CN109709126A - Algae enrichment-X-ray fluorescence spectra heavy metal in water automatic detection device and method - Google Patents
Algae enrichment-X-ray fluorescence spectra heavy metal in water automatic detection device and method Download PDFInfo
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Abstract
The invention discloses a seeds algae enrichment-X-ray fluorescence spectra heavy metal in water automatic detection device and methods, to have the green alga in the freshwater microalgae of stronger absorption property as adsorbent material to heavy metal, using band-like filter membrane as the undertaking carrier of frustule and heavy metal, uniform thin sample, filter-paper-tape transmission, the thin sample drying of heavy metal and XRF spectral measurement are formed to the absorption of heavy metal, algae-heavy metal accumulation by algae and analysis program realize water body various heavy simultaneously rapidly, continuously, automatic on-line detects.The present invention have the characteristics that it is easy to operate, without chemical reagent, without secondary pollution, economic and environment-friendly, operation expense is low, high degree of automation, significantly improve stability, sensitivity that XRF spectroscopic methodology detects heavy metal in water.Used fluid flow accurately controls and continuous suction filtration mode can realize that the multiple of same water sample to be analyzed continuously repeats sample preparation, is more advantageous to and improves the accuracy that XRF spectroscopic methodology detects heavy metal in water.
Description
Technical field
The present invention relates to Heavy-Metal-Contaminated Environments analyte detection technical field more particularly to seeds algae enrichment-x-ray fluorescence light
Compose heavy metal in water automatic detection device and method.
Background technique
In recent years, with the rapid industrial development in our country, heavy metal pollution of water body problem is very prominent, mostly frequently outburst
The heavy metal pollutions event such as " blood lead is exceeded ", " cadmium is exceeded ", " Itai-itai diseases ".Heavy metal is rich because having non-biodegradable and biology
Collection property, and bio-toxicity is significant, can it is carcinogenic, cause disease and mutagenesis, once accumulate in vivo, it will to human health and life
State environment constitutes a serious threat, and causes heavy losses to national economy.Therefore heavy metal in water is quick, real-time, online, automatic
Detection is of great practical significance safely to prevention and treatment heavy metal pollution of water body, guarantee source quality.
Traditional heavy metal detection method such as atomic absorption spectrography (AAS) (AAS), atomic fluorescence spectrometry (AFS), inductive coupling
Plasma-Atomic Emission spectroscopic methodology (ICP-AES), inductively coupled plasma mass spectrometry method (ICP-MS) though etc. have it is sensitive
The advantages that degree is high, accuracy is good, but need spot sampling, then carry out lab analysis, be unable to satisfy heavy metal quickly, in real time,
Line detects demand automatically.The some heavy metal rapid detection methods newly risen in recent years, specifically include that biochemical detection methods (such as
Enzyme inhibition analysis method, immunoassay, microbiological method, chemical staining method etc.), electrochemical detection method (mainly anode
Stripping voltammetry) and spectroscopy detection method (such as laser induced breakdown spectroscopy method and x ray fluorescence spectrometry).Biochemistry detection side
Though method sensitivity with higher, the selectivity of method is poor, cannot achieve various heavy while detecting.Electrochemical Detection
Though method can realize various heavy while measure, electrode manufacturing cost is high, service life is short, and liquid mercury electrode makes
With noxious material mercury can be precipitated in the process, therefore there are problems that testing cost is at high cost and easily cause secondary environmental pollution.Swash
Although photoinduction breakdown spectral technology is quickly grown in recent years, it can be achieved that various heavy while measuring, swash in spectral measurement
The plasma evolution process that photoinduction generates is sufficiently complex, the process be easy to be excited light energy, properties of samples, matrix composition and
The factors such as plasma peripheral gas environment influence, and spectrum repeatability and stability are poor.
Compared to the above, x-ray fluorescence (X-ray Fluorescence, XRF) spectroscopic methodology is as heavy metal spectrum
Important technology in rapid detection method, because have sample to be tested can be measured simultaneously without destructive, multiple element, spectral line interferes
Less, measuring speed is fast, high repeatability and other advantages, be heavy metal element quickly, in real time, a kind of effective means of on-line analysis,
It is the important development direction of heavy metal field quick detection technology.XRF spectroscopic methodology generates sigmatron by X-ray tube to swash
Sample to be tested is sent out, so that it is generated feature secondary X-ray (being also x-ray fluorescence), according to the wavelength or energy of characteristic x-ray fluorescence
And fluorescence intensity to carry out qualitative and quantitative analysis to sample to be tested.Currently, XRF spectral technique is in mining industry, geology and oil sample
Middle metal element content analysis and Atmospheric particulates heavy metal analysis etc. have had a wide range of applications, but XRF spectrum at present
Technology is directly few to heavy metal in water detection and the research of application aspect, this is because XRF spectral technique is directly to water body
Heavy metal analysis is faced with following two main problem:
1. sample irradiated area can lead to part because of local heating when sigmatron direct irradiation water body example
Element chemically reacts, thus phenomena such as will appear bubble, precipitating, being even precipitated, therefore x-ray fluorescence caused by sample
Intensity is extremely unstable, easily changes, and has seriously affected the reproducibility and stability of x-ray fluorescence analysis signal, therefore a huge sum of money
The precision for belonging to detection is poor.
2. after the X-ray direct irradiation water body example that excitaton source generates, since water body has stronger absorption to make X-ray
With, so that the scattering background of higher-strength is generated, while characteristic X-ray the intensity of spectral line that analyzed element is emitted is weaker, because
The noise that this causes heavy metal in water to detect is relatively low, and sensitivity is poor, and the detection limit of x ray fluorescence spectrometry is unable to satisfy ring
The testing requirements of border and industrial circle Heavy Metals in Waters element.
Because of the presence of the above problem, X-ray fluorescence spectra technology directly to heavy metal in water detection application aspect by
Limitation.
Summary of the invention
The object of the invention is to remedy the disadvantages of known techniques, provides a seeds algae enrichment-X-ray fluorescence spectra water body
Heavy metal automatic detection device and method.Using the green alga in freshwater microalgae as adsorbent material Sync enrichment water body various heavy
Element, using band-like filter membrane as the supporting body of frustule and heavy metal, the system in such a way that fluid flow accurately controls and continuously filters
XRF spectral measurement and analysis are carried out at multiple identical equally distributed thin samples of heavy metal of same water body example, with paper tape
The transmission mode realization thin sample of heavy metal is real by enrichment region to heating zone, the automatically delivering to XRF spectral measurement area by heating zone
Existing water body various heavy XRF spectrum detects rapidly, continuously, automatically simultaneously, solves XRF spectral technique directly to heavy metal in water
Detect the low problem of existing stability difference and sensitivity.
The present invention is achieved by the following technical solutions:
One seeds algae enrichment-X-ray fluorescence spectra heavy metal in water automatic detection device, include heavy metal accumulation system,
Paper tape conveyer system, sample drying system, X-ray fluorescence spectra measuring system and acquisition and control system；
The heavy metal accumulation system includes reaction cup, peristaltic pump, flow controller, filter cup, moves up and down dress
It sets, sand core support base, filtrate receiving bottle, vacuum pump and filter-paper-tape, the discharge outlet of the lower end of the reaction cup and described
Peristaltic pump is connected by hose, and the other end of peristaltic pump is connected by the import of hose and flow controller, flow controller
Outlet is connect with the import of filter cup upper end, and the filter cup wall of cup lower end is in infundibulate to contract, and bottom of a cup portion is circle
Leak, filter cup, which is fixedly connected on, to be moved up and down on device, and the sand core support base is by top center embedded with identical thickness
The cylindrical glass and lower end center for spending round sand core are provided with the support base that the cylindrical glass of through-hole is constituted, sand core support base
Top cylindrical shape glass outer diameter is equal to the bottom outside diameter of filter cup, and the bottom that inner circular sand core diameter is greater than filter cup is leaked
Mouth diameter, the outer diameter of the cylindrical glass of sand core support base lower end are less than the outer of sand core support base top cylindrical shape glass
Diameter, internal diameter are greater than the diameter of top circular sand core, and the lower end of sand core support base is connect with the upper end of the filtrate receiving bottle,
The sand core support base lower end cylindrical glass inner wall and filtrate receiving bottle upper end glass outer wall is ground glass wall, mouth
Diameter size is identical, is equipped with exhaust outlet in the middle upper end of filtrate receiving bottle, the exhaust outlet is controlled to a vacuum pump by rubber tube；
The paper tape conveyer system is by filter-paper-tape, paper feeding tep reel, paper pushing motor, roll paper tep reel, roll paper motor, motor
Driver and paper feed position detecting system are constituted, the internal diameter phase of the width and paper feeding tep reel and roll paper tep reel of the filter-paper-tape
Together, the motor driver respectively drives paper pushing motor and the rotation of roll paper motor, and paper pushing motor drives the rotation of paper feeding tep reel to release
Filter-paper-tape is put, roll paper motor drives the rotation of roll paper tep reel to wind filter-paper-tape, and paper feeding tep reel is equal with the revolving speed of roll paper tep reel, institute
The filter-paper-tape stated is placed between the filter cup and sand core support base, and the width of filter-paper-tape is greater than at the top of sand core support base
The diameter of round sand core, when move up and down device drive filter cup move down after, filter cup, filter-paper-tape, sand core support base,
Filtrate receiving bottle and vacuum pump constitute one and filter system；The paper feed position detecting system includes perforating device, photoelectricity inspection
It surveys device one and photoelectric detector two, the perforating device includes stepper motor one and syringe needle, perforating device is located at sand core branch
The side of pedestal is supportted, the photoelectric detector one is located at heating region, and the photoelectric detector two is located at X-ray fluorescence spectra survey
Measure region；
The sample drying system is between heavy metal accumulation system and X-ray fluorescence spectra measuring system, and position
In the underface of filter-paper-tape, for carrying out heating, drying processing, sample drying system to the round thin sample of heavy metal on filter-paper-tape
System is made of carbon fiber heating tube and power supply circuit；
The X-ray fluorescence spectra measuring system includes the X-ray tube and SDD detector above filter-paper-tape, X
Ray tube is excitation light source, for generating the sigmatron for exciting Characteristics of Heavy Metals x-ray fluorescence in thin sample, works as heavy metal
It being excited by sigmatron after energy level transition occurs, the characteristic x-ray fluorescence signal launched is received by SDD detector, by
The conversion of SDD detector progress photosignal；
The acquisition and control system respectively with the control terminal of peristaltic pump, the control terminal of flow controller, up and down
The control terminal of mobile device, the control terminal of vacuum pump, the control terminal of motor driver, the control terminal of stepper motor one, sample dry
The control terminal of dry systems, the control terminal of photoelectric detector one, the control terminal of photoelectric detector two, X-ray tube and SDD detector
Control terminal electrical connection, the acquisition and control system includes power module, data acquisition module, single-chip microcontroller and its control
Circuit processed, the data acquisition module and power module are connect with single-chip microcontroller, and data acquisition module is to SDD detector photoelectricity
Signal after signal conversion is acquired, stores, analyzing and handling, and single-chip microcontroller and its control circuit are respectively to peristaltic pump, flow
Controller moves up and down device, vacuum pump, perforating device, sample drying system, photoelectric detector one, Photoelectric Detection two, motor
Driver, X-ray tube and SDD detector send control signal, realize the control function of whole device, and power module is used for whole
A device power supply.
The filter-paper-tape is strand fiberglass miillpore filter, and pore size is 0.22 μm.
The device that moves up and down includes support frame, vertical rail is equipped on the support frame, on vertical rail
It is slidably fitted with filter cup clamper, the filter cup clamper is connect with stepper motor two, the driving filtering of stepper motor two
Cup clamper moves up and down on the vertical rail of support frame, and the stepper motor two and acquisition and control system connect
It connects.
One seeds algae enrichment-X-ray fluorescence spectra heavy metal in water automatic detection device, each component function are as follows: described is anti-
Answering cup is the reaction vessel of algae adsorbed water body heavy metal；The peristaltic pump is used for the fluid sample in drive response cup to filtering
It is flowed in cup；Flow and volume of the flow controller for the flowing of accurate measurement liquid；The filter-paper-tape is used for algae
The undertaking carrier of cell and heavy metal；The vacuum pump is used to receive filter cup, filter-paper-tape, sand core support base, filtrate
The closed system that bottle is constituted is evacuated, so that the frustule for being adsorbed with heavy metal evenly dispersed in filter cup is acted in pressure
Lower uniform settlement forms the equally distributed thin sample of circle of heavy metal on the filter-paper-tape of filter cup bottom；The sample dries
Dry systems carry out drying and processing for the thin sample of counterweight metal circular, generate to avoid Sample moisture to subsequent XRF spectral measurement
It influences, the power supply circuit in sample drying system is connected with acquisition and control system, by acquisition and control system
Control signal is sent to power supply circuit, is powered after power supply circuit receives control signal to carbon fiber heating tube, carbon fiber adds
Heat pipe transmits electric energy in a manner of infra-red radiation to surrounding, carries out open heating to the round thin sample of the heavy metal in top
Drying and processing, while the conduction time of acquisition and control system control power supply circuit and size of current, to realize to heating
The control of time and temperature, to avoid temperature is excessively high from causing sample and filter-paper-tape deformation occurs and effectively shorten XRF spectrum to survey
Sample cooling time before amount, the heating temperature of sample drying system will be controlled at 45 DEG C；Data are taken to be used for control system
Signal after SDD detector photoelectric signal transformation is acquired, is stored, is analyzed and is handled, and for controlling whole device work
Make the execution that instructs, including peristaltic pump, flow controller, move up and down device, vacuum pump, perforating device, sample drying system,
The control of photoelectric detector, motor driver, X-ray tube and SDD detector, by the control to peristaltic pump, so that reaction cup
In fluid sample flowed into filter cup；By the control to flow controller, with the flow of accurate judgement liquid flowing and
Volume；By the way that device control is moved up and down, filter cup is lifted, so that forming gap between filter cup and filter-paper-tape, it is convenient for
Filter-paper-tape transmission；By the way that device control is moved up and down, filter cup is put down, so that filter cup, filter-paper-tape, sand core support bottom
Seat, filtrate receiving bottle and vacuum pump constitute one and filter system；By the control to vacuum pump, realize to being adsorbed with weight in filter cup
The frustule suspension of metal is filtered；By the control to motor driver, to control paper pushing motor and roll paper motor band
Dynamic paper feeding tep reel and the rotation of roll paper tep reel, realize the function of paper tape transmission；By the control to perforating device, realize in heavy metal
The function of an aperture is accurately made a call at rich region edge；By the control to photoelectric detector, with round on accurate judgement filter-paper-tape
The specific transmission position of thin sample, realize thin sample by enrichment positions to heating location, by heating location to X-ray fluorescence spectra
The function of the accurate positionin of measurement position；By the control to sample drying system, realize to the thin sample for being enriched with heavy metal
The function of flash baking processing；By the control to X-ray tube, it is to be measured to realize that X-ray tube excitaton source generates sigmatron excitation
The function of sample；By the control to SDD detector, realize that SDD detector receives the x-ray fluorescence signal that sample is launched
And carry out the function of photoelectric conversion.
The heavy metal accumulation system acquires in the collective effect and data of peristaltic pump and flow controller and controls system
Under the control of system, it may be implemented to carry out multiplicating sample preparation to same water body example to be analyzed, in the accurate control of flow controller
System is lower so that the liquid sample volume every time in the flowed into filter cup of sample preparation is identical, to realize to the multiple of same water sample to be analyzed
XRF spectral measurement and analysis are conducive to improve the accuracy that XRF spectral technique detects heavy metal in water.
One seeds algae enrichment-X-ray fluorescence spectra heavy metal in water automatic testing method, including algae absorption heavy metal process,
Algae-heavy metal accumulation forms uniform thin specimen, filter paper tape transfer procedure, the thin sample drying process of heavy metal and XRF spectrum
Measurement and analytic process；
Algae adsorbs heavy metal process are as follows: reaction cup is used for the reaction vessel of algae adsorbed water body heavy metal, when in reaction cup
After frustule and heavy metal reach adsorption equilibrium, starts algae-heavy metal accumulation and form uniform thin specimen；
Algae-heavy metal accumulation forms uniform thin specimen are as follows: when the frustule in reaction cup reaches absorption with heavy metal
After balance, moves up and down device control filter cup and decline and be pressed on the filter-paper-tape in sand core support base, be then turned on wriggling
Pump and flow controller, the fluid sample for controlling certain volume are flowed into filter cup, turn off peristaltic pump and flow control later
Device processed, is then turned on vacuum pump, starts to filter the frustule suspension for being adsorbed with heavy metal in filter cup, so that being adsorbed with a huge sum of money
The frustule of category on uniform settlement to filter-paper-tape, forms the equally distributed thin sample of circle of heavy metal under pressure；
Filter paper tape transfer procedure are as follows: after the completion of the fluid sample in filter cup all filters, close vacuum pump, punching dress
An aperture is made a call at the thin sample edge of circle set on filter-paper-tape, moves up and down device control filter cup later and is lifted up, motor
Driver, photoelectric detector one are respectively started, paper pushing motor and roll paper motor driven tapes under the control of motor driver
Disk and roll paper tep reel are rotated clockwise to transmit filter-paper-tape, under the judgement of photoelectric detector one, by the heavy metal on filter-paper-tape
Thin sample is sent to heating region, and motor driver, photoelectric detector one stop working at this time；
The thin sample drying process of heavy metal are as follows: sample drying system starting, to the thin sample of the heavy metal of side placed on it into
The processing of row heating, drying；
XRF spectral measurement and analytic process are as follows: after heating, drying, sample drying system stops working, cooling to thin sample
To room temperature, motor driver, photoelectric detector two start, and paper pushing motor and roll paper motor drive under the control of motor driver
Dynamic paper feeding tep reel and roll paper tep reel are rotated clockwise to transmit filter-paper-tape, will be on filter-paper-tape under the judgement of photoelectric detector two
The thin sample of heavy metal be accurately sent to X-ray fluorescence spectra measured zone, at this time motor driver, photoelectric detector two stop
Work, X-ray tube and the starting of SDD detector are started to work, and X-ray tube generates sigmatron and excites the thin sample of heavy metal, SDD
Detector by the x-ray fluorescence signal detected carry out photoelectric conversion, and transmit signals to acquisition and control system into
Row data acquisition and procession.
The algae is the green alga in freshwater microalgae, specially chlorella or chlorella pyrenoidosa or tiltedly raw China fir algae, because
These types of green alga is all unicellular frond, and there is small cell volume, large specific surface area, cell not to allow easy to reunite be not easy into
Block disperses the features such as more uniform in water body example, in addition, these types of algae to lead (Pb), cadmium (Cd), chromium (Cr), nickel (Ni),
Copper (Cu), cobalt (Co), silver-colored (Ag) etc. all have good absorption property, can adsorbed water body various heavy simultaneously.
The heavy metal is lead (Pb), cadmium (Cd), chromium (Cr), nickel (Ni), copper (Cu), cobalt (Co), two in silver-colored (Ag)
Kind is a variety of.
The invention has the advantages that the present invention is based on algae to have stronger characterization of adsorption to heavy metal, by algae beneficiation technologies, filter
Paper tape tranmission techniques are combined with X-ray fluorescence spectra measuring technique, using filter-paper-tape as frustule-heavy metal undertaking carrier,
Uniform thin sample, filter-paper-tape transmission, the thin sample drying of heavy metal are formed to the absorption of heavy metal, algae-heavy metal accumulation by algae
And XRF spectral measurement and analysis program realize water body various heavy rapidly, continuously, automatic on-line detect, have it is easy to operate,
Without chemical reagent, without secondary pollution, economic and environment-friendly, operation expense is low, high degree of automation the features such as, be conducive to improve
Stability, sensitivity and the accuracy of heavy metal in water XRF spectral detection, various heavy is fast simultaneously suitable for natural water
Speed, continuous, automatic on-line detection.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention.
Fig. 2 is the method for the present invention flow chart.
Specific embodiment
As shown in Figure 1, the Pb that the present embodiment is prepared with laboratory2+And Cr3+Aqueous solution is sample to be analyzed, Pb2+Concentration
For 20mgL-1, Cd3+Concentration be 20mgL-1, using chlorella as adsorbent material, chlorella is to train in use for laboratory BG-11
It supports base inoculation and is 20 DEG C in temperature, intensity of illumination is 200 μm of olm-2·s-1, Light To Dark Ratio be 12h:12h under the conditions of cultivate to
30 days frustule suspension, chlorophyll concentration reach 24000 μ gL-1。
As shown in Figure 1, algae enrichment-X-ray fluorescence spectra heavy metal in water automatic detection device, includes heavy metal accumulation
System, paper tape conveyer system, sample drying system 12, X-ray fluorescence spectra measuring system and acquisition and control system 21；
Heavy metal accumulation system includes reaction cup 1, peristaltic pump 2, flow controller 3, filter cup 4, moves up and down device
5, sand core support base 6, filtrate receiving bottle 7, vacuum pump 8 and filter-paper-tape 18, reaction cup 1 is as a huge sum of money in chlorella adsorbed water body
Belong to Pb2+And Cr3+Reaction vessel, the discharge outlet of lower end connect with peristaltic pump 2 by hose, and the other end of peristaltic pump 2 passes through
Hose is connect with the import of flow controller 3, and the outlet of flow controller 3 is connect with the import of 4 upper end of filter cup, filter cup 4
Wall of cup lower end is in infundibulate to contract, and bottom of a cup portion is round leak, and filter cup 4, which is fixedly connected on, to be moved up and down on device 5, sand
Core support base 6 is that the cylindrical glass and lower end center by top center embedded with same thickness circle sand core are provided with the circle of through-hole
The support base that cylindricality glass is constituted, the bottom outside that 6 top cylindrical shape glass outer diameter of sand core support base is equal to filter cup 4 are straight
Diameter, inner circular sand core diameter are greater than the bottom leak diameter of filter cup 4, the cylindrical glass of 6 lower end of sand core support base
Outer diameter is less than the outer diameter of 6 top cylindrical shape glass of sand core support base, and internal diameter is greater than the diameter of top circular sand core, sand core support
The lower end of pedestal 6 is connect with the upper end of filtrate receiving bottle 7, and 6 lower end cylindrical glass inner wall of sand core support base and filtrate receive
7 upper end glass outer walls of bottle are both designed as ground glass wall, and caliber size is identical, are equipped with exhaust in the middle upper end of filtrate receiving bottle 7
Mouthful, exhaust outlet is connect by rubber tube with vacuum pump 8；
Paper tape conveyer system be by filter-paper-tape 18, paper feeding tep reel 9, paper pushing motor 10, roll paper tep reel 15, roll paper motor 16,
Motor driver 17 and paper feed position detecting system are constituted, the width of filter-paper-tape 18 and paper feeding tep reel 9 and roll paper tep reel 15 it is interior
Diameter is identical, and motor driver 17 respectively drives paper pushing motor 10 and roll paper motor 16 rotates, and paper pushing motor 10 drives paper feeding tep reel 9
Rotation release filter-paper-tape 18, roll paper motor 16 drive the rotation of roll paper tep reel 15 to wind filter-paper-tape 18, paper feeding tep reel 9 and roll paper band
The revolving speed of disk 15 is equal, and filter-paper-tape 18 is placed between filter cup 4 and sand core support base 6, and the width of filter-paper-tape 18 is greater than sand core
The diameter of 6 top circular sand core of support base, when move up and down device drive filter cup 4 move down after, filter cup 4, filter paper
Band 18, sand core support base 6, filtrate receiving bottle 7 and vacuum pump 8 constitute one and filter system；Paper feed position detecting system includes
Perforating device 11, photoelectric detector 1 and photoelectric detector 2 14, perforating device 11 include stepper motor one and syringe needle, are beaten
Aperture apparatus is located at the side of sand core support base, needle diameter 1mm, for being enriched with heavy metal Pb on filter-paper-tape 182+With
Cr3+Thin sample edge punch the aperture that diameter size is 1mm, photoelectric detector 1 is located at heating region, photoelectric detector
II 14 are located at X-ray fluorescence spectra measured zone, and it includes to be respectively arranged in filter-paper-tape 18 that photoelectric detector, which is an optoelectronic switch,
The emitting diode and reception diode of upper and lower corresponding position, when the thin sample of heavy metal is sent to heating region or x-ray fluorescence
When spectral measurement region, the aperture at thin sample edge be located just at photoelectric detector emitting diode and reception diode it
Between, reception diode is according to the specific transmission position of the thin sample of variation accurate judgement of the light intensity signal received；
Sample drying system 12 is located at filter between heavy metal accumulation system and X-ray fluorescence spectra measuring system
The underface of paper tape 18, for the heavy metal Pb on filter-paper-tape 182+And Cr3+Round thin sample carries out heating, drying processing, sample
Product drying system 12 is made of carbon fiber heating tube and power supply circuit；
X-ray fluorescence spectra measuring system includes the X-ray tube 19 and SDD detector 20 above filter-paper-tape, and X is penetrated
Spool 19 is excitation light source, for generating the sigmatron of Characteristics of Heavy Metals x-ray fluorescence in the thin sample of excitation, works as heavy metal
It being excited by sigmatron after energy level transition occurs, the characteristic x-ray fluorescence signal launched is received by SDD detector 20, by
The conversion of the progress photosignal of SDD detector 20；
Acquisition and control system 21 respectively with the control terminal of peristaltic pump 2, the control terminal of flow controller 3, on move down
The dynamic control terminal of device 5, the control terminal of vacuum pump 8, the control terminal of motor driver 17, the control terminal of stepper motor one, sample
The control terminal of drying system 12, the control terminal 13 of photoelectric detector one, the control terminal of photoelectric detector 2 14,19 and of X-ray tube
The control terminal of SDD detector 20 connects, and acquisition and control system 21 includes power module, data acquisition module, monolithic
Machine and control circuit, data acquisition module therein for the signal after 20 photoelectric signal transformation of SDD detector is acquired,
Storage, analysis and processing, single-chip microcontroller and its control circuit respectively to peristaltic pump 2, flow controller 3, move up and down device 5, true
Sky pump 8, perforating device 11, sample drying system 12, photoelectric detector 1, photoelectric detector 2 14, motor driver 17, X
Ray tube 19 and SDD detector 20 send control signal, realize the control function of whole device, and power module is used for entire dress
Set power supply.
Filter-paper-tape is strand fiberglass miillpore filter, and pore size is 0.22 μm, as chlorella algae cell and a huge sum of money
Belong to Pb2+And Cr3+Undertaking carrier.
Algae enrichment-X-ray fluorescence spectra heavy metal in water automatic detection device, each component function are as follows: reaction cup 1 is bead
Algae adsorbed water body heavy metal Pb2+And Cr3+Reaction vessel；Peristaltic pump 2 is used for the fluid sample in drive response cup 1 to filtering
It is flowed in cup 4；Flow and volume of the flow controller 3 for the flowing of accurate measurement liquid；Vacuum pump 8 is used for filter cup 4, filter
The closed system that paper tape 18, sand core support base 6, filtrate receiving bottle 7 are constituted is evacuated, so that evenly dispersed in filter cup 4
Be adsorbed with heavy metal Pb2+And Cr3+Chlorella algae cell uniform settlement under pressure, the filter paper in 4 bottom of filter cup
Heavy metal Pb is formed on band 182+And Cr3+The equally distributed thin sample of circle；Sample drying system 12 is used for heavy metal Pb2+With
Cr3+Round thin sample carries out drying and processing, has an impact to avoid Sample moisture to subsequent XRF spectral measurement, sample drying system
Power supply circuit in system 12 is connected with acquisition and control system 21, from acquisition and control system 21 to power supply circuit
Control signal is sent, is powered after power supply circuit receives control signal to carbon fiber heating tube, carbon fiber heating tube is by electric energy
It is transmitted in a manner of infra-red radiation to surrounding, to the heavy metal Pb for being in top2+And Cr3+Round thin sample carries out open heating
Drying and processing, while acquisition and control system 21 controls conduction time and the size of current of power supply circuit, to realize to adding
The control of hot time and temperature, to avoid temperature is excessively high from causing sample and filter-paper-tape 18 deformation occurs and effectively shorten XRF light
Sample cooling time before spectrometry, the heating temperature of sample drying system 12 will be controlled at 45 DEG C；Data are taken is with control
System 21 is used to control for being acquired the signal after 20 photoelectric signal transformation of SDD detector, storing, analyzing and handling
The execution of whole device work order, including peristaltic pump 2, flow controller 3, move up and down device 5, vacuum pump 8, perforating device
11, sample drying system 12, photoelectric detector 1 and photoelectric detector 2 14, motor driver 17, X-ray tube 19 and SDD
The control of detector 20, by the control to peristaltic pump 2, so that the fluid sample in reaction cup 1 is flowed into filter cup 4；It is logical
The control to flow controller 3 is crossed, with the flow and volume of the flowing of accurate judgement liquid；By to move up and down device 5 control,
Filter cup 4 is lifted, so that forming gap between filter cup 4 and filter-paper-tape 18, is transmitted convenient for filter-paper-tape 18；By to above moving down
Dynamic device 5 controls, and filter cup 4 is put down, so that filter cup 4, filter-paper-tape 18, sand core support base 6, filtrate receiving bottle 7 and true
Sky pump 8 constitutes one and filters system；By the control to vacuum pump 8, realize to being adsorbed with heavy metal Pb in filter cup 42+And Cr3+
Chlorella algae cell suspending liquid filtered；By the control to motor driver 17, to control paper pushing motor 10 and roll paper
Motor 16 drives paper feeding tep reel 9 and roll paper tep reel 15 to rotate, and realizes the function of paper tape transmission；Pass through the control to perforating device 11
System is realized in heavy metal Pb2+And Cr3+Accurately get the function that a pore size is 1mm aperture in rich region edge；By right
The control of photoelectric detector 1 and photoelectric detector 2 14, with the specific transmission of thin sample round on accurate judgement filter-paper-tape 18
Position realizes that thin sample is determined by enrichment positions to heating location, by the accurate of heating location to X-ray fluorescence spectra measurement position
The function of position；By the control to sample drying system 12, realize to being enriched with heavy metal Pb2+And Cr3+Thin sample quickly dry
The function of dry-cure；By the control to X-ray tube 19, realize that 19 excitaton source of X-ray tube generates sigmatron excitation to test sample
The function of product；By the control to SDD detector 20, realize that SDD detector 20 receives the x-ray fluorescence letter that sample is launched
Number and carry out the function of photoelectric conversion.
Collective effect and acquisition and control system 21 of the heavy metal accumulation system in peristaltic pump 2 and flow controller 3
Control under, may be implemented to containing Pb2+And Cr3+Same water body example to be analyzed carry out multiplicating sample preparation, in flow control
The accurate control of device 3 processed is lower so that the liquid sample volume every time in the flowed into filter cup 4 of sample preparation is identical, with realization to containing
Pb2+And Cr3+Same water sample to be analyzed multiple XRF spectral measurement and analysis, be conducive to improve XRF spectral technique to water body
Heavy metal Pb2+And Cr3+The accuracy of detection.
As shown in Fig. 2, algae enrichment-X-ray fluorescence spectra heavy metal in water automatic testing method, including algae adsorb heavy metal
Process, algae-heavy metal accumulation form uniform thin specimen, filter paper tape transfer procedure, the thin sample drying process of heavy metal and XRF
Spectral measurement and analytic process；
Algae adsorbs heavy metal process are as follows: reaction cup 1 is used for chlorella adsorbed water body heavy metal Pb2+And Cr3+Reaction hold
Device, when the chlorella algae cell and heavy metal Pb in reaction cup 12+And Cr3+After reaching adsorption equilibrium, start algae-heavy metal accumulation
Form uniformly thin specimen；
Algae-heavy metal accumulation forms uniform thin specimen are as follows: when the chlorella algae cell and heavy metal in reaction cup 1
Pb2+And Cr3+After reaching adsorption equilibrium, moves up and down device 5 and control the decline of filter cup 4 and be pressed in sand core support base 6
On filter-paper-tape 18, it is then turned on peristaltic pump 2 and flow controller 3, the fluid sample for controlling certain volume is flowed into filter cup 4,
Peristaltic pump 2 and flow controller 3 are turned off later, is then turned on vacuum pump 8, start to be adsorbed with heavy metal Pb in filter cup 42+With
Cr3+Chlorella algae cell suspending liquid filter so that being adsorbed with heavy metal Pb2+And Cr3+Chlorella algae cell pressure act on
On lower uniform settlement to filter-paper-tape 18, heavy metal Pb is formed2+And Cr3+The equally distributed thin sample of circle；
Filter paper tape transfer procedure are as follows: after the completion of the fluid sample in filter cup 4 all filters, close vacuum pump 8, punching
Pb of the device 11 on filter-paper-tape 182+And Cr3+Round thin sample edge punches the aperture that diameter size is 1mm, later on move down
Dynamic device 5 controls filter cup 4 and is lifted up, and motor driver 17, photoelectric detector 1 are respectively started, in motor driver 17
Control under paper pushing motor 10 and roll paper motor 16 drive paper feeding tep reel 9 and roll paper tep reel 15 to rotate clockwise to transmit filter-paper-tape
18, under the judgement of photoelectric detector 1, by the Pb on filter-paper-tape 182+And Cr3+The thin sample of heavy metal is sent to heating zone
Domain, motor driver 17, photoelectric detector 1 stop working at this time；
The thin sample drying process of heavy metal are as follows: sample drying system 12 starts, to the Pb of side placed on it2+And Cr3+With much money
Belong to thin sample and carries out heating, drying processing；
XRF spectral measurement and analytic process are as follows: after heating, drying, sample drying system 12 stops working, cold to thin sample
But to after room temperature, motor driver 17, photoelectric detector 2 14 start, 10 He of paper pushing motor under the control of motor driver 17
Roll paper motor 16 drives paper feeding tep reel 9 and roll paper tep reel 15 to rotate clockwise to transmit filter-paper-tape 18, in photoelectric detector 2 14
Judgement under, by the Pb on filter-paper-tape 182+And Cr3+The thin sample of heavy metal is accurately sent to X-ray fluorescence spectra measured zone,
Motor driver 17, photoelectric detector 2 14 stop working at this time, and X-ray tube 19 and the starting of SDD detector 20 are started to work, X
Ray tube 19 generates sigmatron and excites heavy metal Pb2+And Cr3+Thin sample, the x-ray fluorescence that SDD detector 20 will detect
Signal carries out photoelectric conversion, and transmits signals to acquisition and control system 21 and carry out data acquisition and procession.
Claims (7)
1. a seeds algae enrichment-X-ray fluorescence spectra heavy metal in water automatic detection device, it is characterised in that: include heavy metal
Enrichment system, paper tape conveyer system, sample drying system, X-ray fluorescence spectra measuring system and acquisition and control system；
The heavy metal accumulation system includes reaction cup, peristaltic pump, flow controller, filter cup, moves up and down device, sand
Core support base, filtrate receiving bottle, vacuum pump and filter-paper-tape, the discharge outlet of the lower end of the reaction cup and the peristaltic pump
Connected by hose, the other end of peristaltic pump is connected by the import of hose and flow controller, the outlet of flow controller with
The import of filter cup upper end connects, and the filter cup wall of cup lower end is in infundibulate to contract, and bottom of a cup portion is round leak, mistake
Filter bowl, which is fixedly connected on, to be moved up and down on device, and the sand core support base is by top center embedded with same thickness circle sand
The cylindrical glass of core and lower end center are provided with the support base that the cylindrical glass of through-hole is constituted, sand core support base top cylindrical
Shape glass outer diameter is equal to the bottom outside diameter of filter cup, and inner circular sand core diameter is greater than the bottom leak diameter of filter cup,
The outer diameter of the cylindrical glass of sand core support base lower end is less than the outer diameter of sand core support base top cylindrical shape glass, and internal diameter is big
In the diameter of top circular sand core, the lower end of sand core support base is connect with the upper end of the filtrate receiving bottle, the sand
Core support base lower end cylindrical glass inner wall and filtrate receiving bottle upper end glass outer wall are ground glass wall, caliber size phase
Together, it is equipped with exhaust outlet in the middle upper end of filtrate receiving bottle, the exhaust outlet is controlled to a vacuum pump by rubber tube；
The paper tape conveyer system is by filter-paper-tape, paper feeding tep reel, paper pushing motor, roll paper tep reel, roll paper motor, motor driven
Device and paper feed position detecting system are constituted, and the width of the filter-paper-tape is identical as the internal diameter of paper feeding tep reel and roll paper tep reel, institute
The motor driver stated respectively drives paper pushing motor and the rotation of roll paper motor, and paper pushing motor drives paper feeding tep reel rotation release filter paper
Band, roll paper motor drive the rotation of roll paper tep reel to wind filter-paper-tape, and paper feeding tep reel is equal with the revolving speed of roll paper tep reel, the filter
Paper tape is placed between the filter cup and sand core support base, and the width of filter-paper-tape is greater than sand core support base top circular sand
The diameter of core, when move up and down device drive filter cup move down after, filter cup, filter-paper-tape, sand core support base, filtrate connect
It receives bottle and vacuum pump constitutes one and filters system；The paper feed position detecting system includes perforating device, photoelectric detector one
With photoelectric detector two, the perforating device includes stepper motor one and syringe needle, and perforating device is located at sand core support base
Side, the photoelectric detector one is located at heating region, and the photoelectric detector two is located at X-ray fluorescence spectra measurement zone
Domain；
The sample drying system is located at filter between heavy metal accumulation system and X-ray fluorescence spectra measuring system
The underface of paper tape, for carrying out heating, drying processing to the round thin sample of heavy metal on filter-paper-tape, sample drying system is
It is made of carbon fiber heating tube and power supply circuit；
The X-ray fluorescence spectra measuring system includes the X-ray tube and SDD detector above filter-paper-tape, X-ray
Pipe is excitation light source, for generating the sigmatron for exciting Characteristics of Heavy Metals x-ray fluorescence in thin sample, when heavy metal is high
After energy level transition occurs for energy excitation of X-rays, the characteristic x-ray fluorescence signal launched is received by SDD detector, is visited by SDD
Survey the conversion that device carries out photosignal；
The acquisition and control system respectively with the control terminal of peristaltic pump, the control terminal of flow controller, move up and down
The control terminal of device, the control terminal of vacuum pump, the control terminal of motor driver, the control terminal of stepper motor one, sample drying system
The control of the control terminal of system, the control terminal of photoelectric detector one, the control terminal, X-ray tube and SDD detector of photoelectric detector two
End electrical connection.
2. seeds algae enrichment according to claim 1-X-ray fluorescence spectra heavy metal in water automatic detection device, special
Sign is: the filter-paper-tape is strand fiberglass miillpore filter, and pore size is 0.22 μm.
3. seeds algae enrichment according to claim 1-X-ray fluorescence spectra heavy metal in water automatic detection device, special
Sign is: the device that moves up and down includes support frame, is equipped with vertical rail on the support frame, sliding on vertical rail
Dynamic to be equipped with filter cup clamper, the filter cup clamper is connect with stepper motor two, and stepper motor two drives filter cup
Clamper moves up and down on the vertical rail of support frame, and the stepper motor two is connect with acquisition and control system.
4. the heavy metal in water automatic detection device of seeds algae enrichment-X-ray fluorescence spectra according to claim 3,
Be characterized in that: the acquisition and control system includes power module, data acquisition module, single-chip microcontroller and its control electricity
Road, the data acquisition module and power module are connect with single-chip microcontroller, and data acquisition module is to SDD detector photosignal
Signal after conversion is acquired, stores, analyzing and handling, and single-chip microcontroller and its control circuit are respectively to peristaltic pump, flow control
Device moves up and down device, vacuum pump, perforating device, sample drying system, photoelectric detector one, Photoelectric Detection two, motor driven
Device, X-ray tube and SDD detector send control signal, and power module is used to power to whole device.
5. a seeds algae enrichment-X-ray fluorescence spectra heavy metal in water automatic testing method, it is characterised in that: adsorb weight including algae
Metal process, algae-heavy metal accumulation form uniform thin specimen, filter paper tape transfer procedure, the thin sample drying process of heavy metal
And XRF spectral measurement and analytic process；
Algae adsorbs heavy metal process are as follows: reaction cup is used for the reaction vessel of algae adsorbed water body heavy metal, when the algae in reaction cup is thin
After born of the same parents and heavy metal reach adsorption equilibrium, starts algae-heavy metal accumulation and form uniform thin specimen；
Algae-heavy metal accumulation forms uniform thin specimen are as follows: when the frustule in reaction cup reaches adsorption equilibrium with heavy metal
Afterwards, move up and down device control filter cup decline and is pressed on the filter-paper-tape in sand core support base, be then turned on peristaltic pump with
Flow controller, the fluid sample for controlling certain volume are flowed into filter cup, turn off peristaltic pump and flow controller later,
It is then turned on vacuum pump, starts to filter the frustule suspension for being adsorbed with heavy metal in filter cup, so that being adsorbed with heavy metal
Frustule on uniform settlement to filter-paper-tape, forms the equally distributed thin sample of circle of heavy metal under pressure；
Filter paper tape transfer procedure are as follows: after the completion of the fluid sample in filter cup all filters, close vacuum pump, perforating device exists
An aperture is made a call at the thin sample edge of circle on filter-paper-tape, moves up and down device control filter cup later and is lifted up, motor driven
Device, photoelectric detector one are respectively started, under the control of motor driver paper pushing motor and roll paper motor driven paper feeding tep reel and
Roll paper tep reel is rotated clockwise to transmit filter-paper-tape, under the judgement of photoelectric detector one, by the thin examination of heavy metal on filter-paper-tape
Sample is sent to heating region, and motor driver, photoelectric detector one stop working at this time；
The thin sample drying process of heavy metal are as follows: the starting of sample drying system adds the thin sample of the heavy metal of side placed on it
Hot drying and processing；
XRF spectral measurement and analytic process are as follows: after heating, drying, sample drying system stops working, and is cooled to room to thin sample
Wen Hou, motor driver, Photoelectric Detection two start, paper pushing motor and roll paper motor driven paper feeding under the control of motor driver
Tep reel and roll paper tep reel are rotated clockwise to transmit filter-paper-tape, under the judgement of Photoelectric Detection two, by the heavy metal on filter-paper-tape
Thin sample is accurately sent to X-ray fluorescence spectra measured zone, and motor driver, photoelectric detector two stop working at this time, and X is penetrated
Spool and the starting of SDD detector are started to work, and X-ray tube generates sigmatron and excites the thin sample of heavy metal, and SDD detector will
The x-ray fluorescence signal detected carries out photoelectric conversion, and transmits signals to acquisition and control system progress data and adopt
Collection and processing.
6. seeds algae enrichment according to claim 5-X-ray fluorescence spectra heavy metal in water automatic testing method, special
Sign is: the algae is the green alga in freshwater microalgae, specially chlorella or chlorella pyrenoidosa or tiltedly raw China fir algae.
7. seeds algae enrichment according to claim 5-X-ray fluorescence spectra heavy metal in water automatic testing method, special
Sign is: the heavy metal be lead, cadmium, chromium, nickel, copper, cobalt, silver in two or more.
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