CN105181593B - A kind of bubble-free interference flow cell, flow analysis-optical detection apparatus and purposes - Google Patents
A kind of bubble-free interference flow cell, flow analysis-optical detection apparatus and purposes Download PDFInfo
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Abstract
Flow cell is interfered for flow analysis-optical detection bubble-free the present invention relates to a kind of, a kind of flow analysis-optical detection apparatus of valveless bubble-free interference can continuously analyze the various objects based on optical detection.Based on the flow cell, bubble can be overcome to interfere, simple hsrdware requirements can reduce cost.Sample solution and the alternate flow path designs of cleaning solution can reduce memory effect, improve analysis speed, constant temperature mixing module can heating sample solution and reagent solvent to close to boiling, even more improve reaction speed.
Description
Technical field
The present invention relates to flow analysis field, more specifically to it is a kind of for flow analysis-optical detection without gas
Bubble interference flow cell, a kind of flow analysis-optical detection apparatus that valveless bubble-free is interfered and a kind of interference of valveless bubble-free
Flow analysis-optical detection apparatus purposes.
Background technique
The analysis method of water quality parameter (such as nutritive salt) mostly uses greatly manual operations, analysis essence in national standard at present
Degree, the labor intensity height for reducing manual operation error, a large amount of sample analysis.
Now, bubble interval Continuous Flow Analysis, Flow Injection Analysis, Sequential Injection Analysis, lab-on-valve etc. are a variety of
Flow Analysis Technique is widely applied in Determination of Environmental Samples, and is had commercialization instrument and emerged.But these instruments
There are still following problems:
(1) when the bubble in analysis flow path passes through the flow cell of optical detecting instrument, optical interference can be generated, is caused " false
Signal ".The generation of bubble may originate from sample replacement, solvent mixes, pipeline sealing is bad, pressure change, temperature increase and cause
Gas solubility variation and other unknown reasons, it is difficult to avoid.Existing air bubble eliminating device is in the presence of structure is complicated, molten
The disadvantages of liquid diffusion is serious, effect is undesirable, reduces the efficiency and accuracy of analysis.
(2) flow analysis instrument when analyzing various sample needs that certain sample solution and certain time is spent to clean stream
Road pipeline, otherwise has memory effect；And cleaning step will lead to sample lost, analysis slows.
(3) current flow analysis instrument is required to high-precision computer-controlled multi-position switching valve, multi-center selection valve
Or sampling valve, peristaltic pump, costly, device is complicated for price, limits it and promotes and apply.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of low costs, and meet environmental sample point
The requirement of analysis, promote the development of related fieldss such as environmental science, Marine Sciences is used for flow analysis-optical detection bubble-free
Flow analysis-optical detection apparatus of flow cell and a kind of interference of valveless bubble-free is interfered, and in continuous analysis with optics
The application of object based on detection.
Technical scheme is as follows:
It is a kind of for flow analysis-optical detection bubble-free interfere flow cell, including pedestal, be arranged in it is saturating in pedestal
Light pond body, liquid flow into pipe, liquid effuser；Liquid flows into pipe, liquid effuser is connected to light transmission pond body respectively；Light transmission pond body
Opposite two sides are transparent, and the bottom of light transmission pond body is cambered surface platform, and liquid flows into pipe, liquid effuser is located at light transmission pond body
The corresponding position in two sidewalls, the light source of optical detection is irradiated above the inflection point of cambered surface platform.
Preferably, being located at liquid to flow into the side wall that enters of the light transmission pond body of pipe side is sloping platform.
Preferably, the inflection point of cambered surface platform extends beyond the side out of the light transmission pond body positioned at liquid effuser side
Wall.
Preferably, the top surface of light transmission pond body has extended downwardly baffle.
It is arranged with baffle in identical inclination angle preferably, liquid flows into pipe.
A kind of flow analysis-optical detection apparatus of valveless bubble-free interference, including sample peristaltic pump, reagent peristaltic pump,
Constant temperature mixing module, flow cell, optical detection apparatus, sample peristaltic pump, reagent peristaltic pump are continuous respectively to draw sample and reagent,
It is mixed into constant temperature mixing module, and mixed liquor is delivered to flow cell, tested and analyzed by optical detection apparatus.
Preferably, sample peristaltic pump, reagent peristaltic pump are same multi-channel peristaltic pump, controlled by the internal diameter of peristaltic tube
Flow rate is not provided with feed liquor valve body.
Preferably, constant temperature mixing module includes thermostat water bath, mixer, mixer is that coil pipe, threeway are reacted in threeway
First input end, the second input terminal of reaction coil pipe input sample solution or reagent solution, the liquid of output end and flow cell respectively
Body flows into pipe connection.
Preferably, sample peristaltic pump alternately draws sample solution and cleaning solution.
Flow analysis-optical detection apparatus of the valve bubble-free interference, for continuously analyzing using optical detection as base
The application of the object of plinth.
Beneficial effects of the present invention are as follows:
The flow cell of special designing allows a large amount of bubbles to enter, but is based on buoyancy, and bubble is not on detection light
On the road, light detection will not be impacted.Therefore, it can arbitrarily switch sample and reagent at any time, not need termination of pumping or using fixed
Measure ring；Temperature can be promoted and accelerate reaction, bubble caused by increasing without having to worry about temperature interferes.On the contrary, the introducing of bubble can be with
The degree of mixing for improving sample and reagent, is conducive to react.
A multi-channel peristaltic pump is only needed in package unit, by the internal diameter coutroi velocity ratio of peristaltic tube, without any
Sampling valve or multi-center selection valve.Different from Flow Injection Analysis and Sequential Injection Analysis, flow path designs of the invention are very big
Ground reduces installation cost.
By the switching of sample solution and cleaning solution, the memory effect between sample analysis is reduced, difference is suitable for
The analysis of concentration samples.
It is fast to analyze speed, can achieve 60 samples or higher per hour.
Flow analysis-optical detection apparatus of valveless bubble-free interference of the present invention, can continuously be analyzed and be examined with optics
Various objects based on survey.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of flow cell；
Fig. 2 is flow analysis-optical detection apparatus flow path schematic diagram；
Fig. 3 is the nitrite working curve of different salinity artificial seawater substrate；
Fig. 4 is the reactive phosphate working curve of different salinity artificial seawater substrate；
Fig. 5 is the active silicate working curve of different salinity artificial seawater substrate；
In figure: 10 be pedestal, and 11 be light transmission pond body, and 12 be that liquid flows into pipe, and 13 be liquid effuser, and 14 be that cambered surface is flat
Platform, 15 be light source, and 16 be sloping platform, and 17 be baffle.
Specific embodiment
The present invention is further described in detail with reference to the accompanying drawings and embodiments.
The present invention provides a kind of for flow analysis-light to overcome bubble existing for the analyzer of the prior art to interfere
The bubble-free for learning detection interferes flow cell, as shown in Figure 1, including pedestal 10, the light transmission pond body 11 being arranged in pedestal 10, liquid
Flow into pipe 12, liquid effuser 13；Liquid flows into pipe 12, liquid effuser 13 is connected to light transmission pond body 11 respectively；Light transmission pond body
11 opposite two sides are transparent, and the bottom of light transmission pond body 11 is cambered surface platform 14, and liquid flows into pipe 12, liquid effuser 13 distinguishes position
In the corresponding position in the two sidewalls of light transmission pond body 11, the light source 15 of optical detection is shone above the inflection point of cambered surface platform 14
It penetrates.Bubble flows out under the action of buoyancy from the inner upper of flow cell, and bubble is not in light path, will not be to light
Detection is learned to impact.Liquid flows into pond, and in the bottom of light transmission pond body 11 by carry out optical detection.
It in order to make bubble under the action of buoyancy, is flowed out from the inner upper of flow cell, is located at liquid and flows into 12 side of pipe
Light transmission pond body 11 enter side wall be sloping platform 16.The top surface of light transmission pond body 11 has extended downwardly baffle 17, and effect is main
It is to reduce the dead volume in flow cell.Liquid flows into pipe 12 and baffle 17 and is arranged in identical inclination angle, in order to cooperate liquid flow
Enter being obliquely installed for pipe 12, the top surface of flow cell is provided with sloping platform 16, it is vertical with sloping platform 16 that liquid flows into pipe 12
Connection.
In the present embodiment, flow cell is made of glass or plastic material, specification (length × width × height) (0.1-10) cm ×
Between (0.1-10) cm × (0.1-20) cm, light path is between 0.1-10cm.Liquid flows into pipe 12, liquid effuser 13 by metal
Or glass material is made, internal diameter is between 0.01-10mm, and length is between 0.1-10cm；The horizontal sextant angle θ that liquid flows into end exists
Between 0-180 °；The internal capacity of light transmission pond body 11 is between 0.01-10mL；The length of baffle 17 is between 0.01-5mm, gear
The distance of bottom of pond of the end of plate 17 away from light transmission pond body 11 is between 0.1-5cm.
The inflection point of cambered surface platform 14 extends beyond the side wall out of the light transmission pond body 11 positioned at 13 side of liquid effuser, makes
The path of liquid and the path of bubble are as far away from bubble is preferably minimized the interference of optical detection.
Based on the flow cell, the present invention also provides a kind of flow analysis of valveless bubble-free interference-optical detection dresses
It sets, as shown in Fig. 2, including sample peristaltic pump, reagent peristaltic pump, constant temperature mixing module, flow cell, optical detection apparatus, utilizes
Continuous Flow Analysis technology, sample peristaltic pump, reagent peristaltic pump are continuous respectively to draw sample and reagent, until in constant temperature mixing module
Mixing, and mixed liquor is delivered to flow cell, it is tested and analyzed by optical detection apparatus.The constant temperature mixing module packet
Thermostat water bath, mixer are included, mixer is that coil pipe is reacted in threeway, and first input end, the second input terminal of coil pipe are reacted in threeway
Sample solution or reagent solution, the liquid inflow connection of pipe 12 of output end and flow cell are inputted respectively.Flow cell allows a large amount of gas
Bubble enters, but is based on buoyancy, and bubble is not in light path, will not impact to optical detection.Therefore, may be used
Arbitrarily to switch sample and reagent at any time, does not need termination of pumping or use quantitative loop.Temperature can also be promoted and accelerate reaction, without load
Bubble caused by heart temperature increases interferes.On the contrary, the degree of mixing of sample and reagent can be improved in the introducing of bubble, be conducive to anti-
It answers.
In order to reduce cost of implementation, simplify structure, sample peristaltic pump, reagent peristaltic pump are same multi-channel peristaltic pump, are led to
The internal diameter coutroi velocity ratio for crossing peristaltic tube is not provided with feed liquor valve body (such as sampling valve or multi-center selection valve).Different from flowing
Injection Analysis and Sequential Injection Analysis, flow path designs of the invention significantly reduce installation cost.
Sample peristaltic pump alternately draws sample solution and cleaning solution.Sample solution and the alternate flow path designs of cleaning solution
Memory effect can be reduced, improve analysis speed, constant temperature mixing module can heating sample solution and reagent solvent to close to boiling,
Even more improve reaction speed.
The characteristics of according to object, optical detection apparatus can choose UV-vis detector, fluorophotometric detection
Any one in device, CL and BL detector.
In the present embodiment, sample solution and various reagents, Ge Getong is sucked out in peristaltic pump respectively from sample bottle and reagent bottle
The actual flow velocity of road solution between 0.001-50mL/min, the solution flow rate in each channel 1:100 to 100:1 it
Between.Sample solution and different reagents are more fully mixed in constant temperature mixing module after 1-10 mixer mixes
It closes, and is reacted under set temperature (0-100 DEG C), the product after reaction is detected in flow cell by optical detection apparatus, completes
The overall process of analysis.Wherein, a length of 1-3600s when sample solution and cleaning solution switch, and it is not necessarily to termination of pumping, hand can be passed through
Work or multi-channel electromagnetic valve carry out the switching of sample.
Flow analysis-optical detection apparatus of valve bubble-free interference of the present invention, is examined for continuously analyzing with optics
Object based on survey can continuously analyze the various objects based on optical detection.
Test examples
1, in water sample nitrite measurement
Principle: sample mixes under the push of pump through threeway with color developing agent, and mixed liquor subsequently enters in constant temperature mixing module
Reaction, the rose compound of generation are detected by visible photometric detector.Select 540nm as measurement wavelength, 700nm conduct
Reference wavelength.
1.1, the optimization of reaction condition
This experiment uses single_factor method, optimizes to the reaction condition of nitrous nitrification, including sample injection time, reagent
Concentration, reaction coil lengths, flow velocity, reaction temperature etc..Optimization experiment is made with the pure water mark-on sample containing 2 μm of ol/L nitrite
For test specimens, all samples are at least measured 3 times.
The Optimum Experiment range of sample injection time is 2-35s, selects optimal sample injection time for 25s.
The Optimum Experiment range of sulfanilamide (SN) concentration is 0.5-6.0g/L, and selecting optimal sulfanilamide (SN) concentration is 4.0g/L.
The optimization scope of experiment of hydrochloride naphthodiamide concentration is 0.05-0.60g/L, selects optimal hydrochloride naphthodiamide dense
Degree is 0.4g/L.
The Optimum Experiment range for reacting coil lengths is 0.2-3.0m, and selecting optimal reaction coil lengths is 2.5m.
The Optimum Experiment range of flow velocity is 7.0-12.0mL/min, selects optimal flow velocity for 10.0mL/min.
The Optimum Experiment range of reaction temperature is 20-70 DEG C, selects optimal temperature for 50 DEG C.
1.2, the influence of salinity
Influence of the salinity to this method is investigated, taking salinity is 35 artificial seawater, and salinity point is obtained after being diluted with ultrapure water
Not Wei 0,5,10,15,20,25,30,35 8 artificial seawater samples.Using the seawater sample of these different salinities as substrate,
Working curve solution is prepared respectively, draws corresponding working curve.As shown in figure 3,8 working curve linearly dependent coefficient R2?
Between 0.9973-0.9990, illustrate that linear relationship is good.The relative standard deviation of 8 working curve slopes is 1.2%, therefore
Think, influence of the salinity to this method can be ignored.
1.3, the influence of memory effect
Memory effect refers in analytic process that a sample, which enters to be detained caused by analysis system, rings next sample
The influence that should be worth.The influence of memory effect can be according to memory effect coefficient kCOIt is assessed, and kCOIt can be obtained by calculation.For
Calculating kCO, twice (set specimen coding as i-3, i-2), obtain corresponding light absorption value is respectively measurement low concentration sample first
Ai-3, Ai-2；Then measurement High concentration samples are primary (setting specimen coding as i-1), and obtaining corresponding light absorption value is Ai-1；Finally survey
It is primary (setting specimen coding as i) to determine low concentration sample, obtaining corresponding light absorption value is Ai, as a measurement period.kCOIt can
It is calculated by the following formula and obtains:
kCO=(Ai-Ai-2)/Ai-1；
In order to investigate memory effect when this method measurement nitrite, it is low dense for taking containing 1 μm of ol/L nitrite sample
Spend sample, be High concentration samples containing 30 μm of ol/L nitrite samples, under optimum experimental condition to the sample of various concentration into
Row measurement, changes scavenging period.The experimental results showed that with the increase of scavenging period, memory effect coefficient kCOIt is gradually reduced.It is comprehensive
It closes and considers the factors such as analysis speed, select scavenging period for 30s.
1.4, working curve, method detection limit and collimation
Under optimum experimental condition, draw working curve, the concentration of working curve solution is 0,1,2,4,8,12,16,32,
50 μm of ol/L, obtaining working curve is y=(0.0325 ± 0.0002) x- (0.0092 ± 0.0044) (n=8), R2=
0.9998；The range of linearity is 0-80 μm of ol/L.
0.2 μm of ol/L nitrite of mark-on in ultrapure water is measured in parallel 7 times, calculate the detection of this method is limited to
0.06μmol/L。
Under optimum experimental condition, 2 μm of ol/L and 8 μm of ol/L nitrite samples are distinguished METHOD FOR CONTINUOUS DETERMINATION 8 times, phase is obtained
It is respectively 1.60% and 0.98% to standard deviation, illustrates that the method that this experiment is established has good collimation.
1.5, recovery of standard addition
The concentration of nitrite in different type sample is measured with this method, and carries out substrate recovery of standard addition experiment.Add
The rate of recovery is marked between 100.1-108.7%, illustrates that this method is suitable for the analysis of different base sample, test sample substrate is not dry
It disturbs.
1.6, method validation with compare
In order to verify the reliability of this method, with nitrous in this method and " marine monitoring specification " (GB17378.4-2007)
Hydrochlorate-naphthodiamide spectrophotometry, while different types of sample and standard substance (GSBZ50006-88) are analyzed, two kinds
After the data fitting that method measures, the slope for obtaining equation of linear regression is 1.0295, regression coefficient R2=0.9991.Illustrate two
There was no significant difference for kind method.
2, in water sample reactive phosphate measurement
Principle: mixed color developing agent first mixes under the push of pump through threeway with ascorbic acid, then with sample mixed.Mixed liquor
The reaction of constant temperature mixing module is subsequently entered, P-Mo blue compound generated is detected by visible photometric detector.880nm is selected to make
To measure wavelength.
2.1, the optimization of reaction condition
This experiment uses single_factor method, optimizes to the reaction condition of reactive phosphate measurement, including sample injection time, examination
Agent concentration, reaction coil lengths, flow velocity, reaction temperature etc..Optimization experiment is with the phosphatic pure water mark-on containing 4 μm of ol/L active phosphorus
Sample at least measures 3 times as test specimens, all samples.
The Optimum Experiment range of sample injection time is 2-35s, selects optimal sample injection time for 30s.
The Optimum Experiment range of ammonium molybdate mixed liquid concentration is ammonium molybdate mixed solution stock solution (the dense sulphur of 75mL of 5-20%
Acid is added in 175mL ultrapure water, and after being cooled to room temperature, 7g ammonium molybdate, 0.15g potassium antimony tartrate is added), select optimal molybdic acid
Ammonium mixed liquid concentration is the 12.5% of stock solution.
The Optimum Experiment range of ascorbic acid concentrations is 5-35g/L, selects optimal ascorbic acid concentrations for 25g/L.
The Optimum Experiment range for reacting coil lengths is 0.5-3.5m, and selecting optimal reaction coil lengths is 2.5m.
The Optimum Experiment range of flow velocity is 7.2-12.2mL/min, selects optimal flow velocity for 10.2mL/min.
The Optimum Experiment range of reaction temperature is 25-60 DEG C, selects optimal temperature for 40 DEG C.
2.2, the influence of salinity
Influence of the salinity to this method is investigated, taking salinity is 35 artificial seawater, and salinity point is obtained after being diluted with ultrapure water
Not Wei 0,5,10,15,20,25,30,35 8 artificial seawater samples.Using the seawater sample of these different salinities as substrate,
Working curve solution is prepared respectively, draws corresponding working curve.As shown in figure 4,8 working curve linearly dependent coefficient R2?
Between 0.9988-0.9998, illustrate that linear relationship is good.The relative standard deviation of 8 working curve slopes is 1.2%, therefore
Think, influence of the salinity to this method can be ignored.
2.3, the interference of silicate and arsenate
When measuring the reactive phosphate in water body with molybdenum blue method, since silicate can form similar phosphorus with arsenate
The silicon or As-Mo heteropoly acid of molybdenum heteropolyacid increase the response intensity of detection signal, therefore become the main interference of phosphate determination
Substance.Under optimum experimental condition, 2 μm of ol/L and 4 μm of ol/L phosphate samples are taken, change wherein silicate and arsenate respectively
Concentration, measure light absorption value.
When the additional amount of silicate is between 0-400 μm of ol/L, light absorption value is held essentially constant.Illustrate the concentration range
Silicate it is very small to the interference of this method.When the additional amount of arsenate is between 0-40nmol/L, light absorption value is protected substantially
It holds constant.Illustrate that the arsenate of the concentration range is very small to the interference of this method.
2.4, the influence of memory effect
In order to investigate memory effect when this method measurement reactive phosphate, takes and be containing 1 μm of ol/L reactive phosphate sample
Low concentration sample is High concentration samples containing 10 μm of ol/L reactive phosphate samples, to various concentration under optimum experimental condition
Sample is measured, and changes scavenging period.The experimental results showed that with the increase of scavenging period, memory effect coefficient kCOGradually
Reduce.Comprehensively consider the factors such as analysis speed, selects scavenging period for 30s.
2.5, working curve, method detection limit and collimation
Under optimum experimental condition, working curve is drawn, the concentration of working curve solution is 0,2,4,6,8,10 μm of ol/L,
Obtaining working curve is y=(0.0212 ± 0.0002) x- (0.0008 ± 0.0010) (n=6), R2=0.9998.The range of linearity
For 0-14 μm of ol/L.
0.3 μm of ol/L active phosphorus of mark-on in ultrapure water is measured in parallel 8 times, calculate the detection of this method is limited to 0.08 μ
mol/L。
Under optimum experimental condition, 2 μm of ol/L and 8 μm of ol/L reactive phosphate samples are distinguished METHOD FOR CONTINUOUS DETERMINATION 9 times, are obtained
Relative standard deviation is respectively 1.74% and 0.69%, illustrates that the method that this experiment is established has good collimation.
2.6, recovery of standard addition
The concentration of reactive phosphate in different type sample is measured with this method, and carries out substrate recovery of standard addition experiment.
Recovery of standard addition illustrates that this method is suitable for the analysis of different base sample, not test sample substrate between 91.5-104.0%
Interference.
2.7, method validation with compare
In order to verify the reliability of this method, with activity in this method and " marine monitoring specification " (GB17378.4-2007)
Phosphate-P-Mo blue spectrophotometry, while different types of sample and standard substance (GSBZ50028-94) are measured, two kinds
After the data fitting that method measures, the slope for obtaining equation of linear regression is 1.0074, regression coefficient R2=0.9913.Illustrate two
There was no significant difference for kind method.
3, in water sample active silicate measurement
Principle: sample is successively mixed with ammonium molybdate mixed solution, oxalic acid solution, ascorbic acid solution through threeway, is mixed
It closes liquid and subsequently enters the reaction of constant temperature mixing module, silicon molybdenum blue compound generated is detected by visible photometric detector.Selection
810nm is as measurement wavelength.
3.1, the optimization of reaction condition
This experiment uses single_factor method, optimizes to the reaction condition of active silicate measurement, including sample injection time, examination
Agent concentration, reaction coil lengths, flow velocity, reaction temperature etc..Optimization experiment is with the pure water mark-on containing 25 μm of ol/L active silicates
Sample at least measures 3 times as test specimens, all samples.
The Optimum Experiment range of sample injection time is 2-35s, selects optimal sample injection time for 30s.
The Optimum Experiment range of ammonium molybdate mixed solution concentration is 10-50g/L, selects optimal ammonium molybdate mixed solution dense
Spend 35g/L.
The Optimum Experiment range of the concentration of the concentrated sulfuric acid be 0.05-0.70mol/L, select optimal concentrated sulfuric acid concentration for
0.4mol/L。
The Optimum Experiment range of ascorbic acid concentrations is 10-70g/L, and selecting optimal ascorbic acid concentrations range is 50g/
L。
The Optimum Experiment range for reacting coil lengths is 0.2-6.0m, and selecting optimal reaction coil lengths is 5.0m.
The Optimum Experiment range of ammonium molybdate mixed solution and sample mixed coil lengths is 0.2-5.0m, is selected optimal mixed
Conjunction coil lengths are 4.0m.
The Optimum Experiment range of flow velocity is 8.8-15.8mL/min, selects optimal flow velocity for 13.0mL/min.
The Optimum Experiment range of reaction temperature is 25-60 DEG C, selects optimal temperature for 55 DEG C.
3.2, the influence of salinity
Influence of the salinity to this method is investigated, taking salinity is 35 artificial seawater, and salinity point is obtained after being diluted with ultrapure water
Not Wei 0,5,10,15,20,25,30,35 8 artificial seawater samples.Using the seawater sample of these different salinities as substrate,
Working curve solution is prepared respectively, draws corresponding working curve.As shown in figure 5,8 working curve linearly dependent coefficient R2?
Between 0.9992-0.9998, illustrate that linear relationship is good.8 working curve slopes are gradually reduced, work with the increase of salinity
Following equation is obtained after making the relationship fitting of the slope of curve and salinity:
SX=SMQ-(2.88×10-4)X+(3.21×10-6)X2,R2=0.9957, n=8 (formula -2)
Wherein, salt angle value corresponding to X representing sample；SXIndicate the working curve slope corresponding when salinity is X；SMQ
Indicate the working curve slope for the solution prepared using ultrapure water as substrate.
In real work, solution is usually prepared as substrate using ultrapure water and is worked curve.According to above formula, recoverable is obtained
Out under different salinity working curve slope, to calculate silicate concentration in sample.
3.3, phosphatic interference
When measuring the active silicate in water body with silicon molybdenum blue method, due to reactive phosphate and active silicic acid reactant salt item
Part is similar, phosphatic to there is the response intensity that will increase detection signal, therefore becomes the main interference of active silicate measurement
Substance.Oxalic acid can eliminate this interference.Under optimum experimental condition, sample containing only 25 μm of ol/L active silicates is taken and containing 25
The sample of μm ol/L active silicate and 8 μm of ol/L reactive phosphates adds the oxalic acid of different solubility respectively, measures light absorption value,
Observe the situation of change of light absorption value.
When concentration of oxalic acid is greater than 30g/L, the light absorption value of two kinds of samples is almost the same, illustrates reactive phosphate to this method
Interference it is very small.It is final to determine that oxalic acid solubility is 50g/L.
3.4, the influence of memory effect
In order to investigate memory effect when this method measurement active silicate, takes and be containing 5 μm of ol/L active silicate samples
Low concentration sample is High concentration samples containing 50 μm of ol/L active silicate samples, to various concentration under optimum experimental condition
Sample is measured, and changes scavenging period.The experimental results showed that with the increase of scavenging period, memory effect coefficient kCOGradually
Reduce.Comprehensively consider the factors such as analysis speed, selects scavenging period for 20s.
3.5, working curve, method detection limit and collimation
Under optimum experimental condition, working curve is drawn, the concentration of working curve solution is 0,5,10,20,40,60,80 μ
Mol/L, obtaining working curve is y=(0.0191 ± 0.0001) x- (0.0163 ± 0.0054) (n=7), R2=0.9998.Line
Property range be 0-120 μm of ol/L.
0.3 μm of ol/L active silicate of mark-on in ultrapure water is measured in parallel 8 times, calculate the detection of this method is limited to
0.11μmol/L。
Under optimum experimental condition, 5 μm of ol/L and 30 μm of ol/L active silicate samples are distinguished METHOD FOR CONTINUOUS DETERMINATION 9 times, are obtained
It is respectively 1.67% and 0.38% to relative standard deviation, illustrates that the method that this experiment is established has good collimation.
3.6, recovery of standard addition
The concentration of active silicate in different type sample is measured with this method, and carries out substrate recovery of standard addition experiment.
Recovery of standard addition illustrates that this method is suitable for the analysis of different base sample, test sample substrate is not dry between 95.1-99.2%
It disturbs.
3.7, method validation with compare
In order to verify the reliability of this method, with activity in this method and " marine monitoring specification " (GB17378.4-2007)
Silicate-Silicon Molybdenum Blue Spectrophotometry, while different types of sample is analyzed, after the data fitting that two methods measure, obtain
The slope of equation of linear regression is 1.0043, regression coefficient R2=0.9904.Illustrating two methods, there was no significant difference.
Above-described embodiment is intended merely to illustrate the present invention, and is not used as limitation of the invention.As long as according to this hair
Bright technical spirit is changed above-described embodiment, modification etc. will all be fallen in the scope of the claims of the invention.
Claims (10)
1. a kind of interfere flow cell for flow analysis-optical detection bubble-free, which is characterized in that exist including pedestal, setting
Light transmission pond body, liquid in pedestal flow into pipe, liquid effuser；Liquid flows into pipe, liquid effuser and connects respectively with light transmission pond body
It is logical；The opposite two sides of light transmission pond body are transparent, and the bottom of light transmission pond body is cambered surface platform, and liquid flows into pipe, liquid effuser difference
Positioned at the corresponding position in the two sidewalls of light transmission pond body, the light source of optical detection is irradiated above the inflection point of cambered surface platform；Base
In buoyancy, bubble is not in light path.
2. according to claim 1 interfere flow cell for flow analysis-optical detection bubble-free, which is characterized in that
The side wall that enters that the light transmission pond body of pipe side is flowed into positioned at liquid is sloping platform.
3. according to claim 1 interfere flow cell for flow analysis-optical detection bubble-free, which is characterized in that
The inflection point of cambered surface platform extends beyond the side wall out of the light transmission pond body positioned at liquid effuser side.
4. according to claim 1 interfere flow cell for flow analysis-optical detection bubble-free, which is characterized in that
The top surface of light transmission pond body has extended downwardly baffle.
5. according to claim 4 interfere flow cell for flow analysis-optical detection bubble-free, which is characterized in that
Liquid flows into pipe and is arranged with baffle in identical inclination angle.
6. a kind of flow analysis-optical detection apparatus of valveless bubble-free interference, which is characterized in that including sample peristaltic pump, examination
Agent peristaltic pump, constant temperature mixing module, flow cell such as described in any one of claim 1 to 5, optical detection apparatus, sample are wriggled
Pump, reagent peristaltic pump are continuous respectively to draw sample and reagent, until mixing in constant temperature mixing module, and mixed liquor is delivered to circulation
Pond is tested and analyzed by optical detection apparatus.
7. flow analysis-optical detection apparatus of valveless bubble-free interference according to claim 6, which is characterized in that examination
Sample peristaltic pump, reagent peristaltic pump are not provided with feed liquor by the internal diameter coutroi velocity ratio of peristaltic tube for same multi-channel peristaltic pump
Valve body.
8. flow analysis-optical detection apparatus of valveless bubble-free interference according to claim 6, which is characterized in that permanent
Warm mixing module includes thermostat water bath, mixer, and mixer is that coil pipe is reacted in threeway, and the first input of coil pipe is reacted in threeway
End, the second input terminal input sample solution or reagent solution, the liquid inflow pipe connection of output end and flow cell respectively.
9. flow analysis-optical detection apparatus of valveless bubble-free interference according to claim 6, which is characterized in that examination
Sample peristaltic pump alternately draws sample solution and cleaning solution.
10. flow analysis-optical detection apparatus of the described in any item valveless bubble-free interference of claim 6 to 9, for continuous
Analyze the application of the object based on optical detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510660835.4A CN105181593B (en) | 2015-10-14 | 2015-10-14 | A kind of bubble-free interference flow cell, flow analysis-optical detection apparatus and purposes |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510660835.4A CN105181593B (en) | 2015-10-14 | 2015-10-14 | A kind of bubble-free interference flow cell, flow analysis-optical detection apparatus and purposes |
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| Publication Number | Publication Date |
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| CN105181593A CN105181593A (en) | 2015-12-23 |
| CN105181593B true CN105181593B (en) | 2019-02-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510660835.4A Expired - Fee Related CN105181593B (en) | 2015-10-14 | 2015-10-14 | A kind of bubble-free interference flow cell, flow analysis-optical detection apparatus and purposes |
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| Country | Link |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6617191B1 (en) * | 2018-12-03 | 2019-12-11 | 三井金属鉱業株式会社 | Method and apparatus for separating or analyzing target components in a solution |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH515502A (en) * | 1970-07-06 | 1971-11-15 | Kasparek Vladimir | Flow cell |
| US5550053A (en) * | 1995-01-05 | 1996-08-27 | Si Industrial Instruments, Inc. | Method of calibrating an automatic chemical analyzer |
| US8035809B2 (en) * | 2007-12-21 | 2011-10-11 | Bausch & Lomb Incorporated | Bubble removal system |
| US8493565B1 (en) * | 2008-07-24 | 2013-07-23 | J.A. Wollam Co., Inc. | Small volume cell |
| US8502969B2 (en) * | 2009-12-16 | 2013-08-06 | Boule Medical Ab | Miniature flow-through cuvette and spectrophotometer containing the same |
| AT510765B1 (en) * | 2010-12-15 | 2012-09-15 | Wolfgang Dipl Ing Vogl | DEVICE FOR PHOTOMETRIC OR BZW. SPECTROMETRIC STUDY OF A LIQUID SAMPLE |
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| CN105181593A (en) | 2015-12-23 |
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