WO2020082628A1 - 一种基于led光源的光谱法水质监测模块及其使用方法 - Google Patents

一种基于led光源的光谱法水质监测模块及其使用方法 Download PDF

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Publication number
WO2020082628A1
WO2020082628A1 PCT/CN2019/072164 CN2019072164W WO2020082628A1 WO 2020082628 A1 WO2020082628 A1 WO 2020082628A1 CN 2019072164 W CN2019072164 W CN 2019072164W WO 2020082628 A1 WO2020082628 A1 WO 2020082628A1
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led
light
light source
photodiode
water quality
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English (en)
French (fr)
Inventor
李文涛
张光延
吴亚萍
李雨轩
季闻翔
李爱民
庄建军
左延婷
余维敏
李燕
吴吉春
张志俭
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Nanjing University
Nanjing Tech University
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Nanjing University
Nanjing Tech University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry

Definitions

  • the invention relates to on-line water quality monitoring technology in the field of municipal water treatment or household water purification, in particular to a spectroscopic water quality monitoring module based on LED light source and its use method, which detects water by ultraviolet fluorescence excitation fluorescence signal and blue light scattered light detection Turbidity of water.
  • Dissolved organic matter (DOM) present in natural water bodies mainly includes macromolecular proteins, medium molecular weight humic acid, fulvic acid and other small molecular substances.
  • DOM can generate carcinogenic disinfection by-products in the chlorination disinfection process; in the end pipe network, DOM can provide a carbon source for the growth of microorganisms in the pipeline, forming a biofilm; in addition, DOM can Chelates heavy metals and enhances the dispersion of nanoparticles.
  • the content of DOM in drinking water sources varies greatly from place to place; the dissolved organic carbon (DOC) in drinking water sources in the Yangtze River system is usually less than 2mg / L, while drinking water sources in northern Jiangsu are often around 5mg / L. Even the DOC of individual drinking water sources is as high as 9mg / L.
  • the coagulation-precipitation-filtration-disinfection process commonly used in drinking water plants mainly achieves the effective removal of large-molecular-weight protein substances, but the removal effect of medium-molecular-weight humus substances is poor.
  • Some water plants use ozone-activated carbon technology for advanced treatment, but due to the high cost, they need to optimize the quality of the incoming and outgoing water by monitoring.
  • terminal water purification technology has become an urgent need for drinking water safety.
  • China's terminal water purification industry has developed very rapidly, forming a series of water purifier brands.
  • the main water purification methods of terminal water purification equipment include: (1) PP cotton filtration, which aims to remove turbidity and particulate matter; (2) Activated carbon filtration, which aims to adsorb some organic matter and heavy metals; (3) Membrane material filtration, Among them, ultrafiltration membrane filtration further retains particulate matter, colloids and microorganisms, and protects the subsequent nanofiltration membrane or reverse osmosis membrane, while the nanofiltration membrane or reverse osmosis membrane effectively removes most of the dissolved organic matter and heavy metals.
  • the competition in the terminal water purification market is becoming increasingly fierce. Increasing the additional functions of water purifier products is conducive to improving the brand value and product added value. Among them, water quality online monitoring function components have become the focus of attention of leading manufacturers of terminal water purification equipment.
  • TDS Total Dissolved Solids
  • the concentration of DOM can reflect the level of disinfection by-products generated after adding chlorine to tap water;
  • trace toxic pollutants such as dissolved organic matter, medical care products, and disinfection by-products also have similar removal behaviors during activated carbon filtration and membrane filtration; in addition, the growth of microorganisms in water can lead to high fluorescence signals of proteins. Therefore, by monitoring the degree of removal of dissolved organic matter, in theory, it can simultaneously reflect the removal level of trace pollutants such as heavy metals, medical care products and disinfection by-products, as well as early warning of microbial contamination.
  • the requirements of the terminal water purification products on the water quality monitoring module are small size, low energy consumption, low cost, sensitive and fast, and no reagents.
  • Ultraviolet method and fluorescence method detect DOM without chemical reagent and are sensitive and fast. It is the most suitable DOM detection technology for online application.
  • Turbidity detection also uses optical methods, which can be quantified by detecting scattered light or absorbance. Compared with chemical methods, electrochemical methods, etc., optical methods do not directly contact water bodies, avoiding potential pollution.
  • LEDs Light-emitting diodes
  • LEDs have the advantages of good monochromaticity, small size, low energy consumption and long life, and their light emission wavelength has been extended from the visible light band to the deep ultraviolet band (wavelength less than 300nm). It has achieved a breakthrough and has commercialized mass production capacity, which can be applied in the field of water quality monitoring.
  • the Chinese patent application number CN201410502662.9 discloses an ultraviolet fluorescent dual-signal water quality monitoring device using LED light-emitting diodes as a light source and its application method
  • Chinese patent application number CN201510738667.6, published The application filed on 2017.10.17 discloses an ultraviolet fluorescent three-signal water quality sensor and application using a single UV-LED as the light source.
  • Both of the above applications use ultraviolet LED as the light source and use optoelectronics located at the opposite position of the optical path.
  • the diode detects the ultraviolet absorbance value, and uses a band-pass filter and a photodiode at a position perpendicular to the ultraviolet LED light path to detect two fluorescent signals of protein and humus.
  • the above application can ensure the monitoring of water quality in the water treatment process, but there are still difficulties in embedding into the water purifier system, mainly due to: 1)
  • the LED light source is TO39 metal package, the cost is higher, and it is difficult to integrate it on the circuit board; 2)
  • the light source and the photodiode are designed with mutually perpendicular optical paths. Two quartz plates are required, which is difficult to achieve miniaturization and also increases the difficulty of withstand pressure and waterproof design.
  • China Patent Application No. 201810127420.4 discloses a terminal disinfection water purification component with water quality monitoring function and a method of use. Its design focuses on the disinfection function and uses a patch LED as a light source. The cost is reduced, but in order to achieve the sterilization effect, a plurality of SMD LEDs are used, the design is still large, and the turbidity index cannot be detected.
  • turbidity detection methods include transmission Method, scattering method, ratio method and surface scattering method, wherein the scattering method includes vertical scattering type, forward scattering type and backward scattering type; light sources used in turbidity detection include incandescent lamps, light emitting diodes LED and laser diodes.
  • the current turbidity monitoring probes use red light or infrared light sources> 600nm for detection, in order to maximize the elimination of solution chromaticity. Errors caused by measurement results.
  • the maximum wavelength used to detect fluorescence should be less than twice the wavelength of the incident light, meaning that red or infrared light sources are used to detect turbidity and ultraviolet is used as the excitation light source to detect fluorescence, which is difficult to use together.
  • a photodiode and its detection circuit because red or infrared light sources are used to detect turbidity and ultraviolet is used as the excitation light source to detect fluorescence, which is difficult to use together.
  • blue-green light with a peak wavelength of the light source of about 400 to 550 nm can achieve high turbidity measurement sensitivity, and the tap water processed by the water purifier is characterized by low turbidity and low solubility organic matter.
  • the emission wavelength of humus fluorescence is within 400 ⁇ 500nm. Therefore, using 400-500nm blue light for turbidity detection in the field of water purification can not only obtain higher sensitivity, but also share the photodiode and its amplification circuit with fluorescence detection, while being less disturbed by dissolved organic matter.
  • the water quality of the water purification unit needs to be monitored and adjusted through online monitoring to optimize the adjustment of the treatment process.
  • manufacturers of water purifiers or water purification systems need to Two miniaturized water quality monitoring modules are installed on the water and outlet pipes, and the turbidity and dissolved organic matter concentration are detected at the same time, and the water purification effect of the water purifier is reflected by the difference calculation.
  • the present invention aims to provide a miniaturized embedded water quality monitoring module that detects the concentration of dissolved organic matter by fluorescence method and scatters by scattering
  • Optical method for detecting turbidity has the advantages of miniaturization, low cost, easy installation, quick and sensitive, etc. It can be installed in the water treatment unit or the inlet and outlet pipes of the water purifier, reflecting the water purification effect in real time.
  • a spectroscopic water quality monitoring module based on LED light source includes a fluid chamber, a photoelectric chamber and a light-transmitting waterproof sealing assembly, the fluid chamber, the light-transmitting waterproof sealing assembly and the photoelectric chamber are sequentially connected, and the photoelectric chamber includes optical detection Part and electronic circuit system, the optical detection part is installed on the circuit board of the electronic circuit system, wherein the optical detection part provides a light source and converts the fluorescent and scattered light signals into electrical signals, and the electronic circuit system performs electrical signals Output after processing.
  • the fluid chamber is separated from the photoelectric chamber by a light-transmitting waterproof sealing assembly, and the light-transmitting waterproof sealing assembly includes a quartz piece and a sealing gasket.
  • the water quality monitoring objects realized by the fluorescence and scattered light include (i) three types of fluorescent signals that detect the fluorescent signal of protein, humus, or the total fluorescence of protein and humus by fluorescence. Monitor the dissolved organic matter or microbial pollution in the flow path, (ii) monitor the turbidity in the water by detecting the scattered light generated by the blue light irradiating the particles or colloids.
  • the optical detection part includes a patch-type LED, a band-pass filter and a photodiode, the patch-type LED and the photodiode are arranged in parallel on the same circuit board 1, and the band-pass filter is encapsulated in the photodiode s surface.
  • the photodiode can also be arranged on the circuit board two, the band-pass filter is encapsulated on the surface of the photodiode, the circuit board one is facing the band-pass filter, and the SMD LED is set on The edge of the hole, and the surface of the patch LED is flush with the surface of the band pass filter.
  • the light source of the SMD LED is a monochromatic ultraviolet LED light source or an ultraviolet + blue compound color combination package LED light source or an ultraviolet LED + blue light LED dual light source.
  • the monochromatic ultraviolet LED light source has a wavelength range of 250 to 370 nm, which is mainly used as an excitation light source for fluorescent signal detection, preferably an ultraviolet chip with a center wavelength of 280 ⁇ 5 nm is used to excite proteins Fluorescence or humus-like fluorescence, it is preferable to use an ultraviolet LED chip with a center wavelength of 310 ⁇ 5nm, 330 ⁇ 5nm or 365 ⁇ 5nm for separately exciting humus-like fluorescence;
  • the multi-color combined package LED light source is to package an ultraviolet LED chip for exciting fluorescent signals and a blue (400-500 nm) LED chip for turbidity detection on the same substrate, preferably 280 ⁇ 5nm ultraviolet LED chip and 465 ⁇ 5nm blue LED chip combination package, using 310 ⁇ 5nm ultraviolet LED chip and 465 ⁇ 5nm blue LED chip combination package, using 330 ⁇ 5nm ultraviolet LED chip and 465 ⁇ 5nm blue LED chip combination package, using 365 ⁇ 5nm ultraviolet LED chip and 465 ⁇ 5nm blue LED chip combination package.
  • the band-pass filter is selected to match different types of band-pass filters according to the difference of the patch-type LED light source, which are band-pass filters with a wavelength range of (i) 330-360 nm, It can be used for protein fluorescent signal detection and early warning of microbial contamination.
  • Bandpass filter in the range of 380 ⁇ 500nm is used for detection of humus fluorescent signal
  • 330 ⁇ 500nm bandpass filter is used for protein The total fluorescence signal of quasi-fluorescence and humus-like fluorescence is detected; the cut-off rate of the band-pass filter to the light intensity outside the band-pass wavelength range is more than 99.9%.
  • the photodiode is a silicon photodiode with a high linear response to ultraviolet-visible light in the range of 300-500 nm.
  • the electronic circuit system includes a single chip microcomputer, a power supply module, an op amp module, a low-pass filter module, an analog-to-digital conversion, a communication module, a temperature sensor, a host computer, and a constant current drive module, wherein the power supply module is an electronic circuit system.
  • Power supply for components single-chip output digital signal to control constant current drive circuit to realize the switch control of SMD LED; band-pass filter to input optical signal into photodiode, op amp module amplifies the signal output by photodiode and then transmits to Low-pass filter module.
  • the low-pass filter module is input to the analog-to-digital conversion, and finally collected by the single-chip microcomputer to communicate with the host computer; the temperature sensor monitors the temperature of the circuit board and is used to control the chip LED due to temperature changes. The power output and the photodiode signal are corrected and compensated. The compensation coefficient is determined by measuring the value of the same solution at different temperatures.
  • the op amp module adopts a photovoltaic mode with zero bias voltage, and its operational amplifier adopts transimpedance amplification design to achieve IV conversion; analog-to-digital conversion uses a high-precision AD analog-to-digital conversion chip with more than 12 bits to convert the signal to analog-to-digital ,
  • the one-chip computer communicates with the upper computer through IIC bus way.
  • a method of using a spectroscopic water quality monitoring module based on LED light sources the steps are:
  • the single-chip microcomputer controls the constant current drive circuit, controls the SMD LED switch, and outputs only purple light or alternately blue light or purple light;
  • the bandpass filter filters the light intensity outside the bandpass wavelength range, and transmits the light signal generated by scattered light and / or fluorescence to the photodiode;
  • the photodiode converts the optical signal into an electrical signal
  • the operational amplifier module processes the electrical signal output by the photodiode, amplifies the electrical signal, and transmits it to the low-pass filter module;
  • the electrical signal is input to the analog-to-digital conversion, and then transmitted to the microcontroller;
  • the single chip microcomputer collects and communicates with the host computer, the host computer calculates the difference between the fluorescence signal and / or the scattered light signal of the water treatment unit or the water purifier, and judges the water treatment unit or net The effect of the water machine on the removal of organic matter and turbidity.
  • the fluorescence detection DOM concentration and scattered light detection turbidity the single-chip microcomputer controls the two independent LED constant current driving circuits through the two digital pin output signals, and controls the ultraviolet LED chip and the blue LED chip Alternately lit, because the fluorescence generated by the humus excited by ultraviolet light is blue light, so the scattered light of fluorescence and blue light can share the filter and the photodiode and its amplification circuit.
  • the present invention has the following advantages:
  • the spectroscopic water quality monitoring module based on LED light source according to the present invention has the advantage that the LED light source adopts a patch package, and the cost is less than 1/20 of the TO39 package, which is beneficial to large-scale production.
  • the spectroscopic water quality monitoring module based on LED light source according to the present invention has the advantage that the LED light source and the photodiode are located on parallel planes and face the same direction. Such an optical path design occupies less space and only uses a piece of quartz The film is beneficial to realize the separation of the photoelectric device and the water, and reduces the design difficulty of the waterproof seal.
  • the spectroscopic water quality monitoring module based on LED light source according to the present invention adopts the fluorescence method for online water quality monitoring, which can achieve Linear detection of 10ppb to 5ppm DOC concentration level, and can replace the activated carbon filter or membrane filter according to the competitive adsorption of heavy metals, medical care products, disinfection by-products and humus in activated carbon and the "penetration" behavior in membrane filtration Tips:
  • the fluorescence method can also be applied to the monitoring of the effluent water quality of activated carbon filtration or nanofiltration membrane filtration with poor inorganic salt removal; microorganisms form a biofilm on the surface of the quartz plate due to extracellular polymerization
  • the substance contains a large amount of protein substances. Therefore, the protein fluorescent signal can warn the microbial contamination risk of the internal pipeline of the water purifier to a certain extent.
  • the present invention uses blue light to irradiate particles or colloids to monitor the turbidity of water.
  • blue light is more sensitive than infrared or red light to detect turbidity, and soluble organic matter in tap water
  • concentration is low, and its effect on blue light detection turbidity is negligible.
  • the spectroscopic water quality monitoring module based on LED light source according to the present invention has the advantages that the fluorescence generated by ultraviolet light and the blue light used to detect turbidity have similar wavelengths.
  • FIG. 1 is (a) front view, (b) side view, (c) top view, and (d) isometric view of the appearance structure of the water quality monitoring module of the present invention
  • FIG. 2 is a front view of the exploded exploded view of the structure of the water quality monitoring module of the present invention
  • FIG. 3 is an axonometric view of an exploded view of the structure of the water quality monitoring module of the present invention.
  • FIG. 4 is a schematic diagram of the optical device position of the water quality monitoring module of the present invention.
  • FIG. 5 is a schematic diagram of the electronic circuit system of the water quality monitoring module of the present invention.
  • Figure 6 is a linear fit between the original voltage data before AD acquisition (left Y axis) and the signal value after AD acquisition (right Y axis) and the concentration of dissolved organic matter;
  • Figure 7 is the time-varying graph of the original voltage data before AD acquisition
  • Figure 8 is a direct linear fit of the scattered light signal value measured by the water quality monitoring module and the concentration of hydrazine sulfate turbidity standard solution;
  • FIG. 9 is a schematic diagram of the flow field of the fluid chamber of the water quality monitoring module of the present invention.
  • Fig. 10 is a schematic diagram of the improvement of the inlet and outlet flow paths of the fluid chamber: (a) top view and (b) side view.
  • a water quality monitoring module based on a spectroscopic method based on an LED light source and a method for using the same.
  • the water quality monitoring object using fluorescence and scattered light includes (i) detection of protein-based fluorescent signals, humus-based fluorescent signals or The three fluorescent signals of total fluorescence of protein-based fluorescence and humus-based fluorescence monitor the contamination of dissolved organic matter or microorganisms in the flow path. (Ii) The turbidity of water is monitored by the scattered light generated by the blue light irradiating particles or colloids.
  • a spectroscopic water quality monitoring module based on an LED light source in this embodiment includes a fluid chamber 1, a photoelectric chamber 2, an optical detection section 3, an electronic circuit system 4 and a light-transmitting and waterproof Sealing assembly 5.
  • the fluid chamber 1 is provided with a quick connector 101 at each end, one end is a quick connector 101 for water inlet, and the other end is a quick connector 101 for water outlet;
  • the photoelectric chamber 2 is provided with a top cover 202, and the photoelectric chamber 2 is provided with an annular support frame 201, an optical detection part 3 and an electronic circuit system 4 are provided in the ring-shaped support frame 201;
  • the light-transmitting and waterproof sealing assembly 5 includes a quartz piece 501 and a sealing gasket 502.
  • the top cover 202 of the photoelectric chamber 2 is connected to the upper screw hole 203 and the lower screw hole 103 by screws, and the top cover 202 presses the quartz piece 501 and the sealing gasket 502 through the ring-shaped support frame 201 to realize the photoelectric chamber 2 and the fluid chamber 1
  • the optical detection section 3 includes a patch LED 301, a band-pass filter 302, and a photodiode 303.
  • the positional relationship and optical path between the patch LED 301, a band-pass filter 302, and the photodiode 303 are shown in Figure 4- (a) As shown, the photodiode 303 is soldered in the center on the second circuit board 42, the central portion of the circuit board 41 where the SMD LED301 is located is opened, and the SMD LED301 is soldered to the edge of the 41 hole in the circuit board, with a band-pass filter 302 is packaged on the surface of the photodiode 303, and the distance and position between the two circuit boards are designed so that the band-pass filter 302 passes through the opening of the circuit board 41 where the chip LED 301 is located and the surface of the band-pass filter 302 is The surface of SMD LED301 circuit board 41 is flush.
  • SMD LED301 adopts 5050 specification SMD LED with ultraviolet and blue composite packaging, in which the packaged ultraviolet LED chip has a luminous power of 3mW, the wavelength ⁇ is 280 ⁇ 5nm, and the packaged blue LED chip has a luminous power of 60mW, the wavelength ⁇ It is 465 ⁇ 5nm.
  • the cathodes of the ultraviolet LED chip and the blue LED chip are connected to their respective constant current drive circuits and share the anode to achieve independent switching control.
  • the output angle of the ultraviolet light and blue light are both greater than 140 °.
  • Bandpass filter 302 used in the wavelength range of 380 ⁇ 500nm bandpass filter 302, used to transmit humus-based fluorescence, ultraviolet and visible light cut-off rate for other wavelength ranges is more than 99.9%, bandpass filter
  • the sheet 302 is fixed on the surface of the photodiode 303 and has a size of 4.4 mm in length, 4.0 mm in width, and a thickness of about 2.2. Mm.
  • the photodiode 303 is a silicon photodiode in a chip package with a high linear response to ultraviolet-visible light in the range of 300-500 nm. In this embodiment, the blue-sensitized chip produced by Zhenjiang Gaxin Optoelectronics Technology Co., Ltd. is used.
  • the size of the photodiode is 4.4mm long, 4.0mm wide and about 1.2mm thick.
  • the electronic circuit system 4 includes a single-chip microcomputer 401, a power module 402, an operational amplifier module 403, a low-pass filter module 404, an analog-to-digital converter 405, a communication module 406, and a temperature sensor 407, and the component row of the electronic circuit system 4 It is distributed on two printed circuit boards one 41 and circuit board two 42.
  • the power module 402 supplies power to the components of the electronic circuit system 4.
  • the TI company's tps61040 chip is used for the required DC-DC voltage conversion.
  • the LM317 chip is used to form a constant current drive module 409 to drive the ultraviolet light of the SMD LED301. LED chips and blue LED chips.
  • the optoelectronic signal undergoes signal amplification and noise reduction through the op-amp module 403 and the low-pass filter module 404.
  • the op-amp module 403 selects TI's OPA129 op amp chip to design the circuit in transimpedance amplification, and the selected amplifier resistance is 500M ⁇ ; low pass
  • the filtering module 404 adopts TI's OPA227 operational amplifier chip to design a low-pass filter with a bandwidth of 10 Hz, and its purpose is to reduce 50 Hz power frequency interference by 50 dB.
  • the single chip microcomputer 401 uses the STM32F103C8T6 chip to control the LM317 chip in the constant current drive circuit through the digital output pin to realize the alternately blinking of the ultraviolet LED chip and the blue LED chip in the SMD LED301 light source, that is, within a 1s period, the ultraviolet LED The chip lights up after 0.5s, and then the blue LED chip starts to light up for 0.5s.
  • the ultraviolet LED chip is working, the emitted 280 ⁇ 5nm ultraviolet light is irradiated through the quartz plate 501 to the dissolved organic matter in the water sample of the fluid chamber 1.
  • the proteinaceous matter and humus matter in the organic matter produce wavelengths of 320-350nm and For the fluorescence in the range of 380-500nm, in this embodiment, only the humus-based fluorescent signal is irradiated to the surface of the photodiode 303 through the quartz plate 501 and the band-pass filter 302, and the photodiode 303 uses a photovoltaic mode of zero bias voltage After being processed by the operational amplifier module 403 and the low-pass filter module 404, the generated signal is transmitted to the single-chip microcomputer 401 after the analog-to-digital conversion 405.
  • the emitted 465 ⁇ 5nm blue light is also irradiated on the fine particles in the fluid chamber 1 through the quartz plate 501 to form scattered light. Due to the large luminous angle of the LED light, the scattered light can be formed It is vertical scattering, forward scattering and backward scattering; the scattered light illuminates the surface of the photodiode 303 through the quartz plate 501 and the band-pass filter 302, and the photodiode 303 adopts the photovoltaic working mode of zero bias voltage, and the signal generated After being processed by the op-amp module 403 and the low-pass filter module 404, it is transmitted to the single-chip microcomputer after the analog-to-digital conversion 405. Since both fluorescence and scattered light are faint light, a time-division multiplexing method can be used to share a set of photodiode 303 and its operational amplifier circuit.
  • the single chip microcomputer 401 communicates with the host computer 408, and transmits the fluorescent signal and the scattered light signal to the host computer 408 using the IIC method; the water inlet and outlet of the water purifier are connected to the water quality monitoring module of this example, or a water quality is used.
  • the monitoring module monitors the water quality of the incoming water when the water purifier is not used for water intake and the water quality of the purified effluent when the water purifier takes water, and realizes the pre-treatment and post-treatment of the water purifier through the switch of the solenoid valve.
  • the water quality is monitored successively; the host computer compares and calculates the difference between the fluorescence signal and the scattered light signal measured by the water quality monitoring module of the water purifier inlet and outlet to reflect the effect of the water purifier on the removal of organic matter and turbidity in the water.
  • FIG. 6 the original voltage value before AD analog-to-digital conversion or the fluorescence signal value after AD analog-to-digital conversion and the DOC concentration both show a good linear relationship (R 2 > 0.99), and the corresponding DOC concentration per fluorescence signal unit is 5 / 166mg / L, which is about 30 ⁇ g / L;
  • Figure 7 shows the change of the original voltage value with time before the AD analog-to-digital conversion when the ultraviolet LED chip is constantly lit.
  • the voltage value change is less than 0.8mV, that is Within 12-bit precision AD sampling accuracy; then the voltage value drops, but the value change within 60s is less than 1.5mV. This change is due to the fact that after the LED continues to light up, the chip temperature has increased and the luminous efficiency has decreased. Since the use of the water purifier is often within 1 minute, and the ultraviolet LED chip and the blue LED chip adopt the alternating strobe mode every 0.5s, the duty ratio is 50%, which can effectively solve the heat dissipation problem, so the water quality monitoring module of the embodiment of the invention It can meet the testing needs of water purifiers.
  • Adopt national standard "Determination of Water Turbidity" (GB13200-91) to prepare hydrazine sulfate standard solution and carry out gradient dilution, use blue light scattering to detect turbidity, as shown in Figure 8, the measured light intensity signal and turbidity There is a good linear relationship between NTUs (R 2 > 0.99), and each scattered light intensity signal unit corresponds to 100 / 3882NTU, which is about 0.026NTU.
  • the inflow and outflow of the reverse osmosis water purifier in the laboratory provided by a Nanjing water purifier brand company were also measured.
  • the tap water before purification is ⁇ 48mV higher than the purified water, that is, ⁇ 60 Sampling unit (AU);
  • the effluent height after purification by the fountain pen before purification is ⁇ 29.5mV, ie ⁇ 37 sampling units (AU), corresponding to a turbidity difference of 0.95NTU.
  • This embodiment is basically the same as Embodiment 1, except that:
  • the positional relationship and optical path between the SMD LED301, the bandpass filter 302 and the photodiode 303 are shown in Fig. 4- (b), the SMD LED301 and the photodiode 303 are soldered in parallel on the same circuit board 41
  • the band-pass filter 302 is packaged on the surface of the photodiode 303, and the edge of the SMD LED301 and the photodiode 303 are separated by a certain distance.
  • the photodiode 303 is a TO-5 metal-encapsulated silicon photodiode produced by Zhenjiang Gaxin Optoelectronics Technology Co., Ltd.
  • the analog-to-digital conversion 405 uses the high-end analog-to-digital conversion chip of TI's ADS1118, which has four single-ended inputs and 2 / 3-16 programmable gain amplifiers, while the microcontroller 401 uses a relatively low-end MA82G5B32 microcontroller chip.
  • a solution containing both 2mg / L of DOC dissolved organic matter and 1NTU of turbidity is prepared using the International Humus Association Natural Organic Standards and Hydrazine Sulfate Turbidity Standard Solution.
  • the fluorescence signal measured by the water quality monitoring module of this embodiment is 122AU, per unit
  • the corresponding sensitivity is 2 / 122mg / L, which is about 16 ⁇ g / L; the signal of the blue scattered light is 73AU, and the corresponding sensitivity of each unit is 1 / 73NTU, which is about 0.014NTU.
  • This embodiment is basically the same as Embodiment 1, except that:
  • the inlet and outlet pipe interfaces of the fluid chamber 1 are designed asymmetrically up, down, left, and right to increase the intensity of turbulent flow and reduce the dead circulation volume of the flow field.
  • the band-pass filter 302 has a band-pass wavelength range of 330-500 nm, which is used to detect the total fluorescence signal of protein-based fluorescence and humus-based fluorescence, and the ultraviolet or visible light cutoff rate for other wavelengths is more than 99.9%.
  • the turbidity standard solution of hydrazine sulfate was added to the water sample to increase the turbidity by 1NTU.
  • the total fluorescence signal value obtained in this example is 92AU, and the DOC concentration per fluorescence unit is 1.8 / 92mg / L, which is about 19.6 ⁇ g / L; the measured blue scattered light signal is 39AU, and the corresponding The sensitivity is about 0.0256NTU.
  • This embodiment is basically the same as Embodiment 3, except for:
  • SMD LED301 uses 310 ⁇ 5nm ultraviolet light and 465 ⁇ 5nm blue light to be placed side by side.
  • the luminous power of the ultraviolet LED is 8mW, which is used to excite humus-like fluorescent signals in water.
  • a solution containing both 2 mg / L of DOC dissolved organic matter and approximately 1 NTU of turbidity is prepared using the International Humus Association Natural Organic Standards and Hydrazine Sulfate Turbidity Standard Solution.
  • the fluorescence signal measured by the water quality monitoring module of this embodiment is 86 AU
  • the sensitivity corresponding to the unit is 2 / 86mg / L, which is about 23 ⁇ g / L; the signal of the measured blue scattered light is 40AU, and the sensitivity corresponding to each unit is 1 / 40NTU, which is about 0.025NTU.
  • This embodiment is basically the same as Embodiment 3, except for:
  • SMD LED301 adopts a compound package of 330 ⁇ 5nm ultraviolet LED chip and 465 ⁇ 5nm blue LED chip.
  • the luminous power of the ultraviolet LED chip is 8mW, which is used to excite humus-like fluorescent signals in water.
  • a solution containing both 2 mg / L of DOC dissolved organic matter and approximately 1 NTU of turbidity was prepared using the International Humus Association Natural Organic Standards and Hydrazine Sulfate Turbidity Standard Solution.
  • the fluorescence signal measured by the water quality monitoring module of this embodiment was 136 AU, each The sensitivity corresponding to the unit is 2 / 136mg / L, which is about 15 ⁇ g / L; the signal of the blue scattered light is measured to be 40AU, and the sensitivity corresponding to each unit is 1 / 40NTU, which is about 0.025NTU.
  • This embodiment is basically the same as Embodiment 3, except for:
  • SMD LED301 adopts 365 ⁇ 5nm ultraviolet LED chip and 465 ⁇ 5nm blue LED chip composite package, in which the ultraviolet LED chip has a luminous power of 40mW, which is used to excite humus-like fluorescent signals in water.
  • a solution containing both 2 mg / L of DOC dissolved organic matter and approximately 1 NTU of turbidity is prepared using the International Humus Association Natural Organic Standards and Hydrazine Sulfate Turbidity Standard Solution.
  • the fluorescence signal measured by the water quality monitoring module of this embodiment is 255 AU, each The sensitivity corresponding to the unit is 2 / 255mg / L, which is about 8 ⁇ g / L; the signal of the blue scattered light is measured to be 40AU, and the sensitivity corresponding to each unit is 1 / 40NTU, which is about 0.025NTU.
  • This embodiment is basically the same as Embodiment 1, except that:
  • the SMD LED301 is a monochromatic ultraviolet LED light source with a wavelength of 280 ⁇ 5nm; the bandpass wavelength range of the bandpass filter 302 is 330-500nm. In this embodiment, only the total fluorescence signals of protein-based fluorescence and humus-based fluorescence of dissolved organic matter in water are detected, and the turbidity signal is not detected.
  • Yangtze River water sample (DOC about 1.8mg / L) after 0.45 ⁇ m membrane treatment, it is divided into two parts, one part is added hydrazine sulfate turbidity standard reagent to make the solution turbidity is 2NTU, the other part is not added turbidity, this
  • the total fluorescence signals of protein fluorescence and humus fluorescence measured by two water samples measured by the water quality monitoring module in the embodiment are 89AU and 92AU, respectively. Because the absorbance of the 2NTU hydrazine sulfate solution at 280nm is about 0.026, which is about 94% light transmittance per cm, the internal masking effect on fluorescence is small. Normally, the turbidity of tap water is less than 1NTU, so the turbidity of tap water has little effect on the detection of fluorescence signals.
  • This embodiment is basically the same as Embodiment 1, except that:
  • the amplification resistance used in the op-amp module 403 is 1 G ⁇ , and the band-pass filter 302 has a band-pass wavelength range of 330-360 nm, which is used to detect protein-based fluorescent signals, while the ultraviolet or visible light cut-off rate for other wavelengths is 99.9% or more.
  • the band-pass filter 302 has a band-pass wavelength range of 330-360 nm, which is used to detect protein-based fluorescent signals, while the ultraviolet or visible light cut-off rate for other wavelengths is 99.9% or more.
  • the band-pass filter 302 has a band-pass wavelength range of 330-360 nm, which is used to detect protein-based fluorescent signals, while the ultraviolet or visible light cut-off rate for other wavelengths is 99.9% or more.
  • the Yangtze River water sample (DOC is about 1.8mg / L) after 0.45 ⁇ m membrane treatment is used, and the protein measured by the water quality monitoring module
  • the fluorescence-like signal is 38AU.
  • This embodiment is basically the same as Embodiment 1, except that:
  • SMD LED301 is a monochromatic ultraviolet LED light source with a wavelength of 310 ⁇ 5nm and an output optical power of about 8mW. In this embodiment, only the humus-like fluorescence of dissolved organic matter in water is detected alone, and the turbidity signal is not detected.
  • Dissolved organic matter containing about 2mg / L of DOC is prepared using the International Humus Association Natural Organic Standards.
  • the humus-like fluorescence signal measured by the water quality monitoring module of this embodiment is 86AU, and the corresponding sensitivity per unit is 2 / 86mg / L, that is About 23 ⁇ g / L DOC.
  • This embodiment is basically the same as Embodiment 1, except that:
  • SMD LED301 is a monochromatic ultraviolet LED light source with a wavelength of 330 ⁇ 5nm and an output optical power of about 8mW. In this embodiment, only the humus-like fluorescence of dissolved organic matter in water is detected alone, and the turbidity signal is not detected.
  • Dissolved organic matter containing about 2 mg / L of DOC is prepared using the International Humus Association Natural Organic Standards.
  • the humus-like fluorescence signal measured by the water quality monitoring module of this embodiment is 137AU, and the corresponding sensitivity per unit is 2 / 137mg / L, that is About 15 ⁇ g / L DOC.
  • This embodiment is basically the same as Embodiment 1, except that:
  • SMD LED301 is a monochromatic ultraviolet LED light source with a wavelength of 365 ⁇ 5nm and an output optical power of 40mW. In this embodiment, only the humus-like fluorescence of dissolved organic matter in water is detected alone, and the turbidity signal is not detected.
  • Dissolved organic matter containing about 2 mg / L of DOC is prepared using the International Humus Association Natural Organic Standards.
  • the humus-like fluorescence signal measured by the water quality monitoring module of this embodiment is 257AU, and the corresponding sensitivity per unit is 2 / 257mg / L, ie About 8 ⁇ g / L DOC.

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Abstract

一种基于LED光源的光谱法水质监测模块及其使用方法，属于水质在线监测技术领域。该水质监测模块包括流体室（1）、光电室（2）、光学探测部分（3）、电子电路系统（4）和透光防水密封组件（5）。流体室（1）与光电室（2）之间连接透光防水密封组件（5）实现防水分离，光学探测部分（3）安装在电子电路系统（4）的电路板（41，42）上，透光防水密封组件（5）包括石英片（501）；光学探测部分（3）包括贴片式LED（301）、带通滤光片（302）和光电二极管（303），电子电路系统（4）包括单片机（401）、电源模块（402）、运放模块（403）、低通滤波模块（404）、模数转换（405）和通信模块（406）。该装置及方法通过紫外光激发荧光信号来检测水中蛋白类与腐殖质类物质，通过蓝光的散射检测水的浊度，具有体积小、能耗低、成本低、灵敏快速和无需试剂的优点。

Description

一种基于LED光源的光谱法水质监测模块及其使用方法 技术领域
本发明涉及市政水处理或家用净水领域的在线水质监测技术，具体涉及一种基于LED光源的光谱法水质监测模块及其使用方法，通过紫外光激发荧光信号来检测水中，通过蓝光散射光检测水的浊度。
背景技术
自然水体中所存在的溶解性有机物(dissolved organic matter,DOM)，主要包括大分子蛋白类、中等分子量的腐殖酸、富里酸以及其他小分子物质。在饮用水处理过程中，DOM可在氯化消毒工艺中生成具有致癌作用的消毒副产物；在末端管网中，DOM可为管道中微生物的生长提供碳源，形成生物膜；此外，DOM可以螯合重金属，增强纳米粒子的分散性。
各地饮用水源水中DOM含量存在较大差异；长江水系饮用水源中溶解性有机碳(dissolved organic carbon,DOC)通常小于2mg/L，而江苏北部地区饮用水源水往往在5mg/L左右，甚至个别饮用水源地DOC高达9mg/L。目前饮用水厂所普遍采用的混凝-沉淀-过滤-消毒工艺，主要对其中的大分子量蛋白类物质实现有效去除，而对中等分子量腐殖质类物质去除效果较差。一些水厂采用臭氧-活性炭工艺进行深度处理，但由于成本较高，需要通过监测进出水水质进行优化。
随着水质污染事件频发，末端净水技术成为饮用水安全保障的迫切需求。近年来，中国末端净水产业发展十分迅速，形成了一系列净水机品牌。目前的末端净水设备主要采用的净水方式包括：(1)PP棉过滤，目的在于去除浊度和颗粒物；(2)活性炭过滤，目的在于吸附部分有机物和重金属；(3)膜材料过滤，其中超滤膜过滤进一步截留颗粒物、胶体和微生物，对后续纳滤膜或反渗透膜起到保护作用，而纳滤膜或反渗透膜则对大部分溶解性有机物及重金属实现有效去除。末端净水市场领域竞争日趋激烈，增加净水器产品的附加功能，有利于提高品牌价值和产品附加值。其中水质在线监测功能组件成为末端净水设备领先制造商的关注热点。
目前的净水机主要采用总溶解性固体(TDS)的指标评价水质监测结果，然而有害的重金属浓度往往是微量的，通常难以被TDS指标所反映。DOM的在线监测可以作为末端净水水质的重要评价方法。一方面，水中的重金属离子大多以与DOM形成的络合态存在，去除DOM的同时可以去除重金属；另一方面，DOM浓度可以反映出自来水中加氯后的消毒副产物生成水平；另一方面，溶解性有机物、医药护理品和消毒副产物等微量有毒污染物在活性炭过滤和膜滤过程中也存在相似的去除行为；此外，水中微生物的滋生会导致蛋白类荧光信号的偏高。因此，通过监测溶解性有机物的去除程度，理论上可以同时反映重金属、医药护理品和消毒副产物等微量污染物的去除水平以及进行微生物污染预警。供水管网中生物膜的脱落、管道腐蚀与破损会导致饮用水具有较高的浊度。尽管浊度比DOM更容易在净水机中实现去除，即净水器对DOM去除效率高意味着其浊度去除效率也高，但净水机厂商希望在不显著增加成本的前提下能够同时监测DOM浓度和浊度两个指标。
末端净水产品对水质监测模块的要求是体积小、能耗低、成本低、灵敏快速和无需试剂。紫外法和荧光法探测DOM，无需化学试剂且灵敏快速，是最适合在线应用价值的DOM探测技术。浊度探测同样采用光学方法，可通过探测散射光或吸光度来实现定量。与化学法、电 化学法等方法相比，光学法不直接接触水体，避免了潜在污染。
发光二极管(LED)具有单色性好、体积小、能耗低和寿命长等优点，且其发光波长已由可见光波段拓展到深紫外波段(波长小于300nm)，近年来深紫外波段LED的发展获得突破，已具备商业化大批量生产能力，可在水质监测领域进行应用。
如中国专利申请号CN201410502662.9，公开日为2014.12.10的申请案公开了一种以LED发光二极管为光源的紫外荧光双信号水质监测装置及其应用方法，中国专利申请号CN201510738667.6，公开日为2017.10.17的申请案公开了一种以单个UV-LED为光源的紫外荧光三信号水质传感器及应用，上述两个申请案均采用了以紫外LED为光源，采用处于光路相对位置的光电二极管探测紫外吸光度值，并采用与紫外LED光路垂直位置的带通滤光片和光电二极管探测蛋白类和腐殖质类两种荧光信号。上述申请案能够保证水处理过程中的水质监测，然而嵌入到净水机系统中仍存在困难，主要在于：1)LED光源采用TO39金属封装，成本较高，难以集成到电路板上；2)为实现荧光探测，光源和光电二极管采用相互垂直的光路设计，需要两块石英片，难以实现微型化，也增加了耐压防水设计难度。
中国专利申请号201810127420.4，公开日为2018.07.20的申请案公开了一种含水质监测功能的末端消毒净水组件及使用方法，其设计以消毒功能为主，采用了贴片式LED作为光源，降低了成本，但为实现杀菌效果，采用多颗贴片式LED，设计仍体积较大，而且不能够检测浊度指标。
南京信息工程大学研究生王志丹在2016.06.14公开了一篇名为光学浊度传感器的设计与实现的论文，该论文系统地总结了浊度测量的基础理论和方法，目前浊度的检测方法包括透射法、散射法、比值法和表面散射法，其中散射法包括垂直散射式、前向散射式和后向散射式；浊度探测所采用的光源包括白炽灯、发光二极管LED和激光二极管。在实际应用中，由于溶解性有机物对波长小于500nm的入射光有显著的吸收作用，目前的浊度监测探头均采用>600nm的红光或红外光源进行探测，以最大程度地消除溶液色度对测量结果带来的误差。然而，由于二级瑞利散射的存在，探测荧光所用的最大波长应小于入射光波长的2倍，意味着采用红光或红外光源探测浊度和采用紫外作为激发光源来探测荧光，难以共同使用一个光电二极管及其探测电路。另一方面，采用光源峰值波长在400～550nm左右的蓝绿光可以达到较高的浊度测量灵敏度，而净水机所处理的自来水的特点是低浊度和低溶解性有机物。腐殖质荧光的发射波长范围在400～500nm内。因此，在净水领域采用400～500nm蓝光进行浊度探测不仅可以获得较高的灵敏度，而且还可以与荧光探测共用光电二极管及其放大电路，同时所受溶解性有机物的干扰较小。
综上所述，在饮用水厂需要通过在线监测净水单元前后的水质来进行处理工艺的优化调整；净水机或净水系统厂商为了更好地反映净水前后的水质差异，需要在进水和出水管路上安装两个微型化的水质监测模块，同时对浊度和溶解性有机物浓度进行探测，通过差值计算，来反映净水器净水效果。
发明内容
1.要解决的问题
针对饮用水厂或民用净水系统迫切需要在线监测水中浊度和溶解性有机物浓度的需求，本发明旨在提供一种微型化嵌入式水质监测模块，通过荧光法探测溶解性有机物浓度，通过散射光法探测浊度，具有微型化、成本低、易安装、灵敏快速等优点，可安装在水处理单元或净水机进水和出水管路，实时反映净水效果。
2.技术方案
为了解决上述问题，本发明所采用的技术方案如下：
一种基于LED光源的光谱法水质监测模块，包括流体室、光电室和透光防水密封组件，所述的流体室、透光防水密封组件、光电室依次连接，所述的光电室内包括光学探测部分和电子电路系统，所述的光学探测部分安装在电子电路系统的电路板上，其中光学探测部分提供光源及将荧光与散射光信号转换成电信号，所述的电子电路系统对电信号进行处理后输出。
进一步地，所述的流体室通过透光防水密封组件实现与光电室的透光防水分离，所述的透光防水密封组件包括石英片和密封垫圈。
进一步地，所述的流体室两端设置快接头连接进出水管路。
进一步地，所述的荧光与散射光所实现的水质监测对象，包括(i)通过荧光法探测蛋白类荧光信号、腐殖质类荧光信号或蛋白类荧光和腐殖质类荧光的总荧光信号三种荧光信号对流路中的溶解性有机物或微生物污染进行监测，(ii)通过探测蓝光照射到颗粒物或胶体上所产生的散射光来监测水中的浊度。
进一步地，所述的光学探测部分包括贴片式LED、带通滤光片和光电二极管，贴片式LED和光电二极管并列设置于同一块电路板一上，带通滤光片封装在光电二极管的表面。
进一步地，所述的光电二极管还可以设置在电路板二上，带通滤光片封装于光电二极管表面，电路板一上正对于带通滤光片处开孔，贴片式LED设置于开孔的边缘，且贴片式LED的表面与带通滤光片的表面齐平。
进一步地，所述的贴片式LED的光源为单色紫外LED光源或紫外+蓝光复色组合封装LED光源或紫外LED+蓝光LED双光源。
进一步地，其中所述的单色紫外LED光源所选用的波长范围为250～370nm，主要用于作为荧光信号探测的激发光源，优选地采用中心波长在280±5nm的紫外芯片用于激发蛋白类荧光或腐殖质类荧光，优选地采用中心波长在310±5nm、330±5nm或365±5nm处的紫外LED芯片用于单独激发腐殖质类荧光；
进一步地，其中所述的复色组合封装LED光源是将用于激发荧光信号的紫外LED芯片和用于浊度探测的蓝光(400～500nm)LED芯片组合封装于同一基底上，优选地采用280±5nm紫外LED芯片和465±5nm蓝光LED芯片组合封装，采用310±5nm紫外LED芯片和465±5nm蓝光LED芯片组合封装，采用330±5nm紫外LED芯片和465±5nm蓝光LED芯片组合封装，采用365±5nm紫外LED芯片和465±5nm蓝光LED芯片组合封装。
进一步地，所述的带通滤光片根据贴片式LED光源的不同，选择匹配不同类型的带通滤光片，分别是波长范围为(i)330～360nm范围的带通滤光片，可用于蛋白类荧光信号探测和微生物污染预警，(ii)380～500nm范围的带通滤光片用于腐殖质类荧光信号的探测，(iii)330～500nm的带通滤光片用于对蛋白类荧光和腐殖质类荧光的总荧光信号进行探测；所述的带通滤光片对带通波长范围外光强的截止率为99.9％以上。
进一步地，所述的光电二极管是对300～500nm范围中的紫外-可见光具有较高线性响应的硅光电二极管。
进一步地，所述的电子电路系统包括单片机、电源模块、运放模块、低通滤波模块、模数转换、通信模块、温度传感器、上位机和恒流驱动模块，其中电源模块为电子电路系统各元器件供电；单片机输出数字信号控制恒流驱动电路来实现贴片式LED的开关控制；带通滤光片将光信号输入光电二极管，运放模块对光电二极管输出的信号放大处理后再传输给低通 滤波模块，低通滤波模块处理后输入到模数转换，最后由单片机进行采集后与上位机进行通信；所述的温度传感器监测电路板温度，用于因温度变化对贴片式LED的功率输出和光电二极管的信号进行校正补偿，其补偿系数通过测定同一溶液在不同温度下的数值进行确定。
进一步地，所述的运放模块采用零偏置电压的光伏模式，其运算放大器采用跨阻放大设计实现I-V转换；模数转换采用12位以上高精度AD模数转换芯片将信号进行模数转换，单片机与上位机通过IIC总线方式进行通信。
一种基于LED光源的光谱法水质监测模块的使用方法，其步骤为：
(1)打开电源模块，单片机控制恒流驱动电路，控制贴片式LED开关，只输出紫光或交替输出蓝光或紫光；
(2)贴片式LED发出的蓝光透过石英片照射到流体室水样中的细小颗粒物形成散射光，贴片式LED发出的紫光经过石英片照射到流体室水样中的溶解性有机物产生荧光；
(3)带通滤光片过滤带通波长范围外的光强，将散射光和/或荧光产生的光信号传输给光电二极管；
(4)光电二极管将光信号转换成电信号；
(5)运放模块对光电二极管输出的电信号进行处理，放大电信号，传输到低通滤波模块；
(6)低通滤波模块处理后将电信号输入到模数转换，再传输给单片机；
(7)单片机进行采集后与上位机进行通信，上位机计算水处理单元或净水机进水和出水两处荧光信号的差值和/或散射光信号的差值，判断水处理单元或净水机对有机物和浊度的去除效果。
作为本发明更进一步的阐述，所述的荧光探测DOM浓度与散射光探测浊度，单片机通过两个数字引脚输出信号控制两个独立的LED恒流驱动电路，控制紫外LED芯片和蓝光LED芯片交替点亮，由于腐殖质受紫外光激发所产生的荧光为蓝光，因此荧光和蓝光的散射光可以共用滤光片和光电二极管及其放大电路。
3.有益效果
相比于最接近的现有技术，本发明的有益之处在于：
(1)本发明所述的一种基于LED光源的光谱法水质监测模块，其优点在于LED光源采用贴片式封装，成本为TO39封装的1/20以下，有利于规模化生产。
(2)本发明所述的一种基于LED光源的光谱法水质监测模块，其优点在于LED光源和光电二极管位于平行面上，朝向相同，这样的光路设计所占空间较小，仅采用一块石英片，有利于实现光电器件与水的分离，降低防水密封的设计难度。
(3)本发明所述的一种基于LED光源的光谱法水质监测模块，根据水体中广泛存在的蛋白类或腐殖质类所具有的内在荧光特性特点，采用荧光法进行水质在线监测，可以实现对10ppb至5ppm DOC浓度水平的线性探测，并可根据重金属、医药护理品、消毒副产物与腐殖质在活性炭中的竞争吸附和膜过滤中的“穿透”行为，对活性炭滤芯或膜滤芯的更换进行提示；与TDS在线监测方法相比，荧光法还可适用于对无机盐去除效果较差的活性炭过滤或纳滤膜过滤的出水水质监测；微生物在石英片表面附着形成生物膜，由于胞外聚合物中含有大量蛋白类物质，因此，蛋白类荧光信号可以在一定程度上预警净水机内部管路的微生物污染风险。
(4)本发明采用蓝光照射到颗粒物或胶体上所产生的散射光来监测水中的浊度，对于低浊度的自来水，蓝光比红外或红光探测浊度更加灵敏，同时自来水中溶解性有机物的浓度较 低，其对蓝光探测浊度的影响可以忽略。
(5)本发明所述的一种基于LED光源的光谱法水质监测模块，其优点在于紫外光所激发产生的荧光和探测浊度所用蓝光的波长相近，通过对紫外LED芯片和蓝光LED芯片封装成复合光源，巧妙地利用同一光电二极管和带通滤光片组合，采用分时复用方式对荧光信号和浊度信号进行探测，进一步降低了探测成本。
附图说明
图1为本发明水质监测模块的外观结构的(a)正视图、(b)侧视图、(c)俯视图和(d)轴测图；
图2为本发明水质监测模块结构的爆炸分解图的正视图；
图3为本发明水质监测模块结构的爆炸分解图的轴测图；
图4为本发明水质监测模块的光学器件位置示意图；
图5为本发明水质监测模块的电子电路系统示意图；
图6为AD采集前原始电压数据(左侧Y轴)和AD采集后信号值(右侧Y轴)与溶解性有机物浓度之间的线性拟合；
图7为AD采集前原始电压数据随时间的变化图；
图8为水质监测模块所测得散射光信号值与硫酸肼浊度标准液浓度直接的线性拟合；
图9为本发明水质监测模块的流体室的流场示意图；
图10流体室的进出水流路改进示意图：(a)俯视图和(b)侧视图。
1、流体室；2、光电室；3、光学探测部分；4、电子电路系统；5、透光防水密封组件；101、快接头；102、垫圈凹槽；103、下螺丝孔；201、环形支撑架；202、顶盖；203、上螺丝孔；301、贴片式LED；302、带通滤光片；303、光电二极管；41、电路板一；42、电路板二；401、单片机；402、电源模块；403、运放模块；404、低通滤波模块；405、模数转换；406、通信模块；407、温度传感器；408、上位机；409、恒流驱动模块；501、石英片；502、密封垫圈。
具体实施方式
下面结合说明书附图和具体的实施例，对本发明作详细描述。
实施例1
本实施例的一种基于LED光源的光谱法水质监测模块及其使用方法，使用荧光与散射光所实现的水质监测对象，包括(i)通过荧光法探测蛋白类荧光信号、腐殖质类荧光信号或蛋白类荧光和腐殖质类荧光的总荧光三种荧光信号对流路中的溶解性有机物或微生物污染进行监测，(ii)通过蓝光照射到颗粒物或胶体上所产生的散射光来监测水中的浊度。
如图1、图2和图3所示，本实施例的一种基于LED光源的光谱法水质监测模块，包括流体室1、光电室2、光学探测部分3、电子电路系统4和透光防水密封组件5。流体室1两端各设有一个快接头101，一端是进水的快接头101，另一端是出水的快接头101；光电室2上方设有顶盖202，光电室2内设有环形支撑架201，环形支撑架201中设置光学探测部分3和电子电路系统4；透光防水密封组件5包括石英片501和密封垫圈502。光电室2的顶盖202通过螺丝将上螺丝孔203和下螺丝孔103进行连接，顶盖202通过环形支撑架201来顶紧石英片501和密封垫圈502，实现光电室2与流体室1的防水透光分离密封的目的。
光学探测部分3包括贴片式LED301、带通滤光片302和光电二极管303，贴片式LED301、 带通滤光片302和光电二极管303之间的位置关系和光路如图4-(a)所示，光电二极管303居中焊接在电路板二42上，贴片式LED301所在的电路板一41中央部分开孔，贴片式LED301焊接于电路板一41开孔的边缘，带通滤光片302封装于光电二极管303表面，设计两块电路板之间距离和位置，使带通滤光片302透过贴片式LED301所在电路板一41的开孔并且带通滤光片302的表面与贴片式LED301电路板一41的表面齐平。贴片式LED301采用紫外加蓝光复合封装的5050规格贴片LED，其中所封装的紫外光LED芯片发光功率为3mW，波长λ为280±5nm，所封装的蓝光LED芯片发光功率为60mW，波长λ为465±5nm，紫外光LED芯片和蓝光LED芯片的阴极分别连接各自的恒流驱动电路，共用阳极，实现独立开关控制，所输出的紫外光和蓝光的发光角均大于140°。带通滤光片302，所用波长范围为380～500nm范围的带通滤光片302，用于透过腐殖质类荧光，对其他波长范围的紫外和可见光截止率为99.9％以上，带通滤光片302固定于光电二极管303表面，其尺寸为长4.4mm，宽4.0mm，厚约2.2.mm。光电二极管303是对300～500nm范围中的紫外-可见光具有较高线性响应的贴片式封装的硅光电二极管，本实施例中选用镇江镓芯光电科技有限公司所生产的蓝光增敏型贴片式光电二极管，其尺寸为长4.4mm，宽4.0mm，厚约1.2mm。
如图5所示，电子电路系统4包括单片机401、电源模块402、运放模块403、低通滤波模块404、模数转换405、通信模块406和温度传感器407，电子电路系统4的元器件排布于两块印刷电路板一41和电路板二42上。
电源模块402为电子电路系统4各元器件供电，选用TI公司的tps61040芯片用于所需的DC-DC电压转换，采用LM317芯片分别构成恒流驱动模块409，分别驱动贴片式LED301的紫外光LED芯片和蓝光LED芯片。
光电信号经过运放模块403和低通滤波模块404进行信号放大和降噪，其中运放模块403选用TI公司的OPA129运算放大器芯片以跨阻放大方式设计电路，选用的放大电阻为500MΩ；低通滤波模块404采用TI公司的OPA227运算放大器芯片设计带宽为10Hz的低通滤波器，其目的在于将50Hz的工频干扰削减50dB。
单片机401选用采用STM32F103C8T6芯片，通过数字输出引脚控制恒流驱动电路中的LM317芯片来实现贴片式LED301光源中紫外LED芯片和蓝光LED芯片的交替闪亮，即在1s的周期内，紫外LED芯片点亮0.5s后熄灭，然后蓝光LED芯片开始点亮0.5s。当紫外LED芯片工作时，所发出的280±5nm紫外光透过石英片501照射到流体室1水样中的溶解性有机物，有机物中蛋白类物质和腐殖质类物质分别产生波长在320～350nm和380～500nm范围内的荧光，在本实施例中仅有腐殖质类荧光信号透过石英片501和带通滤光片302照射到光电二极管303表面，光电二极管303采用零偏置电压的光伏工作模式，所产生的信号经运放模块403和低通滤波模块404处理后，经模数转换405后传输给单片机401。当蓝光LED芯片工作时，所发出的465±5nm蓝光同样透过石英片501照射到流体室1中的细小颗粒物上而形成散射光，由于LED光的发光角度较大，所形成的散射光可以是垂直散射、前向散射和后向散射；散射光透过石英片501和带通滤光片302照射到光电二极管303表面，光电二极管303采用零偏置电压的光伏工作模式，所产生的信号经运放模块403和低通滤波模块404处理后，经模数转换405后传输给单片机。由于荧光和散射光都是微弱光，因此可采用分时复用的方式，共用一套光电二极管303及其运算放大电路。
单片机401与上位机408进行通讯，采用IIC方式将荧光信号和散射光信号传送给上位机408；在净水机中的进水和出水两处分别接入本实例水质监测模块，或者采用一个水质监 测模块在未使用净水机取水时监测进水的水质而在净水机取水时监测净化出水的水质，通过电磁阀的开关实现所监测水路的切换来实现对净水机处理前和处理后水质的先后监测；上位机通过比较计算净水机进水和出水两处水质监测模块所测得的荧光信号和散射光信号差值，来反映净水机对水中有机物和浊度的去除效果。
采用国际腐殖质协会自然有机物标准品配制5mg/L DOC溶液并进行梯度稀释，所测数据如图6和图7所示。在图6中，AD模数转换前原始电压数值或AD模数转换后的荧光信号值与DOC浓度均呈现出良好的线性关系(R 2>0.99)，每荧光信号单位对应的DOC浓度为5/166mg/L，即约为30μg/L；在图7中显示采用紫外LED芯片恒亮时AD模数转换前原始电压数值随时间的变化，在前30s内，电压数值变化小于0.8mV，即在12位精度AD采样精度以内；随后电压数值下降，但在60s内的数值变化小于1.5mV。这种变化是由于LED持续点亮后，芯片温度有所上升导致发光效率下降。由于净水机的使用往往在1分钟以内，且紫外LED芯片和蓝光LED芯片采用每0.5s交替频闪模式，占空比50％，可以有效解决散热问题，因此本发明实施例的水质监测模块能够满足净水器的测试需求。
采用国家标准《水质浊度的测定》(GB13200-91)配制硫酸肼标准溶液并进行梯度稀释，采用蓝光的散射进行浊度探测，如图8所示，所测得的光强信号与浊度NTU之间具有很好的线性关系(R 2>0.99)，每散射光强信号单位对应100/3882NTU，即约0.026NTU。
另外，还实测了南京某净水机品牌公司所提供的其实验室内的反渗透净水机的进出水，对于荧光信号，净化前自来水比净化后的出水高出～48mV，即～60个采样单位(arbitrary unit,AU)；对于浊度，净化前自来水笔净化后的出水高～29.5mV，即～37个采样单位(AU)，对应0.95NTU的浊度差值。
实施例2
本实施例基本与实施例1相同，不同之处在于：
如图9所示，实施例1中的流体室1的流场存在一定的死体积，本实施例中将进出水管轴线两侧的死循环区域进行实体填充，以减少流体室(1)中的死体积。
贴片式LED301、带通滤光片302和光电二极管303之间的位置关系和光路如图4-(b)所示，贴片式LED301和光电二极管303并列焊接于同一块电路板一41上，带通滤光片302封装在光电二极管303的表面，贴片式LED301和光电二极管303边缘相距一定距离，本实施例中采用2mm，使贴片式LED301的部分发光能够斜照到光电二极管303和带通滤光片302的上方空间，光电二极管303采用镇江镓芯光电科技有限公司所生产的TO-5金属封装的硅光电二极管。
模数转换405采用TI公司的ADS1118的高端模数转换芯片，具有四路单端输入和2/3-16可编程增益放大器，而单片机401采用相对低端的MA82G5B32单片机芯片。
采用国际腐殖质协会自然有机物标准品和硫酸肼浊度标准溶液配制同时含有2mg/L DOC的溶解性有机物和1NTU的浊度的溶液，本实施例的水质监测模块测得荧光信号为122AU，每单位对应的灵敏度为2/122mg/L，即约16μg/L；测得蓝光散射光的信号为73AU，每个单位对应的灵敏度为1/73NTU，即约为0.014NTU。
实施例3
本实施例基本与实施例1相同，不同之处在于：
如图10所示，本实施例中将流体室1的进出水管接口采用上下左右非对称设计，以增加紊流强度，减少流场死循环体积。
带通滤光片302的带通波长范围为330-500nm，用于对蛋白类荧光和腐殖质类荧光的总荧光信号进行探测，而对其他波长的紫外或可见光截止率为99.9％以上。
采用长江水水样(DOC约为1.8mg/L)经0.45μm过膜处理后，再往水样中添加硫酸肼浊度标准溶液增加1NTU的浊度。本实施例中所获得的总荧光信号值为92AU，每荧光单位代表的DOC浓度为1.8/92mg/L，即约为19.6μg/L；所测得蓝光散射光信号为39AU，每单位对应的灵敏度约为0.0256NTU。
实施例4
本实施例基本与实施例3相同，不同之处在于：
贴片式LED301采用310±5nm紫外和465±5nm蓝光两颗LED光源并列放置，其中紫外LED的发光功率为8mW，用于激发水中的腐殖质类荧光信号。
采用国际腐殖质协会自然有机物标准品和硫酸肼浊度标准溶液配制同时含有约2mg/L DOC的溶解性有机物和约1NTU的浊度的溶液，本实施例的水质监测模块测得荧光信号为86AU，每单位对应的灵敏度为2/86mg/L，即约23μg/L；测得蓝光散射光的信号为40AU，每个单位对应的灵敏度为1/40NTU，即约为0.025NTU。
实施例5
本实施例基本与实施例3相同，不同之处在于：
贴片式LED301采用330±5nm紫外LED芯片和465±5nm蓝光LED芯片复合封装，其中紫外LED芯片的发光功率为8mW，用于激发水中的腐殖质类荧光信号。
采用国际腐殖质协会自然有机物标准品和硫酸肼浊度标准溶液配制同时含有约2mg/L DOC的溶解性有机物和约1NTU的浊度的溶液，本实施例的水质监测模块测得荧光信号为136AU，每单位对应的灵敏度为2/136mg/L，即约15μg/L；测得蓝光散射光的信号为40AU，每个单位对应的灵敏度为1/40NTU，即约为0.025NTU。
实施例6
本实施例基本与实施例3相同，不同之处在于：
贴片式LED301采用365±5nm紫外LED芯片和465±5nm蓝光LED芯片复合封装，其中紫外LED芯片的发光功率为40mW，用于激发水中的腐殖质类荧光信号。
采用国际腐殖质协会自然有机物标准品和硫酸肼浊度标准溶液配制同时含有约2mg/L DOC的溶解性有机物和约1NTU的浊度的溶液，本实施例的水质监测模块测得荧光信号为255AU，每单位对应的灵敏度为2/255mg/L，即约8μg/L；测得蓝光散射光的信号为40AU，每个单位对应的灵敏度为1/40NTU，即约为0.025NTU。
实施例7
本实施例基本与实施例1相同，不同之处在于：
贴片式LED301为单色紫外LED光源，波长为280±5nm；带通滤光片302的带通波长范围为330-500nm。本实施例仅对水中的溶解性有机物的蛋白类荧光和腐殖质类荧光的总荧光信号进行探测，不探测浊度信号。
采用长江水水样(DOC约为1.8mg/L)经0.45μm过膜处理后分成两份，一份添加硫酸肼浊度标准试剂使得溶液浊度为2NTU，另一份不添加浊度，本实施例水质监测模块所测得两个水样的蛋白类荧光和腐殖质类荧光的总荧光信号分别为89AU和92AU。因为2NTU的硫酸肼溶液在280nm处的吸光度约为0.026，即每厘米约为94％透光率，对荧光的内部掩盖效应较小。通常情况下，自来水的浊度小于1NTU，所以自来水中的浊度对荧光信号的探测 影响很小。
实施例8
本实施例基本与实施例1相同，不同之处在于：
运放模块403中所采用的放大电阻为1GΩ，带通滤光片302的带通波长范围为330-360nm，用于对蛋白类荧光信号进行探测，而对其他波长的紫外或可见光截止率为99.9％以上。本实施例中仅单独对水中的溶解性有机物的蛋白类荧光，不探测浊度信号。
因为国际腐殖质协会自然有机物标准品的蛋白类荧光很弱，所以本实施例中采用经0.45μm过膜处理的长江水水样(DOC约为1.8mg/L)，水质监测模块所测得的蛋白类荧光信号为38AU。
实施例9
本实施例基本与实施例1相同，不同之处在于：
贴片式LED301为单色紫外LED光源，波长为310±5nm，输出光功率约为8mW。本实施例仅单独对水中的溶解性有机物的腐殖质类荧光，不探测浊度信号。
采用国际腐殖质协会自然有机物标准品配制含有约2mg/L DOC的溶解性有机物，本实施例的水质监测模块所测得腐殖质类荧光信号为86AU，每单位对应的灵敏度为2/86mg/L，即约23μg/L DOC。
实施例10
本实施例基本与实施例1相同，不同之处在于：
贴片式LED301为单色紫外LED光源，波长为330±5nm，输出光功率约为8mW。本实施例仅单独对水中的溶解性有机物的腐殖质类荧光，不探测浊度信号。
采用国际腐殖质协会自然有机物标准品配制含有约2mg/L DOC的溶解性有机物，本实施例的水质监测模块所测得腐殖质类荧光信号为137AU，每单位对应的灵敏度为2/137mg/L，即约15μg/L DOC。
实施例11
本实施例基本与实施例1相同，不同之处在于：
贴片式LED301为单色紫外LED光源，波长为365±5nm，输出光功率为40mW。本实施例仅单独对水中的溶解性有机物的腐殖质类荧光，不探测浊度信号。
采用国际腐殖质协会自然有机物标准品配制含有约2mg/L DOC的溶解性有机物，本实施例的水质监测模块所测得腐殖质类荧光信号为257AU，每单位对应的灵敏度为2/257mg/L，即约8μg/L DOC。

Claims (11)

  1. 一种基于LED光源的光谱法水质监测模块，包括流体室(1)、光电室(2)和透光防水密封组件(5)，其特征在于：所述的流体室(1)、透光防水密封组件(5)和光电室(2)依次连接，所述的光电室(2)内包括光学探测部分(3)和电子电路系统(4)，所述的光学探测部分(3)安装在电子电路系统(4)的电路板上，其中光学探测部分(3)提供光源及将荧光或散射光信号转换成电信号，所述的电子电路系统(4)对电信号进行处理后输出。
  2. 根据权利要求1所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的光学探测部分(3)包括贴片式LED(301)、带通滤光片(302)和光电二极管(303)，贴片式LED(301)和光电二极管(303)并列设置于电路板一(41)上，且贴片式LED(301)的光可以照到光电二极管(303)的上方，带通滤光片(302)封装在光电二极管(303)的表面。
  3. 根据权利要求1所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的光电二极管(303)设置在电路板二(42)上，带通滤光片(302)封装于光电二极管(303)表面，电路板一(41)上正对于带通滤光片(302)处开孔以使带通滤光片(302)穿过该孔，贴片式LED(301)设置在电路板一(41)上，且贴片式LED(301)的光可以照到光电二极管(303)的上方。
  4. 根据权利要求2或3任意一项所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的贴片式LED(301)的光源为单色紫外LED光源或紫外+蓝光复色组合封装LED光源或紫外LED+蓝光LED双光源。
  5. 根据权利要求4所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的单色紫外LED光源所选用的波长范围为250～370nm，优选地采用中心波长为280±5nm或310±5nm或330±5nm或365±5nm的紫外LED芯片。
  6. 根据权利要求4所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的复色组合封装LED光源是将紫外波长250～370nm范围内的LED芯片和蓝光波长400～500nm范围内的LED芯片组合封装于同一基底上，优选地采用280±5nm紫外LED芯片和465±5nm蓝光LED芯片组合封装，或采用310±5nm紫外LED芯片和465±5nm蓝光LED芯片组合封装，或采用330±5nm紫外LED芯片和465±5nm蓝光LED芯片组合封装，或采用365±5nm紫外LED芯片和465±5nm蓝光LED芯片组合封装。
  7. 根据权利要求6任意一项所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的带通滤光片(302)根据LED光源的不同，选择匹配不同类型的带通滤光片(302)，分别是波长范围为330～360nm或380～500nm或330～500nm的带通滤光片(302)，所述的带通滤光片(302)对带通波长范围外光强的截止率为99.9％以上。
  8. 根据权利要求2或3任意一项所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的光电二极管(303)是对300～500nm范围中的紫外-可见光具有较高线性响应的硅光电二极管。
  9. 根据权利要求1所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的电子电路系统(4)包括单片机(401)、电源模块(402)、运放模块(403)、低通滤波模块(404)和模数转换(405)，其中电源模块(402)为电子电路系统(4)各元器件供电；单片机(401)输出数字信号控制恒流驱动电路(409)来实现贴片式LED(301)的开关控制；光电二极管(303)接收透过带通滤光片(302)的光并将其转换为电信号输出，运放模块(403)对光电二极管(303)输出的信号放大处理后再传输给低通滤波模块(404)，低通滤波模块(404)处理后输入到模数转换(405)，最后由单片机(401)进行采集后与上位机(408)进行通信。
  10. 根据权利要求9所述的一种基于LED光源的光谱法水质监测模块，其特征在于：所述的运放模块(403)采用零偏置电压的光伏模式，其运算放大器采用跨阻放大设计；模数转换(405)采用12位以上高精度AD模数转换芯片将信号进行模数转换。
  11. 一种基于LED光源的光谱法水质监测模块的使用方法，其步骤为：
    (1)打开电源模块(402)，单片机(401)控制恒流驱动电路(409)，控制贴片式LED(301)输出紫光或交替输出蓝光或紫光；
    (2)贴片式LED(301)发出的蓝光透过石英片(501)照射到流体室(1)水样中的细小颗粒物形成散射光；贴片式LED(301)发出的紫光经过石英片(501)照射到流体室(1)水样中的溶解性有机物产生荧光；
    (3)带通滤光片(302)过滤带通波长范围外的光强，将交替产生的散射光和/或荧光光信号传输给光电二极管(303)；
    (4)光电二极管(303)将光信号转换成电信号；
    (5)运放模块(403)对光电二极管(303)输出的电信号进行处理，放大电信号，传输到低通滤波模块(404)；
    (6)低通滤波模块(404)将电信号中的50Hz工频干扰滤除处理后，输入到模数转换(405)，再传输给单片机(401)，或直接输入到带有模数转换功能的单片机(401)中；
    (7)单片机(401)进行采集后与上位机(408)进行通信，上位机(408)计算净水系统进水和出水两处荧光信号的差值和/或散射光信号的差值，判断净水处理单元对有机物和浊度的去除效果。
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