CN104483164A - On-site multi-spot water-sample sampling device and COD (chemical oxygen demand) content detection method - Google Patents
On-site multi-spot water-sample sampling device and COD (chemical oxygen demand) content detection method Download PDFInfo
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Abstract
The invention relates to the technical field of spectrum detection, in particular to an on-site multi-spot water-sample sampling device and a COD (chemical oxygen demand) content detection method. The device comprises a submarine-type armature device, a sampling device and a remote control device. The method comprises the steps of (a) preparation of equipment, (b) sampling, (3) multi-point sampling, wherein the step (b) is repeated until all samples in a sampling chamber are taken, (d) sample recycling and (e) spectrum detection. Accurate advancing information and position information of the submarine-type armature device can be obtained in a water body, the device is more convenient to operate and control, and the COD content distribution condition of the water body can be measured more accurately; multiple samples can be collected after the device is launched once, and the collection efficiency is high; the COD content of the water body can be quickly and accurately measured through spectra, and no second pollution is caused to the water body.
Description
Technical field
The present invention relates to technical field of spectral detection, particularly relate to the on-the-spot multi-point sampling device of a kind of water sample and COD detection method of content.
Background technology
When evaluating water pollution situation, chemical oxygen demand (COD) (chemical oxygen demand, COD) be an important indicator weighing water body organism pollution level, a lot of correlative study shows when the COD concentration in water body exceedes certain limit value, negative effect can be caused to the growth of water quality and aquatic products, and the processing cost of water body can be increased, therefore the COD concentration detected in water body is of great practical significance fast.Traditional COD assay method comprises dichromate method and rapid-digestion spectrophotometric method etc., the new method such as electrochemical method and flow injection analysis is also for the measurement of COD, but these methods all also exist length analysis time, need to consume reagent, there is secondary pollution equivalent risk, take into account the accuracy of determination data, simple operation and environment friendly and pollution-free characteristic, utilize spectroscopy technology substitute conventional chemical analysis method application to a certain extent.Generally once can only gather the water sample of a point at present to water body sampling, can not accomplish that multiple spot is sampled simultaneously, can not determine the depth information of sampling, the water body representativeness of sample that this sample mode collects is not enough, limited to production practices directive function.
Summary of the invention
For solving the problem, the object of the present invention is to provide a kind of multi-point sampling more truly can reflect the water body COD content on site multi-point sampling device and method of water body COD content distribution situation, Quick Measurement.
For reaching above-mentioned purpose, the technical scheme of the present invention's sampling is: the on-the-spot multi-point sampling device of a kind of water sample COD, include submarine formula electricity driving device, sampling apparatus, telechiric device, wherein: submarine formula electricity driving device, by housing, electricity drives screw propeller, lifting water pump, reserve tank forms, housing is hollow structure, electricity drives screw propeller suspension and is arranged on housing, lifting water pump and reserve tank are fixedly installed in enclosure interior, water inlet/the water delivering orifice of lifting water pump is communicated with reserve tank, water delivering orifice/the water inlet of lifting water pump is communicated with outside, water inlet/water delivering orifice is equipped with anti-sealing and pours in down a chimney non-return valve into housing, sampling apparatus includes sampling pump, storage sample case, and the water inlet of sampling pump is communicated with outside, water delivering orifice is communicated with storage sample case, and water inlet and water delivering orifice are equipped with the non-return valve preventing water sample from refluxing, telechiric device, includes monitoring probe, remote control transceiver module, electronic control module and remote-control handle, and monitoring probe is arranged on the outer wall of housing head end, remote control transceiver module is arranged on the sidewall of housing rear end, remote control transceiver module and remote-control handle wireless telecommunications, electronic control module with monitoring probe, remote control transceiver module, be elevated the start and stop solenoid valve of pump, the start and stop solenoid valve of sampling pump is electrically connected, send the Detection Information of monitoring probe, and receive remote-control handle instruction control lifting pump, sampling pump action, remote-control handle is provided with directional control rocking bar, liquid shows module, and directional control rocking bar controls the motion in comprehensive direction with oscilaltion all around of submarine formula electricity driving device, and liquid shows the information of the real-time display monitoring probe of module.
Preferably, described lifting water pump includes rising water pump and decline water pump, and the water delivering orifice of rising water pump is communicated with the apopore being arranged on housing bottom, water inlet is communicated with reserve tank; The water delivering orifice of decline water pump is communicated with reserve tank, water inlet is communicated with the inlet opening being arranged on case top.
Preferably, described rising water pump, decline water pump and sampling pump are Mini gear pump.
Preferably, described electricity drives screw propeller and comprises three screw propellers, hangs the afterbody being arranged on housing two flank and housing respectively.
Preferably, described storage sample case is provided with the storage sample room of more than 4 autonomous closure, and each storage sample room is communicated with sampling pump water delivering orifice respectively by pipeline, and is provided with solenoid valve at every root pipeline.
Preferably, described housing is syllogic splicing structure, by front end end cover, body and rear end cap thread connection, is provided with O-ring seal between connection.
Preferably, the drive motor plastic cement sealing of described screw propeller, power lead is wrapped in seal.
Preferably, described monitoring probe comprises camera and ultrasonic probe, and video information is transmitted feeding and shows module display by camera, and depth information is transmitted feeding and shows module display by ultrasonic probe.
One utilizes above-mentioned sampling apparatus water body COD detection method of content, it is characterized in that: include following steps:
(1) equipment prepares: submarine formula electricity driving device is put into examination water tank, debugging lifting water pump and sampling pump, and whether after lifting water pump and sampling pump normal operation, then it is normal to debug screw propeller motor, camera and ultrasonic probe state; After all debugging are normal, empty reserve tank and sampling box, submarine formula electricity driving device is put into the water body in tested region; Starting outfit;
(2) sample: coordinate camera and ultrasonic probe, remote control submarine formula electricity driving device enters sampled point, opens the electromagnetic valve on sampling pump and corresponding sampler chamber pipeline, completes this sampled point sampling work;
(3) multi-point sampling: repeat above-mentioned steps (2), until sampler chamber has all been adopted;
(4) sample reclaims: rising water pump is opened in remote control, and submarine formula electricity driving device emerges, and drives screw propeller that submarine formula electricity driving device is pushed to sample recovery point, takes out sampling box water sample;
(5) spectral detection:
Spectral scan is carried out to water sample, deionized water is adopted to do baseline correction, the quartz colorimetric utensil optical path length of water sample is 10 mm, utilizes the absorption spectrum that wavelength is 208 nm, 223 nm, 238 nm, 340 nm, 355 nm, 362 nm, 372 nm, 380 nm and 392 nm are right at spectroscopic probe head acquisition testing point place; Physics and chemistry value calculates:
Y=15.336X1+20.256X2+32.114X3-26.458X4+358.542X5-489.668X6+256.334
X7+214.789X8-395.225X9+32.15, calculate COD content, in formula, Y is COD content, and X1 ~ X9 is respectively the absorption spectrum of 208 nm, 223 nm, 238 nm, 340 nm, 355 nm, 362 nm, 372 nm, 380 nm and the water corresponding to 392 nm.
Beneficial effect of the present invention: (1) submarine formula electricity driving device can oscilaltion in water, solves the present situation that prior art exists sampling difficulty under water; (2) camera and ultrasonic probe cooperation can obtain submarine formula electricity driving device accurate travel information and positional information in water body, and manipulate more convenient, it is more accurate that water body COD content distribution situation is measured; (3) sampling box has multiple sampler chamber, and disposable lower water can gather multiple sample, and collecting efficiency is high; (4) remote pilot mode of operation, simple to operation; (5) collection point image information and depth information show in real time on liquid crystal display, simple and clear; (6) spectral measurement water body COD content, quick and precisely, can not cause secondary pollution to water body.
Accompanying drawing explanation
Fig. 1 is submarine formula electricity driving device profile three-dimensional structure schematic diagram in the embodiment of the present invention;
Fig. 2 is submarine formula electricity driving device interior three-dimensional structural representation in the embodiment of the present invention;
Fig. 3 is remote-control handle three-dimensional structure schematic diagram in the embodiment of the present invention;
Fig. 4 is spectral detection structural representation in the embodiment of the present invention;
Fig. 5 is spectral detection result figure in the embodiment of the present invention.
Description of symbols in figure:
101---front end end cover, 102---body, 103---rear end cap, 104---electricity drives screw propeller;
201---radio receiving transmitting module, 202---ultrasonic probe, 203---camera, 204---electronic control module, 205---left and right directions control lever, 206---antenna, 207---remote-control handle body, 208---above-below direction control lever, 209---start-stop button, 210---liquid shows;
301---reserve tank, 302---decline water inlet pipe, 303---is elevated water pump, 304---rising rising pipe; 401---solenoid valve, 402---storage sample room, 403---sampling pipe, 404---sampling pump;
501---computer, 502---spectrometer, 503---receiving transducer, 504---quartz colorimetric utensil; 505---light source probe, 506---light source switch.
Embodiment
For understanding the present invention better, illustrating below in conjunction with accompanying drawing and with embodiment, technical scheme of the present invention to be described further, see Fig. 1 to Fig. 5:
By the on-the-spot multi-point sampling device of water sample of the invention process and COD detection method of content, in order to the multiple spot water sample sampling of the water surface and different depth under water can be realized, this sampling apparatus provides power by submarine formula electricity driving device, complete advancing in water body region between each sampled point, because waters distribution is wide, submarine formula electricity driving device radio range can reach the telechiric device wireless remote control of 500 meters.
Submarine formula electricity driving device concrete structure drives screw propeller by housing, electricity, lifting water pump 303, reserve tank 301 form, housing is hollow structure, in order to the mounting or dismounting of inner structure are convenient, housing is syllogic splicing structure, by front end end cover 101, body 102 and rear end cap 103 thread connection, be provided with O-ring seal between connection and avoid into water.Electricity drives screw propeller suspension and is arranged on housing, and described in the present embodiment, electricity drives the mode that screw propeller adopts three screw propellers, hangs the afterbody being arranged on housing two flank and housing respectively.Two flank electricity drive screw propeller and can conveniently turn, and the electricity of afterbody drives screw propeller and is responsible for propelling.The drive motor plastic cement of screw propeller seals, and power lead is wrapped in seal.
Lifting water pump 303 and reserve tank 301 are fixedly installed in enclosure interior, for the ease of controlling, described lifting water pump 303 comprises rising water pump and decline water pump, and the water delivering orifice of rising water pump is communicated with the apopore being arranged on housing bottom, water inlet is communicated with reserve tank 301; The water delivering orifice of decline water pump is communicated with reserve tank 301, water inlet is communicated with the inlet opening being arranged on case top.When such submarine formula electricity driving device needs to rise, only need start rising water pump, water extraction drains into housing from reserve tank 301 by rising water pump, and suffered by device, buoyancy is greater than gravity, and submarine formula electricity driving device rises.When needing to decline, then start decline water pump, water is evacuated to the reserve tank 301 of enclosure interior by decline water pump from external source, and suffered by device, buoyancy is less than gravity, and submarine formula electricity driving device rises.Because whole enclosure interior space is less, in order to ensure that rising water pump, decline water pump and sampling pump 404 all adopt Mini gear pump, and the material of Mini gear pump is plastics not by space constraint, gravity is light, and cost is low.The pipeline of water inlet/water delivering orifice is equipped with anti-sealing and pours in down a chimney non-return valve into housing.
Sampling apparatus includes sampling pump 404, storage sample case, and the water inlet of sampling pump 404 is communicated with outside, water delivering orifice is communicated with storage sample case, and water inlet and water delivering orifice are equipped with the non-return valve preventing water sample from refluxing.In order to the water sample once descending water can adopt multiple point, to understand the distribution of COD in waters more realistically, storage sample case is provided with the storage sample room 402 of more than 4 autonomous closure, and each storage sample room 402 is communicated with sampling pump 404 water delivering orifice respectively by pipeline, and is provided with solenoid valve 401 at every root pipeline.The number of storage sample room 402 is too much unsuitable, and solenoid valve 401 needed for internal duct is also corresponding to be increased, and weight and requisite space be corresponding increase also.
Telechiric device, include monitoring probe, remote control transceiver module, electronic control module 204 and remote-control handle, the effect of monitoring probe mainly obtains submarine formula electricity driving device video information and depth information in water body, video information is convenient to the operation attitude and the traffic direction that control whole device, and roughly determines that the turbidity of water body determines the need of sampling to help operator.Depth information then marked the depth of sample in water body, is convenient to the distribution situation recording water body COD.So in the present embodiment, monitoring probe comprises and is arranged on camera 203 on housing head end outer wall and ultrasonic probe 202, video information is transmitted the aobvious 210 module displays of feeding by camera 203, and depth information is transmitted the aobvious 210 module displays of feeding by ultrasonic probe 202.Remote control transceiver module is arranged on the sidewall of housing rear end, remote control transceiver module and remote-control handle wireless telecommunications.Electronic control module 204 is connected with start and stop solenoid valve 401 electric wire of monitoring probe, remote control transceiver module, the start and stop solenoid valve 401 being elevated pump, sampling pump 404, electronic control module 204 is control cores of submarine formula electricity driving device, send the Detection Information of monitoring probe to remote-control handle, and receive remote-control handle instruction control lifting pump, sampling pump 404 action.Remote-control handle is provided with directional control rocking bar, aobvious 210 modules of liquid, and directional control rocking bar controls the motion in comprehensive direction with oscilaltion all around of submarine formula electricity driving device, and liquid shows the information of 210 module display monitorings probes.
One utilizes above-mentioned sampling apparatus water body COD detection method of content, includes following steps:
(1) equipment prepares: submarine formula electricity driving device is put into examination water tank, debugging lifting water pump 303 and sampling pump 404, whether after lifting water pump 303 and sampling pump 404 normal operation, then it is normal to debug screw propeller motor, camera 203 and ultrasonic probe 202 state.After all are normal, turn on front end end cover 101, empty reserve tank 301 and sampling box.Reserve tank 301 and sampling box are reinstalled, then submarine formula electricity driving device is put into the water body in tested region, use remote-control handle, press start and stop key, starting outfit.
(2) sample: the video information sent according to camera 203 and ultrasonic probe 202 depth information, remote control submarine formula electricity driving device enters sampled point, and the adjustment of device attitude and traffic direction relies on operator to use operating grip to control.After putting in place, open the solenoid valve 401 on sampling pump 404 and corresponding sampler chamber pipeline, complete this sampled point sampling work.Sampling time is determined by the size of the size of sampler chamber and sampling pump 404 flow, and in the present embodiment, the sampling time is 5S.
(3) multi-point sampling: in order to once descend water, multi-point sampling, repeats above-mentioned steps (2), till sampler chamber is all adopted completely.
(4) sample reclaims: rising water pump is opened in remote control, and submarine formula electricity driving device emerges, and drives screw propeller that submarine formula electricity driving device is pushed to sample recovery point, turns on housing forward end lid 101, take out sampling box water sample, carry out next step spectral detection.
(5) spectral detection:
Open computer 501, start light source switch 506, make light source preheating 15 minutes, keep light stability, carry out spectral scan to water sample, adopt deionized water to do baseline correction, the quartz colorimetric utensil optical path length of water sample is 10 mm.Water sample is put into quartz colorimetric utensil 504, detect for coordinating, light source probe 505 and receiving transducer 503 height adjustable, regulate height by 3 pilot holes, utilize the absorption spectrum that wavelength is 208 nm, 223 nm, 238 nm, 340 nm, 355 nm, 362 nm, 372 nm, 380 nm and 392 nm are right at receiving transducer 503 acquisition testing point place; Physics and chemistry value calculates:
Y=15.336X1+20.256X2+32.114X3-26.458X4+358.542X5-489.668X6+256.334
X7+214.789X8-395.225X9+32.15, calculate COD content, in formula, Y is COD content, and X1 ~ X9 is respectively the absorption spectrum of 208 nm, 223 nm, 238 nm, 340 nm, 355 nm, 362 nm, 372 nm, 380 nm and the water corresponding to 392 nm.
The present invention the characteristic wavelength selected only for the quick detection of the COD content of water body, by multiple linear regression, Modling model, calculates corresponding desired value.
Utilize the index of correlation of method establishment model provided by the invention in table 1, wherein, during modeling set representations Modling model, the COD content matching utilizing the absorbance of water body and the test of existing method to obtain water body obtains model equation, forecast set represents, during prediction, after namely having set up model, according to model equation, the characteristic wavelength absorbance of water spectral is substituted into the COD content of the water body that model equation calculates.
Table 1
| Data set | Number of samples | The coefficient of determination | Root-mean-square error (mg/L) |
| Modeling collection | 90 | 0.7632 | 16.69 |
| Forecast set | 30 | 0.7435 | 17.46 |
Embodiment 1 ~ 10
Utilize apparatus and method provided by the invention to test water body COD content, test result is in table 2.
Table 2
By table 2 data, can find out, it is close that the water body COD content utilizing the inventive method to record and existing method test the data obtained, and utilizes the present invention can Fast Measurement water body COD content, reliable results.
Claims (9)
1. the on-the-spot multi-point sampling device of water sample COD, is characterized in that: include submarine formula electricity driving device, sampling apparatus, telechiric device, wherein:
Submarine formula electricity driving device, drive screw propeller by housing, electricity, lifting water pump, reserve tank form, housing is hollow structure, electricity drives screw propeller suspension and is arranged on housing, lifting water pump and reserve tank are fixedly installed in enclosure interior, water inlet/the water delivering orifice of lifting water pump is communicated with, is elevated water pump water delivering orifice/water inlet with reserve tank is communicated with outside, and water inlet/water delivering orifice is equipped with anti-sealing and pours in down a chimney non-return valve into housing;
Sampling apparatus includes sampling pump, storage sample case, and the water inlet of sampling pump is communicated with outside, water delivering orifice is communicated with storage sample case, and water inlet and water delivering orifice are equipped with the non-return valve preventing water sample from refluxing;
Telechiric device, includes monitoring probe, remote control transceiver module, electronic control module and remote-control handle, and monitoring probe is arranged on the outer wall of housing head end; Remote control transceiver module is arranged on the sidewall of housing rear end, remote control transceiver module and remote-control handle wireless telecommunications, electronic control module with monitoring probe, remote control transceiver module, be elevated the start and stop solenoid valve of pump, the start and stop solenoid valve of sampling pump is electrically connected, send the Detection Information of monitoring probe, and receive remote-control handle instruction control lifting pump, sampling pump action; Remote-control handle is provided with directional control rocking bar, liquid shows module, and directional control rocking bar controls the motion in comprehensive direction with oscilaltion all around of submarine formula electricity driving device, and liquid shows the information of module display monitoring probe.
2. the on-the-spot multi-point sampling device of water sample COD according to claim 1, it is characterized in that: described lifting water pump includes rising water pump and decline water pump, the water delivering orifice of rising water pump is communicated with the apopore being arranged on housing bottom, water inlet is communicated with reserve tank; The water delivering orifice of decline water pump is communicated with reserve tank, water inlet is communicated with the inlet opening being arranged on case top.
3. the on-the-spot multi-point sampling device of water sample COD according to claim 2, is characterized in that: described rising water pump, decline water pump and sampling pump are Mini gear pump.
4. the on-the-spot multi-point sampling device of water sample COD according to claim 1, is characterized in that: described electricity drives screw propeller and comprises three screw propellers, hangs the afterbody being arranged on housing two flank and housing respectively.
5. the on-the-spot multi-point sampling device of water sample COD according to claim 1, it is characterized in that: described storage sample case is provided with the storage sample room of more than 4 autonomous closure, each storage sample room is communicated with sampling pump water delivering orifice respectively by pipeline, and is provided with solenoid valve at every root pipeline.
6. the on-the-spot multi-point sampling device of water sample COD according to claim 1, is characterized in that: described housing is syllogic splicing structure, by front end end cover, body and rear end cap thread connection, is provided with O-ring seal between connection.
7. the on-the-spot multi-point sampling device of water sample COD according to claim 1, is characterized in that: the drive motor plastic cement sealing of described screw propeller, power lead is wrapped in seal.
8. the on-the-spot multi-point sampling device of water sample COD according to claim 1, it is characterized in that: described monitoring probe comprises camera and ultrasonic probe, video information is transmitted feeding and shows module display by camera, and depth information is transmitted feeding and shows module display by ultrasonic probe.
9. utilize an above-mentioned sampling apparatus water body COD detection method of content, it is characterized in that: include following steps:
(1) equipment prepares: submarine formula electricity driving device is put into examination water tank, debugging lifting water pump and sampling pump, and whether after lifting water pump and sampling pump normal operation, then it is normal to debug screw propeller motor, camera and ultrasonic probe state; After all debugging are normal, empty reserve tank and sampling box, submarine formula electricity driving device is put into the water body in tested region; Starting outfit;
(2) sample: coordinate camera and ultrasonic probe, remote control submarine formula electricity driving device enters sampled point, opens the electromagnetic valve on sampling pump and corresponding sampler chamber pipeline, completes this sampled point sampling work;
(3) multi-point sampling: repeat above-mentioned steps (2), until sampler chamber has all been adopted;
(4) sample reclaims: rising water pump is opened in remote control, and submarine formula electricity driving device emerges, and drives screw propeller that submarine formula electricity driving device is pushed to sample recovery point, takes out sampling box water sample;
(5) spectral detection:
Spectral scan is carried out to water sample, deionized water is adopted to do baseline correction, the quartz colorimetric utensil optical path length of water sample is 10 mm, utilizes the absorption spectrum that wavelength is 208 nm, 223 nm, 238 nm, 340 nm, 355 nm, 362 nm, 372 nm, 380 nm and 392 nm are right at spectroscopic probe head acquisition testing point place; Physics and chemistry value calculates:
Y=15.336X1+20.256X2+32.114X3-26.458X4+358.542X5-489.668X 6+256.334 X7+214.789X8-395.225X9+32.15, calculate COD content, in formula, Y is COD content, and X1 ~ X9 is respectively the absorption spectrum of 208 nm, 223 nm, 238 nm, 340 nm, 355 nm, 362 nm, 372 nm, 380 nm and the water corresponding to 392 nm.
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| CN106442014A (en) * | 2016-12-08 | 2017-02-22 | 山东科技大学 | Water sampling device |
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| CN114397416A (en) * | 2022-01-19 | 2022-04-26 | 深圳市丹耐美克环保科技有限责任公司 | Environment-friendly law enforcement automatic monitoring system and method |
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