development of analytical instrument, instrument analytical method is occupied an leading position in the modern analysis method.
Flame atomic absorption spectrometry: the method measurement effect is fine, and disturbing factor seldom mainly is that chemistry disturbs but disturb is not very serious, but the required equipment price costliness of this kind method, cost performance is not high.
Ion selective electrode method: this method principle mainly is that the variation that utilizes fluoride electrode to contact by cell emf with fluorine-containing test solution comes the quantitative measurement fluoride, but this method disturbing factor is more, and detection time is than the long purpose that is difficult for realizing fast measuring, precise determination.
Summary of the invention
The purpose of this invention is to provide a kind of method and device thereof of rapid analysis of fluoride through flowing injection, adopt the flow injection spectrophotometric method exactly, design and exploitation are suitable for the full-automatic in-line analyzer of fluoride measurement in the day water, sewage and the industrial waste water.
The present invention adopts following technical scheme:
A kind of method of rapid analysis of fluoride through flowing injection, adopt following step:
A. be current-carrying liquid with sodium acetate-glacial acetic acid buffer solution, current-carrying liquid injected pipeline capillaceous continuously by current-carrying liquid syringe pump;
B. by annotating the sample valve sample and indicator are injected the current-carrying liquid of above-mentioned kapillary pipeline, sample spreads in the current-carrying liquid of directed flow, with indicator and current-carrying liquid hybrid reaction, and the blue ternary complexes of reaction generation;
C. blue ternary complexes enter the colorimetric flow cell with current-carrying liquid, at wavelength is the blue ternary complexes in irradiation and the colorimetric detection colorimetric flow cell under the light source of 620nm, complex compound is directly proportional with fluorinion concentration in the absorbance at 620nm wavelength place, the quantitative measurement fluoride, because blue ternary complexes absorb the difference that is absorbed with under maximum and the variable concentrations to the light of 620nm wavelength, according to the changing value that sees through light intensity, acquisition has the response curve of corresponding peak height, utilizing peak height, is that spectrophotometric method is calculated the content of trying to achieve fluoride in the sample by absorbance and opto-electronic conversion;
D. last current-carrying liquid flows out from the outlet kapillary of flow cell.
Described indicator was by fluorine reagent, sodium acetate-glacial acetic acid buffer solution, acetone, 0.002mol/L lanthanum nitrate hexahydrate, 3: 1: 3 by volume: 3 is mixed.
A kind of rapid analysis of fluoride through flowing injection device comprises that pressure transducer, photoelectricity flow cell, back pressure pipe, indicator reservoir, current-carrying liquid reservoir, first peristaltic pump, current-carrying liquid syringe pump, second peristaltic pump, current-carrying liquid four-way valve, first annotate first solenoid valve and second solenoid valve that sample six-way valve, second is annotated sample six-way valve, capillary sampling pipe, kapillary, the first standard specimen source, the second standard specimen source, switched mutually with the water sample source;
Wherein current-carrying liquid syringe pump, current-carrying liquid reservoir, pressure transducer are connected with current-carrying liquid four-way valve by kapillary respectively, current-carrying liquid four-way valve by kapillary through first annotating sample six-way valve, photoelectricity flow cell, being connected the waste liquid discharge with the back pressure pipe;
The water sample source is connected with first solenoid valve by kapillary, the first standard specimen source is connected with second solenoid valve by kapillary respectively with the second standard specimen source, second solenoid valve is annotated the sample six-way valve by kapillary through first solenoid valve, first peristaltic pump and first and is connected, and waste liquid is discharged;
The indicator reservoir is annotated the sample six-way valve by kapillary through second peristaltic pump and second and is connected, and waste liquid is discharged;
Second annotates the sample six-way valve is connected by the capillary sampling pipe and the first notes sample six-way valve.
Described internal diameter 0.5-1mm capillaceous, pipe thickness 〉=0.8mm.
The constant flow pump of described current-carrying liquid syringe pump for making by the pottery or the stainless steel material of acid corrosion-resistant.
The device of another kind of rapid analysis of fluoride through flowing injection comprises photoelectricity flow cell, back pressure pipe, current-carrying liquid syringe pump, indicator reservoir, current-carrying liquid reservoir, hyperchannel selection valve, memotron, the first standard specimen source, the second standard specimen source, water sample source and kapillary;
Wherein current-carrying liquid syringe pump is connected with the back pressure pipe through memotron, hyperchannel selection valve, photoelectricity flow cell by kapillary, and waste liquid is discharged;
Indicator reservoir, current-carrying liquid reservoir, the first standard specimen source, the second standard specimen source and water sample source are connected with the hyperchannel selection valve by kapillary respectively.
Beneficial effect:
The advantage that the present invention compared with prior art has:
(1) analysis to measure time weak point, the each measurement from being sampled to out measurement result, needed only 10 minutes measuring period the shortest, and this makes truly " on-line monitoring " be achieved.
(1) favorable reproducibility, the measuring accuracy height.Use the amount of highly sensitive 620nm light source colorimetric estimation reactant, not only detection limit reduces greatly, and stable constant current pottery current-carrying liquid syringe pump makes the measurement reappearance higher.
(2) because FIA is the kapillary trace analysis, the reagent consumption seldom.And agents useful for same almost do not have toxicity, and the secondary pollution degree is low.
(3) because simple in structure, the failure rate of stream is very low.Independently developed patented technology and device as the corrosion-resistant high pressure current-carrying of pottery liquid syringe pump, annotate the sample valve, do not retain bubble flow cell or the like, make this instrument overcome shortcomings such as like product weak point in serviceable life, failure rate height.
Description of drawings
Fig. 1 is the schematic diagram of rapid analysis of fluoride through flowing injection device.
Fig. 2 is the accompanying drawing of embodiment 1, and wherein notes sample six-way valve V4, V5 are in the measurement state.
Fig. 3 is the accompanying drawing of embodiment 1, and wherein notes sample six-way valve V4, V5 are in sample states.
Fig. 4 is the accompanying drawing of embodiment 2.
Among the figure: V1-water sample three-way solenoid valve, V2-standard specimen three-way solenoid valve, V4-first annotate the sample six-way valve, V5-second annotates sample six-way valve, V6-current-carrying liquid four-way valve, P1-current-carrying liquid syringe pump, P2-first peristaltic pump, P3-second peristaltic pump, Ls-capillary sampling pipe, L
X-indicator quantity tube, T-photoelectricity flow cell, S-water sample source, the B1-first standard specimen source, the B2-second standard specimen source, H-current-carrying liquid reservoir, M-indicator reservoir, W-waste liquid bottle, L
1-storage tube, Y-pressure transducer, N-back pressure pipe.
Embodiment
Example structure and test process below in conjunction with this rapid analysis of fluoride through flowing injection of description of drawings device.
The method of a kind of rapid analysis of fluoride through flowing injection among the present invention, adopt following step:
A. be current-carrying liquid with sodium acetate-glacial acetic acid buffer solution, current-carrying liquid injected pipeline capillaceous continuously by current-carrying liquid syringe pump;
B. by annotating the sample valve sample and indicator are injected the current-carrying liquid of above-mentioned kapillary pipeline, sample spreads in the current-carrying liquid of directed flow, with indicator and current-carrying liquid hybrid reaction, and the blue ternary complexes of reaction generation;
C. blue ternary complexes enter the colorimetric flow cell with current-carrying liquid, at wavelength is the blue ternary complexes in irradiation and the colorimetric detection colorimetric flow cell under the light source of 620nm, complex compound is directly proportional with fluorinion concentration in the absorbance at 620nm wavelength place, the quantitative measurement fluoride, because blue ternary complexes absorb the difference that is absorbed with under maximum and the variable concentrations to the light of 620nm wavelength, according to the changing value that sees through light intensity, acquisition has the response curve of corresponding peak height, utilizing peak height, is that spectrophotometric method is calculated the content of trying to achieve fluoride in the sample by absorbance and opto-electronic conversion;
D. last current-carrying liquid flows out from the outlet kapillary of flow cell.
Described indicator was by 0.002mol/L fluorine reagent, sodium acetate-glacial acetic acid buffer solution, acetone, 0.002mol/L lanthanum nitrate hexahydrate, 3: 1: 3 by volume: 3 is mixed.
Computing formula is as follows:
In the formula: A: absorbance
V
1: the baseline voltage value
V
2: the peak height magnitude of voltage
V
3: bias light magnitude of voltage (the photovoltage value during unglazed entering)
The agents useful for same compound method is as follows:
(1) 0.002mol/L fluorine reagent
Take by weighing 0.386g fluorine reagent [3-methyl amine-alizarin-oxalic acid, ALC, C
14H
7O
4CH
2N (CH
2COOH)
2] to add the 5mL deionized water moistening, drips the 1mol/L sodium hydroxide solution and make its dissolving, adds 0.25g sodium acetate (CH again
3COONaH
2O), regulate pH to 5.0, be diluted to 500ml, store in the brown bottle with deionized water with the 1mol/L hydrochloric acid solution.
(2) buffer solution
Take by weighing 35g anhydrous sodium acetate (CH
3COONa) be dissolved in the 800mL deionized water, add 75mL glacial acetic acid (CH3COOH), be diluted to 1000mL with deionized water, regulating pH with acidometer is 4.1.
(3) fluoride standard stock solution
Take by weighing in the pure sodium fluoride of top grade (NaF) 0.2210g of 105 ℃ of oven dry 2h and be dissolved in the deionized water, move in the 1000mL volumetric flask, be diluted to graticule, store in the polyethylene bottle standby, every milliliter of fluorine-containing 100 μ g of this solution.This solution is used for the preparation of standard specimen solution standard specimen B1, standard specimen B2.
(4) 0.002mol/L lanthanum nitrate hexahydrate
Take by weighing 0.886g lanthanum nitrate [La (NO
3) H
2O] with a small amount of 1mol/L dissolve with hydrochloric acid solution, regulating pH with the 1mol/L sodium acetate solution is 4.1, is diluted to 1000mL with deionized water.
(5) indicator
Get 0.002mol/L fluorine reagent, buffer solution, acetone, 0.002mol/L lanthanum nitrate hexahydrate, 3: 1: 3 by volume: 3 mix promptly.Face the time spent preparation.
Shown in Fig. 1 is the schematic diagram of one of apparatus of the present invention, comprises that pressure transducer Y, photoelectricity flow cell T, back pressure pipe N, indicator reservoir M, current-carrying liquid reservoir H, the first peristaltic pump P2, current-carrying liquid syringe pump P1, the second peristaltic pump P3, current-carrying liquid four-way valve V6, first annotate the first solenoid valve V1 and the second solenoid valve V2 that sample six-way valve V4, second annotates sample six-way valve V5, capillary sampling pipe Ls, kapillary, the first standard specimen source B1, the second standard specimen source B2, switches mutually with water sample source S;
Wherein current-carrying liquid syringe pump P1, current-carrying liquid reservoir H, pressure transducer Y are connected with current-carrying liquid four-way valve V6 by kapillary respectively, current-carrying liquid four-way valve V6 by kapillary through first annotating sample six-way valve V4, photoelectricity flow cell T, being connected the waste liquid discharge with back pressure pipe N;
Water sample source S is connected with the first solenoid valve V1 by kapillary, the first standard specimen source B1 is connected with the second solenoid valve V2 by kapillary respectively with the second standard specimen source B2, the second solenoid valve V2 annotates sample six-way valve V4 by kapillary through the first solenoid valve V1, the first peristaltic pump P2 and first and is connected, and waste liquid is discharged;
Indicator reservoir M annotates sample six-way valve V5 by kapillary through the second peristaltic pump P3 and second and is connected, and waste liquid is discharged;
Second annotates sample six-way valve V5 is connected by the capillary sampling pipe Ls and the first notes sample six-way valve V4.
Pipeline in this example is internal diameter 0.8mm, the kapillary of external diameter 2.5mm;
Principle of work: the used principle of the present invention can react at normal temperatures, need not heating, makes apparatus simpler.
Pipeline among the present invention is corrosion resistant fluoroplastic kapillary, be connected to first on the capillary pipeline and annotate sample six-way valve V4, V5, can be with in water sample and the indicator incision current-carrying liquid, and with " current-carrying liquid || water sample || indicator || water sample || current-carrying liquid " order distribute.Anhydrous sodium acetate-glacial acetic acid mixed liquor is carried continuously by current-carrying liquid syringe pump, and the colorimetric of flowing through flow cell comes out after return in the reagent bottle current-carrying liquid of formation continuous flow behind the three meters long back pressure pipe from flow cell.During detection, annotate the sample valve and go to the test position, when annotate the sample valve with water sample and indicator incision reacting pipe in after, the sample band is advanced by current-carrying liquid and diffusion mixing gradually in progradation, and sample and reagent present gradient and mixes, and the gradient mixed zone enters and flows through flow cell, by wavelength is the value of 620nm light source irradiation and colorimetric measured reaction thing, acquisition has the response curve of corresponding peak height and peak width, with peak height or peak width through with the curve ratio of blank test, calculate the content of trying to achieve fluoride in the water sample.
For the water sample that contains solid impurity, remove a large amount of impurity except that adopting general filtration treatment, for prevent＞the 0.8mm granule foreign enters pick-up unit, water sample was delivered to one earlier respectively vertical can differs from outflow downwards behind separator tube and the ejector by the submersible pump that has filter screen before feed annotating the sample valve, can differ from the downward current of formation in the separator tube at vertical, annotate the sample valve and from downward current, draw water sample by from up to down stretching into the sampling pipe utilization that can differ from the separator tube and the negative pressure of ejector generation.In the water＞granule foreign of 0.8mm moves downward because of gravity, avoids entering in the water sample.
The constant current syringe pump of carrying current-carrying liquid also must have the function of anti-oxidant and antiacid corrosion except that requiring to produce the elevated pressures.
As shown in Figure 2, wherein first first interface of annotating sample six-way valve V4 is connected with the first solenoid valve V1, second interface through peristaltic pump P2 by kapillary, first annotates sample six-way valve V4 the 3rd interface is connected by the 4th interface of kapillary with current-carrying liquid four-way valve V6, first annotates sample six-way valve V4 the 4th interface is connected with the back pressure pipe through flow cell by kapillary, first annotates sample six-way valve V4 second interface is connected by the 3rd interface that capillary sampling pipe Ls and second annotates sample six-way valve V5, first annotates sample six-way valve V4 the 5th interface is connected by the 4th interface that capillary sampling pipe Ls and second annotates sample six-way valve V5, and the first notes sample six-way valve V4 the 6th interface is a waste liquid outlet;
Second first interface of annotating sample six-way valve V5 is connected with indicator reservoir M through peristaltic pump P3 by kapillary, and second notes sample six-way valve V5 second interface and the 5th interface are by indicator capillary quantity tube L
XBe connected, the 6th interface is a waste liquid outlet;
Current-carrying liquid four-way valve V6 first interface is connected with current-carrying liquid reservoir H by kapillary, and current-carrying liquid four-way valve V6 second interface is connected with syringe pump P1 by kapillary, and current-carrying liquid four-way valve V6 the 3rd interface is connected with pressure transducer;
The first solenoid valve V1 is provided with first interface, second interface, the 3rd interface, wherein the first solenoid valve V1 the 3rd interface is connected with water sample source S by kapillary, and the first solenoid valve V1, second interface and the first solenoid valve V1, first interface, the first solenoid valve V1 the 3rd interface are selected one and communicated and be connected through first interface that peristaltic pump P3 and first annotates sample six-way valve V4 by kapillary;
The second solenoid valve V2 is provided with first interface, second interface, the 3rd interface, wherein the second solenoid valve V2 the 3rd interface by kapillary be connected with the first standard specimen source B1, the second solenoid valve V2, first interface is connected with the second standard specimen source B2 by kapillary, the second solenoid valve V2 second selects one and communicates with the second solenoid valve V2, first interface, the second solenoid valve V2 the 3rd interface, and is connected by second interface of kapillary with the first solenoid valve V1.
The first notes sample six-way valve V4 and second annotates sample six-way valve V5 and is six-way valve, and valve seat is provided with six interfaces 1～6, and the inboard of valve gap is provided with and six three arc grooves that interface is corresponding; Sample loop Ls is two sections kapillaries, is connected to first interface 2 and second of annotating sample six-way valve V4 and annotates the interface 4 that the interface 5 and second of interface 3, the first notes sample six-way valve V4 of sample six-way valve V5 is annotated sample six-way valve V5; Indicator sampling ring L
XTwo ends be connected to second interface 2 and the interface 5 of annotating sample six-way valve V5; Rotary spool makes deep-slotted chip breaker forward or reversely turn over radian at interval, can be with Ls and L
XSampling and measuring and select between two states to switch, be i.e. sampling pipe Ls and L
XAnnexation in device converts sample states shown in Figure 3 to.
Current-carrying liquid is sucked by current-carrying liquid syringe pump from current-carrying liquid bottle, enters the measurement stream.As shown in Figure 3, as the first notes sample six-way valve V4, when the second notes sample six-way valve V5 is in and measures the position, circulation status is: current-carrying liquid → L
SSampling ring → L
XSampling ring → L
SSampling ring → flow cell → back pressure pipe → waste liquid bottle; When notes sample valve was in sample bits, the logical state of liquid is: current-carrying liquid → flow cell → back pressure pipe → waste liquid bottle, sample and indicator then were full of L respectively
SSampling ring and L
XSampling ring.
As shown in Figure 2: when being in measurement state, the first notes sample six-way valve V4 and second annotates sample six-way valve V5 interface 2 separately and communicates respectively with interface 5 with interface 3, interface 4, and their interfaces 1 separately disconnect with interface 6 with interface 4, interface 5 respectively with interface 2, interface 3;
As shown in Figure 3: when being in the sampling attitude, the first notes sample six-way valve V4 and second annotates sample six-way valve V5 interface 1 separately and communicates respectively with interface 6 with interface 4, interface 5 with interface 2, interface 3, and interface 2 separately all disconnects with interface 5 with interface 3, interface 4;
The present invention uses operating process as follows:
At first with current-carrying liquid device is cleaned: current-carrying liquid four-way valve V6 is chosen as interface 2 and communicates with interface 1, starts current-carrying liquid syringe pump P1 to sucking attitude, sucks current-carrying liquid to the chamber of syringe pump P1 from current-carrying liquid storage bottle H, is filled the back termination of pumping; Subsequently current-carrying liquid four-way valve V6 is gone to interface 2 and interface 4 communicating states, the first notes sample six-way valve V4 and second is annotated sample six-way valve V5 transfer to measurement state as shown in Figure 3, start current-carrying liquid syringe pump P1 to injecting attitude, make the current-carrying liquid in the syringe pump P1 chamber inject following stream:
P1 → V6 interface 2,4 → V4 interface 3,2 → sampling pipe L
S → V5 interface 3,2 → indicator quantity tube L
X → V5 interface 5,4 → sampling pipe L
S → V4 interface 5,4 → flow cell → back pressure pipe → waste liquid bottle W; Current-carrying liquid is to cleaning from above stream.Cleaning finishes, termination of pumping P1.
Enter sampling routine then: as shown in Figure 3, the first solenoid valve V1 is in the state that the interface 2 as Fig. 2 communicates with interface 3, annotating sample six-way valve V4 and second with first annotates sample six-way valve V5 and goes to as shown in Figure 3 sampling attitude, start peristaltic pump P2, water sample S feeds as shown in Figure 3 stream through peristaltic pump P2: the interface 1 of S → valve V4, interface 2 → sampling pipe L
SThe interface 3 of → valve V5, interface 4 → sampling pipe L
SThe interface 5 of → valve V4, interface 6 → waste liquid bottle W1, two sections sampling pipe L at this moment
SAll filled with water sample.Start peristaltic pump P3 simultaneously, indicator M passes through by following stream shown in Figure 2 through peristaltic pump P3: indicator M → valve V5 interface 1, interface 2 → indicator quantity tube L
XThe interface 5 of → valve V5, interface 6 → waste liquid bottle W, quantity tube L at this moment
XPromptly filled with indicator solution.
Then enter process of measurement: close peristaltic pump P2 and peristaltic pump P3, and annotate sample six-way valve V4 and the 2nd ` with first and annotate sample six-way valve V5 and go to as shown in Figure 2 measurement state, start current-carrying liquid syringe pump P1 once more, make current-carrying liquid once more by current-carrying liquid syringe pump P1 → current-carrying liquid four-way valve V6 interface 2, interface 4 → V4 interface 3, interface 2 → sampling pipe L
S→ V5 interface 3, interface 2 → indicator quantity tube L
X→ V5 interface 5, interface 4 → sampling pipe L
S→ V4 interface 5, the flow path of interface 4 → flow cell T → back pressure pipe N → waste liquid bottle W, at this moment, liquid in the above capillary pipeline with " current-carrying liquid || water sample || indicator || water sample || current-carrying liquid " order distribute, be that indicator is between two sections water samples, in by current-carrying liquid progradation, water sample spreads gradually and presents gradient with indicator and mixes, the two reacts and produces blue ternary complexes, its blue depth of color is directly proportional with fluorine content in the water, after the mixed liquor section is advanced flow cell, by wavelength is the value of 620nm light source irradiation and colorimetric measured reaction thing, acquisition has the response curve of corresponding peak height and peak width, with peak height or peak width through with the standard specimen water test curve ratio of known fluorine concentration, by calculating the content that promptly draws fluoride in the water sample.
Set L
SSampling ring length: 500mm, developer length: 600mm.
Record 1: the first section 0.1～4mg/L of data such as following table
Another kind is used for the device of the rapid analysis of fluoride through flowing injection of the surplus fluorine of branch bleed, as shown in Figure 4, comprises photoelectricity flow cell T, back pressure pipe N, current-carrying liquid syringe pump P1, indicator reservoir M, current-carrying liquid reservoir H, hyperchannel selection valve V, memotron L
1, the first standard specimen source B1, the second standard specimen source B2, water sample source S and kapillary;
Wherein current-carrying liquid syringe pump P1 is by kapillary process memotron L
1, hyperchannel selection valve V, photoelectricity flow cell T be connected with back pressure pipe N, waste liquid is discharged;
Indicator reservoir M, current-carrying liquid reservoir H, the first standard specimen source B1, the second standard specimen source B2 and water sample source S are connected with hyperchannel selection valve V by kapillary respectively.
The valve seat of said hyperchannel selection valve V is provided with a plurality of minutes interfaces of a hub-interface 0 and circumferential arrangement, each minute, interface 1,2,3,4,5,6 was connected with photoelectricity flow cell T, water sample S, the first standard specimen source B1, the second standard specimen source B2, indicator reservoir M, current-carrying liquid reservoir H with kapillary respectively, said hub-interface 0 be connected with current-carrying liquid syringe pump P1 by kapillary, and on the capillary pipeline between this hub-interface 0 and the current-carrying liquid syringe pump P1, include the capillary storage tube; Valve gap is provided with a radially groove, and radially an end of groove communicates with hub-interface 0, and the other end communicates with each minute interface selection by the rotation of valve gap.
When detecting in the water surplus fluorine water sample with above device, optionally rotate valve gap, hub-interface 0 is sequentially communicated with required minute interface, and sequentially suck sample, reagent or the current-carrying liquid of aequum to memotron L1 from different branch interface by current-carrying liquid syringe pump, form the different solutions band that distributes by section among the memotron L1, by current-carrying liquid syringe pump the solution band is pushed into the reaction tube reaction then, goes into flow cell subsequently and carry out Photoelectric Detection.
But the present invention's setting program control device, the rotation of valve gap and suction liquid measure automatically perform by control program.
As shown in Figure 4, the valve seat of hyperchannel selection valve V is provided with a hub-interface 0, is distributed with 1～6 six interface all around, and the inboard of valve gap is provided with a groove, and the end of groove can correspondingly overlap on six interfaces on the valve seat; The rotation valve gap can make groove turn over a radian at interval, thus the annexation of conversion hyperchannel selection valve V; Memotron L1 is one section capillary, is connected to 1～6 interface of hyperchannel selection valve V respectively, and the rotation valve gap can make groove turn over a radian at interval, the annexation of L1 can be changed, thus the collection of realization reagent.
Wherein the valve seat of hyperchannel selection valve V is provided with six branch interfaces of a hub-interface 0 and circumferential arrangement, first interface is by kapillary and photoelectricity flow cell, second interface is by kapillary and water sample, the 3rd interface is by the kapillary and the first standard specimen source B1, the 4th interface is by the kapillary and the second standard specimen source B2, the 5th interface is by kapillary and indicator reservoir M, the 6th interface is connected with current-carrying liquid reservoir H by kapillary, hub-interface 0 is connected with current-carrying liquid syringe pump P1 by kapillary, and is provided with the capillary storage tube on the capillary pipeline between this hub-interface 0 and the current-carrying liquid syringe pump P1; Valve gap is provided with a radially groove, and radially an end of groove communicates with hub-interface 0, and the other end communicates with each minute interface selection by the rotation of valve gap.
With current-carrying liquid device is cleaned earlier before the present invention uses, operating process is as follows:
Hyperchannel selection valve V is chosen as interface 0 and communicates with interface 6, starts current-carrying liquid syringe pump P1 to sucking attitude, sucks current-carrying liquid to the chamber of current-carrying liquid syringe pump P1 from current-carrying liquid storage bottle H, is filled the back termination of pumping; Subsequently hyperchannel selection valve V is gone to interface 0 and communicates, start current-carrying liquid syringe pump P1, make the current-carrying liquid in the current-carrying liquid syringe pump P1 chamber inject following stream to injecting attitude with interface 1:
P1 → sampling pipe L
S→ V interface 0, interface 1 → back pressure N → flow cell T → waste liquid bottle W; Current-carrying liquid is to cleaning from above stream.Cleaning finishes, and closes current-carrying liquid syringe pump Pl.
Enter sampling routine then.The state that the interface 0 of hyperchannel selection valve V communicates with interface 6 starts current-carrying liquid syringe pump P1 to sucking attitude, sucks current-carrying liquid to the chamber of syringe pump P1 from current-carrying liquid storage bottle H, after the suction regular hour, and sampling pipe L
SIn stored a part of current-carrying liquid, hyperchannel selection valve V goes to interface 0 and interface 2 (measuring the process of water sample); Perhaps interface 0 and interface 3 (measuring the process of mark two); Perhaps interface 0 and interface 4 (measuring the process of mark one or two), this moment, current-carrying liquid syringe pump P1 sucked water sample, sampling pipe L
SIn stored one section water sample again, hyperchannel selection valve V goes to interface 0 and interface 5; This moment, current-carrying liquid syringe pump P1 sucked developer, sampling pipe L
SIn stored one section DPD developer again, hyperchannel selection valve V goes to interface 0 and interface 6; This moment, current-carrying liquid syringe pump P1 sucked current-carrying liquid, termination of pumping.At this moment, the liquid in the memotron distributes with the order of " current-carrying liquid || water sample || DPD|| current-carrying liquid ".
Then enter process of measurement.Hyperchannel selection valve V is gone to the position that interface 0 communicates with interface 1, start current-carrying liquid syringe pump P1 once more, make liquid in the memotron once more according to current-carrying liquid syringe pump P1 → sampling pipe L
S→ hyperchannel selection valve V interface 0, the flow path of interface 1 → back pressure pipe N → flow cell T → waste liquid bottle W, at this moment, liquid in the memotron distributes with the order of " current-carrying liquid || water sample || DPD|| current-carrying liquid ", be that the indicator indicator is between two sections water samples, in by current-carrying liquid progradation, water sample spreads gradually and presents gradient with indicator and mixes, the two reacts and produces blue ternary complexes, its blue depth of color is directly proportional with fluorine content in the water, after the mixed liquor section is advanced flow cell, by wavelength is the value of 620nm light source irradiation and colorimetric measured reaction thing, acquisition has the response curve of corresponding peak height and peak width, with peak height or peak width through with the standard specimen water test curve ratio of known fluorine concentration, by calculating the content that promptly draws fluoride in the water sample.
Record 2: the first sections 5～9mg/L of data such as following table
The inventive method can contain effectively that the bubble in the detection system generates, and test result is accurate; Measurement range is wide, and this apparatus measures scope is 0.1～10mg/L, and the reappearance height, and measurement result is accurate.The water sample of the each incision of this method is micro-, has only about 100 μ l, and the consumption of reagent is very extremely low, has saved operation cost greatly.
Claims (6)
1. the method for a rapid analysis of fluoride through flowing injection is characterized in that adopting following step:
A. be current-carrying liquid with sodium acetate-glacial acetic acid buffer solution, current-carrying liquid injected pipeline capillaceous continuously by current-carrying liquid syringe pump;
B. by annotating the sample valve sample and indicator are injected the current-carrying liquid of above-mentioned kapillary pipeline, sample spreads in the current-carrying liquid of directed flow, with indicator and current-carrying liquid hybrid reaction, and the blue ternary complexes of reaction generation;
C. blue ternary complexes enter the colorimetric flow cell with current-carrying liquid, at wavelength is the blue ternary complexes in irradiation and the colorimetric detection colorimetric flow cell under the light source of 620nm, complex compound is directly proportional with fluorinion concentration in the absorbance at 620nm wavelength place, the quantitative measurement fluoride, because blue ternary complexes absorb the difference that is absorbed with under maximum and the variable concentrations to the light of 620nm wavelength, according to the changing value that sees through light intensity, acquisition has the response curve of corresponding peak height, utilizing peak height, is that spectrophotometric method is calculated the content of trying to achieve fluoride in the sample by absorbance and opto-electronic conversion;
D. last current-carrying liquid flows out from the outlet kapillary of flow cell.
2. the method for rapid analysis of fluoride through flowing injection according to claim 1 is characterized in that described indicator was by 0.002mol/L fluorine reagent, sodium acetate-glacial acetic acid buffer solution, acetone, 0.002mol/L lanthanum nitrate hexahydrate, 3: 1: 3 by volume: 3 is mixed.
3. a device of implementing the method for the described rapid analysis of fluoride through flowing injection of claim 1 is characterized in that comprising pressure transducer (Y), photoelectricity flow cell (T), back pressure pipe (N), indicator reservoir (M), current-carrying liquid reservoir (H), first peristaltic pump (P2), current-carrying liquid syringe pump (P1), second peristaltic pump (P3), current-carrying liquid four-way valve (V6), first annotates sample six-way valve (V4), second annotates sample six-way valve (V5), capillary sampling pipe (Ls), kapillary, the first standard specimen source (B1), the second standard specimen source (B2), first solenoid valve (V1) and second solenoid valve (V2) that switch mutually with water sample source (S);
Wherein current-carrying liquid syringe pump (P1), current-carrying liquid reservoir (H), pressure transducer (Y) are connected with current-carrying liquid four-way valve (V6) by kapillary respectively, current-carrying liquid four-way valve (V6) by kapillary through first annotating sample six-way valve (V4), photoelectricity flow cell (T), being connected the waste liquid discharge with back pressure pipe (N);
Water sample source (S) is connected with first solenoid valve (V1) by kapillary, the first standard specimen source (B1) is connected with second solenoid valve (V2) by kapillary respectively with the second standard specimen source (B2), second solenoid valve (V2) is annotated sample six-way valve (V4) by kapillary through first solenoid valve (V1), first peristaltic pump (P2) and first and is connected, and waste liquid is discharged;
Indicator reservoir (M) is annotated sample six-way valve (V5) by kapillary through second peristaltic pump (P3) and second and is connected, and waste liquid is discharged;
Second annotates sample six-way valve (V5) is connected by the capillary sampling pipe (Ls) and the first notes sample six-way valves (V4).
4. the device of a kind of rapid analysis of fluoride through flowing injection according to claim 3 is characterized in that described internal diameter 0.5-1mm capillaceous, pipe thickness 〉=0.8mm.
5. the device of a kind of rapid analysis of fluoride through flowing injection of stating according to claim 3 is characterized in that the constant flow pump of described current-carrying liquid syringe pump (P1) for being made by the pottery or the stainless steel material of acid corrosion-resistant.
6. a device of implementing the method for the described rapid analysis of fluoride through flowing injection of claim 1 is characterized in that comprising photoelectricity flow cell (T), back pressure pipe (N), current-carrying liquid syringe pump (P1), indicator reservoir (M), current-carrying liquid reservoir (H), hyperchannel selection valve (V), memotron (L
1), the first standard specimen source (B1), the second standard specimen source (B2), water sample source (S) and kapillary;
Wherein current-carrying liquid syringe pump (P1) is by kapillary process memotron (L
1), hyperchannel selection valve (V), photoelectricity flow cell (T) be connected with back pressure pipe (N), waste liquid is discharged;
Indicator reservoir (M), current-carrying liquid reservoir (H), the first standard specimen source (B1), the second standard specimen source (B2) are connected with hyperchannel selection valve (V) by kapillary respectively with water sample source (S).
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| CN106546687A (en) * | 2016-12-08 | 2017-03-29 | 北京莱伯泰科仪器股份有限公司 | For the miniaturization device and its using method of GPC cleanup system system |
| CN112729852A (en) * | 2020-12-22 | 2021-04-30 | 西安精密机械研究所 | Three-component turbine power combustion subsystem combined test device and test method |
| US11041800B2 (en) | 2018-09-06 | 2021-06-22 | Harbin Medical University | Method for detecting content of fluoride ions in microsamples |
| US11193883B2 (en) | 2018-09-06 | 2021-12-07 | Harbin Medical University | Kits for detecting content of fluoride ions in microsamples |
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| CN103558168A (en) * | 2013-10-31 | 2014-02-05 | 大连大公环境检测有限公司 | Detection method for fluoride content |
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| US11041800B2 (en) | 2018-09-06 | 2021-06-22 | Harbin Medical University | Method for detecting content of fluoride ions in microsamples |
| US11193883B2 (en) | 2018-09-06 | 2021-12-07 | Harbin Medical University | Kits for detecting content of fluoride ions in microsamples |
| CN112729852A (en) * | 2020-12-22 | 2021-04-30 | 西安精密机械研究所 | Three-component turbine power combustion subsystem combined test device and test method |
| CN112729852B (en) * | 2020-12-22 | 2023-08-04 | 西安精密机械研究所 | Combined test device and test method for power combustion subsystem of three-component turbine |
| CN114235545A (en) * | 2022-02-21 | 2022-03-25 | 山东东润仪表科技股份有限公司 | High-precision sample introduction system and use method thereof |
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