CN106501424A - The residual detection method of agriculture based on automatization's preprocessing system - Google Patents
The residual detection method of agriculture based on automatization's preprocessing system Download PDFInfo
- Publication number
- CN106501424A CN106501424A CN201610988208.8A CN201610988208A CN106501424A CN 106501424 A CN106501424 A CN 106501424A CN 201610988208 A CN201610988208 A CN 201610988208A CN 106501424 A CN106501424 A CN 106501424A
- Authority
- CN
- China
- Prior art keywords
- liquid
- reactor
- valve
- drain pipe
- sample liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The present invention provides a kind of agriculture based on automatization's preprocessing system residual detection method, comprises the following steps:1) sample liquid is extracted;2) sample liquid is purified;3) chromogenic assay;4) extractive analysis;Sample is placed into formation sample liquid in sample liquid extraction element first, and the sample liquid for then being obtained is passed in sample liquid purifier, and to remove the pigment in sample liquid and particulate matter, then taking a part of sample liquid after purifying first carries out colour developing test in chromogenic reaction device;Control device carries out rough estimate according to chromogenic reaction result to the residual quantity of pesticide, draws the approximate range of agriculture residual, and calculates condition needed for extractive analysis and consumption;When sample liquid is passed into extractive analysis device, condition and consumption that extractive analysis device is drawn using control device carry out practical operation, and ultimate analysis obtains the concrete residual quantity of pesticide.The present invention carries out the residual detection of agriculture using automatization's preprocessing system, and detection efficiency is high.
Description
Technical field
The invention belongs to technical field of analytical chemistry, is related to a kind of residual detection method of agriculture, particularly a kind of based on automatization
The residual detection method of the agriculture of preprocessing system.
Background technology
Pesticide residual contamination affects being smoothed out for the quality of life of people and food trade always." people to eat are
My god ", as the mouth benefit of people's living standard is improved, the safety consciousness of food is also constantly being strengthened.The safety of food is food
The prerequisite fundamental of product.In daily life, many peasants lack due scientifical use pesticide knowldgde, abuse agriculture
Medicine.In order to strive for that water fruits and vegetables early go public, using early maturation technology, using chemicals, hormonal substance, fruit and vegerable are promoted to surmount
The link of its growth stage is accelerated the ripening.Some fruit and vegerable peasants violate the regulation in Safe period after applying pesticides, and listing of being eager is sold, and causes
Fruit and vegetable food Pesticide Residues are not only contaminated ecological environment, are more seriously compromised beyond national standard
Consumer healthy.Pesticide residues harm can not be despised, although will not go out to appear immediately after we have eaten vegetable and fruit
Body pathological changes, but, it is a kind of slow poison, accumulates gradually in vivo, reach a certain amount of after, will break out, its consequence cannot
Prediction.Therefore, pesticide residues are always government and social question of common concern.
Realize that the use of the automatization, onlineization and minimizing organic solvent of trying one's best of sample pre-treatments has become analytical chemistry
One of hot fields of research., there is cumbersome consumption in traditional Sample Pretreatment Technique such as liquid-liquid extraction, precipitation and filtration etc.
When, need using substantial amounts of to human body and environmental toxic or harmful organic solvent, be difficult to automatization the shortcomings of.
Secondly, in sample pre-treatments, as contained persticide residue in sample is unknown state, in actual treatment
When, generally using many experiments, change treatment conditions, analysis result could be obtained, being susceptible to wastage of material or consumption makes
With not enough situation, precision and detection efficiency are all low.
Content of the invention
The purpose of the present invention is there are the problems referred to above for existing technology, it is proposed that a kind of based on pre-treatment system of automatization
The residual detection method of the agriculture of system, it is possible to increase the precision of raw material dosage during detection, and improve detection efficiency.
The purpose of the present invention can be realized by following technical proposal:
The residual detection method of agriculture based on automatization's preprocessing system, comprises the following steps:
1) sample liquid is extracted:The solid fruit-vegetable sample of chopping is put in sample liquid extraction element, and is added to sample liquid extraction element
Enter a certain amount of organic solvent and buffer, the pesticide after stirring in fruit and vegerable sample is extracted in solution, form sample liquid;
2) sample liquid is purified:Sample liquid extraction element discharges sample liquid, and sample liquid is transported in sample liquid purifier, and net to sample liquid
The middle pigment and particulate matter for adding a certain amount of solid absorbent, removing in sample liquid is put in makeup;
3) chromogenic assay:A part of sample liquid after by purification is delivered in the reactor three of chromogenic reaction device, first to anti-
Addition acetylcholine solution is answered in device three, a certain amount of sample liquid-acetylcholine mixed liquor is taken in colour developing ware one;Then to reaction
Acetylcholinesterase is added in device three, after standing a period of time, a certain amount of sample liquid-acetylcholine-acetylcholinesterase group is taken
Into mixed liquor in colour developing ware two in, and to colour developing ware two in add nitrite ion;The solution that colour developing ware one is gathered with ccd cameras one
Color image, the solution colour image that gathers colour developing ware two with ccd cameras two, ccd cameras one and ccd cameras two will be collected
Solution colour image information feeds back to the image analysis module of control device, and image analysis module combines the default ratio of typing module
Colour atla color image, the solution colour image of the feedback of ccd cameras one and the feedback solution colour image of ccd cameras two are made and being compared,
The scope value of persticide residue is calculated, and according to needed for the scope exploitation of the persticide residue obtains extractive analysis
Condition and consumption;
4) extractive analysis:Take a certain amount of sample liquid to be passed in extractive analysis device, first add in extractive analysis device
Internal standard mixed solution, extractant and dispersant, form into emulsion after vibration, then add demulsifier in emulsion, stand
After be layered, take upper strata extraction phase for gas chromatographic analysiss, extractive analysis are using above-mentioned steps 3) calculated condition and use
Amount.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, solid absorbent be Graphon and
C18 bonded silica gel mixture, organic solvent is acetonitrile, and buffer is 0.1~0.5mol/L phosphate buffers, and extractant is selected from 1
One kind in one undecyl alcohol, 1 one lauryl alcohols, 2 one lauryl alcohols, hexadecane or hexamethylene, dispersant select methanol, acetonitrile or third
Ketone, demulsifier is from methanol or acetonitrile.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, sample liquid extraction element includes reactor
First, organic solvent tank, buffering flow container and distillation water pot, organic solvent tank contain organic solvent, and buffering flow container contains buffer, steams
Distilled water tank contains distilled water;There is reactor one feeding mouth, inlet and liquid outlet, solid sample to put into reactor by feeding mouth
One, organic solvent, buffer or distilled water put into reactor one by inlet, and the sample liquid that reactor one is formed is arranged by liquid outlet
Go out to sample liquid purifier, inside reactor one, be provided with the agitating roller of stirring.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, reactor one includes housing and lid,
Cover cap is located on housing, and housing includes that outer casing plate, internal layer shell plate and base plate, internal layer shell plate define installation cavity,
Reactor one also includes that open-topped reaction container, reaction container have reaction chamber installed in intracavity, reaction container is installed, reaction container
Perisporium is connected by several connection ribs being spaced with inner panel shell plates;The feeding mouth and inlet of reactor one is opened in lid
On, feeding mouth and inlet are in the overthe openings of reaction container, and agitating roller is connected with the transmission of motor one by shaft coupling, motor one
It is arranged in lid, agitating roller extend into reaction intracavity;Outer casing plate and internal layer shell plate are that gap is arranged, outer casing plate
The outside of internal layer shell plate is enclosed in, heating chamber between outer casing plate and internal layer shell plate, is formed, heating intracavity is inoculated with water, and
Heating intracavity is installed with electric heating piece, and electric heating piece is heated to the water for heating intracavity after being powered, and the heat produced after water heating expands
Installation intracavity is spilt into, the gas heating of intracavity will be installed, and finally reaction container be heated by gas.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, reactor one is additionally provided with and rocks reaction container
Oscillation component, oscillation component includes that oscillating plate, the first spring, second spring, motor two and moving block, oscillating plate are arranged on peace
The bottom behaveing affectedly, the size for being smaller in size than installation cavity of oscillating plate, motor two are fixed in the base plate of reactor one, motor two-way
Cross shaft coupling and prejudicially connect moving block;Oscillating plate is in the lower section of reaction container, and there is between reaction container interval, oscillating plate
Upper surface be connected with the bottom of reaction container by the first spring, base plate offers mounting groove, second spring in mounting groove,
And second spring is connected with the lower surface of oscillating plate;The lower surface of oscillating plate is concaved with receiving slit, and moving block is placed in reception
In groove, when motor two starts, moving block can be driven prejudicially to rotate and collide receiving slit, connection rib adopts elastomeric material.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, sample liquid purifier includes reactor
2nd, drug tube and fluid reservoir, reactor two have feed pathway, reaction chamber and liquid outlet channel, the liquid outlet of reactor one with anti-
The feed pathway of device two is answered to be connected, top of the feed pathway in reaction chamber, drug tube obliquely penetrate reaction chamber, drug tube
Outlet is located at the lower section of the outlet of feed pathway;Solid absorbent purifies sample liquid by drug tube input reaction intracavity, after purification
Sample liquid is expelled to fluid reservoir by liquid outlet channel.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, the feed pathway of reactor two is in bending
Shape, has been positioned apart from least two-layer filter membrane one in feed pathway, in liquid outlet channel, compartment of terrain is provided with least one of which filter membrane two, filter
Aperture of the aperture of film two less than filter membrane one.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, chromogenic reaction device includes reactor
Three, washing device, substrate solution tank, reaction enzymes tank and colour developing flow container, colour developing ware one and colour developing ware two, washing device are contained and are rinsed
Liquid, substrate solution tank contain acetylcholine solution, and reaction enzymes tank contains acetylcholinesterase, and colour developing flow container contains nitrite ion, instead
Answer device three that there is inlet and liquid outlet, the sample liquid in flushing liquor, acetylcholine solution, acetylcholinesterase and fluid reservoir point
Reactor three is not put into by inlet, the liquid outlet of reactor three is provided with three-way valve, the one outlet connecting passage of three-way valve
One, the mixed liquor being made up of sample liquid, acetylcholine is passed through colour developing ware by another outlet connecting passage two of three-way valve, runner one
One, the mixed liquor being made up of sample liquid, acetylcholine, acetylcholinesterase is passed through colour developing ware two by runner two;Nitrite ion is put into
To colour developing ware two;Chromogenic reaction device also includes gathering the ccd cameras one of solution colour and collection colour developing ware two in colour developing ware one
The ccd cameras two of interior solution colour, ccd cameras one are fixed on the top of colour developing ware one, ccd camera two-ways by camera support one
Cross the top that camera support two is fixed on colour developing ware two;Ccd cameras one and ccd cameras two are electrically connected in control device.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, extractive analysis device includes reactor
4th, gas chromatograph, inner mark solution tank, extractant tank, dispersant tank, demulsifier tank, liquid valve one, liquid valve two, liquid valve
3rd, liquid valve four, drain pipe one, drain pipe two, drain pipe three, drain pipe four;Inner mark solution tank contains inner mark solution, extractant
Tank contains extractant, and dispersant tank contains dispersant, and demulsifier tank contains demulsifier, and reactor four has inlet and goes out liquid
Mouthful, the import of the outlet connection liquid valve one of inner mark solution tank, the outlet connection drain pipe one of liquid valve one;Extractant tank goes out
The import of mouth connection liquid valve two, the outlet connection drain pipe two of liquid valve two;The outlet connection liquid valve three of dispersant tank
Import, the outlet connection drain pipe three of liquid valve three, the import of the outlet connection liquid valve four of demulsifier tank, liquid valve four go out
Mouth connection drain pipe four;Fluid reservoir is connected with liquid valve five, the outlet connection drain pipe five of liquid valve five, drain pipe one, goes out liquid
Pipe two, drain pipe three, drain pipe four are connected with the inlet of reactor four with drain pipe five;The extraction phase that reactor four is generated
Discharged by its liquid outlet and be injected into gas chromatographicanalyzer.
In the residual detection method of the above-mentioned agriculture based on automatization's preprocessing system, control device have central processing unit,
The image that image analysis module, valve pump control module, display module and typing module, ccd cameras one and ccd cameras two will be gathered
Image analysis module is transferred to, liquid valve one, liquid valve two, liquid valve three, liquid valve four, liquid valve five are controlled by valve pump control
Molding block, drain pipe one, drain pipe two, drain pipe three, drain pipe four, drain pipe five are equipped with flow sensor, each
Flow sensor is communicatively coupled to valve pump control module respectively;Visual comparison's result is fed back to valve pump by image analysis module
Control module, typing module preset dose information, preset dose information and image point of the valve pump control module according to typing module
The feedback information control liquid valve one of analysis module, liquid valve two, liquid valve three, liquid valve four, the keying of liquid valve five, show mould
Block is used for the numerical information for showing liquid outlet quantity.
Compared with prior art, the present invention has the advantage that:
This method using extractive analysis device to fruit and vegerable in agriculture residual carry out quantitative analyses, while be provided with chromogenic reaction dress again
Put and control device, assosting effect is served to the operating condition and consumption of extractive analysis device, before extracting the pesticide in sample liquid,
First taking a part of sample liquid carries out chromogenic reaction, residual so as to estimate out the agriculture substantially content, according to this substantially content, draws
The operating condition and raw material dosage of reason, is precisely controlled consumption by control device, not only contributes to the accuracy rate for improving detection, reduces
Experiment number, and the detection of automatization is achieved, detection efficiency is improve, can be suitably used for large-scale sample detection.
Description of the drawings
Fig. 1 is the schematic flow sheet of the detection method of the present invention.
Fig. 2 is the principle schematic diagram. of automatization's preprocessing system of the present invention.
Fig. 3 is the structural representation of the sample liquid extraction element of automatization's preprocessing system of the present invention.
Fig. 4 is the structural representation of the reactor one of the sample liquid extraction element of automatization's preprocessing system of the present invention.
Fig. 5 is the structural representation of the sample liquid purifier of automatization's preprocessing system of the present invention.
Fig. 6 is the structural representation of the chromogenic reaction device of automatization's preprocessing system of the present invention.
Fig. 7 is the structural representation of the extractive analysis device of automatization's preprocessing system of the present invention.
Fig. 8 is the structured flowchart of the control device of automatization's preprocessing system of the present invention.
In figure, 1, reactor one;2nd, organic solvent tank;3rd, flow container is buffered;4th, water pot is distilled;5th, reactor two;6th, offer medicine
Pipe;7th, fluid reservoir;8th, feed pathway;9th, reaction chamber;10th, liquid outlet channel;11st, reactor three;12nd, washing device;13rd, substrate is molten
Flow container;14th, reaction enzymes tank;15th, develop the color flow container;16th, develop the color ware one;17th, develop the color ware two;18th, runner one;19th, runner two;20、
Ccd cameras one;21st, ccd cameras two;22nd, camera support one;23rd, camera support two;24th, control device;25th, reactor four;
26th, gas chromatograph;27th, inner mark solution tank;28th, extractant tank;29th, dispersant tank;30th, demulsifier tank;31st, liquid valve one;
32nd, liquid valve two;33rd, liquid valve three;34th, liquid valve four;35th, liquid valve five;36th, liquid valve six;37th, liquid valve seven;38th, go out
Liquid valve eight;39th, liquid valve nine;40th, liquid valve ten;41st, liquid valve 11;42nd, liquid valve 12;43rd, drain pipe one;44th, go out
Liquid pipe two;45th, drain pipe three;46th, drain pipe four;47th, drain pipe five;48th, drain pipe six;49th, drain pipe seven;50th, drain pipe
Eight;51st, drain pipe nine;52nd, drain pipe ten;53rd, drain pipe 11;54th, drain pipe 12;55th, drain pipe 13;56th, go out liquid
Guan Shisi;57th, flow sensor;58th, waste liquid barrel;59th, filter membrane one;60th, filter membrane two;61st, lid;62nd, outer casing plate;
63rd, internal layer shell plate;64th, base plate;65th, installation cavity;66th, reaction container;67th, connect rib;68th, agitating roller;69th, motor one;70th, add
Hot chamber;71st, electric heating piece;72nd, oscillating plate;73rd, the first spring;74th, second spring;75th, motor two;76th, moving block;77th, block
Piece;78th, drainage plate
Specific embodiment
The following is the specific embodiment of the present invention and combine accompanying drawing, technical scheme is further described,
But the present invention is not limited to these embodiments.
As shown in Fig. 1 to 8, the invention provides a kind of residual detection method of agriculture based on automatization's preprocessing system, including
Following steps:
1) sample liquid is extracted:The solid fruit-vegetable sample of chopping is put in sample liquid extraction element, and is added to sample liquid extraction element
Enter a certain amount of organic solvent and buffer, the pesticide after stirring in fruit and vegerable sample is extracted in solution, form sample liquid;
2) sample liquid is purified:Sample liquid extraction element discharges sample liquid, and sample liquid is transported in sample liquid purifier, and net to sample liquid
The middle pigment and particulate matter for adding a certain amount of solid absorbent, removing in sample liquid is put in makeup;
3) chromogenic assay:A part of sample liquid after by purification is delivered in the reactor 3 11 of chromogenic reaction device, first to
In reactor 3 11 add acetylcholine solution, take a certain amount of sample liquid-acetylcholine mixed liquor in colour developing ware 1 in;Then
Acetylcholinesterase is added in reactor 3 11, after standing a period of time, a certain amount of sample liquid-acetylcholine-acetyl gallbladder is taken
The mixed liquor of alkali esterase composition is in colour developing ware 2 17, and in colour developing ware 2 17 adds nitrite ion;Gathered with ccd cameras 1
The solution colour image of colour developing ware 1, the solution colour image for gathering colour developing ware 2 17 with ccd cameras 2 21, ccd cameras one
The solution colour image information for collecting is fed back to 20 and ccd cameras 2 21 image analysis module of control device 24, image
Analysis module combines solution colour image and the ccd phases that the default colorimetric card color image of typing module, ccd cameras 1 feed back
The feedback solution colour image of machine 2 21 makes comparison, calculates the scope value of persticide residue, and according to the pesticide residues
The scope exploitation of amount obtains condition needed for extractive analysis and consumption;
4) extractive analysis:Take a certain amount of sample liquid to be passed in extractive analysis device, first add in extractive analysis device
Internal standard mixed solution, extractant and dispersant, form into emulsion after vibration, then add demulsifier in emulsion, stand
After be layered, take upper strata extraction phase for gas chromatographic analysiss, extractive analysis are using above-mentioned steps 3) calculated condition and use
Amount.
The capillary gas chromatographic column that gas chromatograph 26 is adopted is KB-Wax capillary columns, its specification be 30m ×
0.32mm × 0.25um, 300 DEG C of injector temperature, split sampling, sample size 0.50ul, carrier gas are in nitrogen, neon or argon
One kind, flow velocity is 30ml/min, 80 DEG C of initial temperature, keeps 1min, rises to 200 DEG C with 20 DEG C/min, keeps 2min, then with
40 DEG C/min rises to 240 DEG C, keeps 3min cleaning pillars.
The detection method is carried out outside aforesaid operations based on automatization's preprocessing system, also includes preparing mixed standard solution
Step:Dichlorvos, metrifonate, Rogor, omethoate, Bayer 71628, phonamiphoss, thimet, terbufos, disulfoton, methyl pair
Sulfur phosphorus, parathion, Diothyl, isofenphos, the third sea phosphorus, Ethodan, triazophos, Methomyl, dimethyl phenyl carbamate, Aldicarb, cloethocarb, benzene
Oxygen prestige, butocarboxim, dimehypo, nitrofen, Chlorphenamidine, Biphenthrin, flucythrinate, Fenpropathrin respectively take 0.1000g, use acetone
Solution dissolving is configured to the storing solution of 28 kinds of 10ug/ml;Dichlorvos, metrifonate, Rogor, omethoate, Bayer 71628, phonamiphoss,
Thimet, terbufos, disulfoton, parathion-methyl, parathion, Diothyl, isofenphos, the third sea phosphorus, Ethodan, triazophos 16
Plant storing solution and respectively take 1ml, be made into 0.1ug/ml mixed solutions one;Methomyl, dimethyl phenyl carbamate, Aldicarb, cloethocarb, fenoxycarb, fourth
6 kinds of storing solutions of ketone prestige respectively take 1ml, are made into 0.1ug/ml mixed solutions two;Dimehypo, nitrofen, Chlorphenamidine, Biphenthrin, fluorine
Cyano chrysanthemate, 6 kinds of storing solutions of Fenpropathrin respectively take 1ml, are made into 0.1ug/ml mixed solutions three;Mixed solution one, mixed solution two,
Mixed solution three respectively takes 1ml, is settled to the mixed standard solution with Concentraton gradient.
Gas chromatographic analysiss specifically include the formulation and quantitative analyses of standard working curve:Blank sample is taken, by mixing mark
Quasi- solution is added in blank sample, carries out extractive analysis using above-mentioned identical treatment conditions, by the peak of each pesticide for obtaining
Area carries out regression analyses with the ratio of internal standard substance peak area with the concentration of corresponding pesticide, calculates the standard work of each pesticide
Make curve and regression equation;The peak area of each pesticide obtained after sample liquid is detected brings phase into the ratio of internal standard substance peak area
The concentration of each pesticide in sample extracting solution in the regression equation that answers, is obtained, the residual quantity of each pesticide in sample is calculated.
Specifically, automatization's preprocessing system includes sample liquid extraction element, sample liquid purifier, chromogenic reaction device, extraction
Analytical equipment and control device 24 is taken, automatization's preprocessing system is used for detecting organophosphors or the amino first remained in fruit and vegerable
Esters of gallic acid pesticide concentration, solid fruit-vegetable sample is put in sample liquid extraction element, using sample liquid extraction element by fruit and vegerable sample
Pesticide extract in solution, formed sample liquid, then the sample liquid of acquisition is passed in sample liquid purifier, using sample liquid purify
Device removes pigment and particulate matter in sample liquid, to eliminate pigment to chromogenic reaction and the interference of chromatography.After taking purification
A part of sample liquid first carry out colour developing test in chromogenic reaction device, control device 24 is according to chromogenic reaction result to pesticide
Residual quantity carries out rough estimate, show that the approximate range of agriculture residual, control device 24 draw extraction according to agriculture residual range computation
Condition and consumption needed for analysis.When sample liquid is passed into extractive analysis device, extractive analysis device is obtained using control device 24
The condition for going out and consumption carry out practical operation, finally obtain the concrete residual quantity of pesticide.
Specifically, sample liquid extraction element includes reactor 1, organic solvent tank 2, buffering flow container 3 and distillation water pot 4, has
Machine solvent tank 2 contains organic solvent, and buffering flow container 3 contains buffer, and distillation water pot 4 contains distilled water.Reactor 1 have into
Material mouth, inlet and liquid outlet, solid sample by feeding mouth put into reactor 1, organic solvent, buffer or distilled water by
Inlet puts into reactor 1, and the sample liquid that reactor 1 is formed is expelled to sample liquid purifier by liquid outlet.Organic solvent tank
2nd, buffering flow container 3 and distillation water pot 4 are respectively at the top of reactor 1, organic solvent tank 2, buffering flow container 3 and distillation water pot
After 4 liquid outlet is opened, organic solvent, buffer and distilled water can drop downward into the inlet of reactor 1.
Reactor 1 includes housing and lid 61, and the lid of lid 61 is located on housing, and housing includes outer casing plate 62, interior
Layer shell plates 63 and base plate 64, internal layer shell plate 63 define installation cavity 65, and reactor 1 also includes open-topped reaction container
66, in installation cavity 65, there is reaction container 66 reaction container 66 reaction chamber, the perisporium of reaction container 66 to be passed through with inner panel shell plates
The connection rib 67 at several intervals is connected.
The feeding mouth and inlet of reactor 1 is opened on lid 61, and feeding mouth and inlet are in reaction container 66
Overthe openings, feeding mouth pass through for solid sample, and solid sample is entered and fallen into by feeding mouth reaction intracavity, and inlet is for organic
Solvent, buffer and distilled water these liquid pass through, and organic solvent, buffer and distilled water are entered simultaneously by the inlet of lid 61
Fall into reaction intracavity;Sample, organic solvent, buffer are added as required in reaction intracavity mixing, distilled water, the agriculture in sample
Medicine is extracted in solution to form sample liquid, is the extraction for accelerating pesticide, and reactor 1 is additionally provided with agitating roller 68, agitating roller
68 are connected with the transmission of motor 1 by shaft coupling, and motor 1 is arranged in lid 61, and agitating roller 68 extend into reaction intracavity,
Under the driving of motor 1, agitating roller 68 is rotated with the mixture of stirring reaction intracavity, is had up and down wherein on agitating roller 68
The stirring vane being intervally arranged, stirring scope are wide.
Further, be accelerate sample liquid formation, to react intracavity mixture also adopt mode of heating, specifically, outward
Layer shell plates 62 and internal layer shell plate 63 are that gap is arranged, and outer casing plate 62 is enclosed in the outside of internal layer shell plate 63, outer layer
Heating chamber 70 is formed between shell plates 62 and internal layer shell plate 63, is inoculated with being installed with electricity in water, and heating chamber 70 in heating chamber 70
Backing 71, electric heating piece 71 are heated to the water in heating chamber 70 after being powered, and the heat diffusion produced after water heating enters installation cavity
In 65, the gas in installation cavity 65 is heated, finally reaction container 66 is heated by gas.It is noted that reaction container
66 mutually do not recline with internal layer shell plate 63, and heating chamber 70 is that indirectly reaction container 66 is heated, and makes the heating of reaction container 66
Temperature is gentleer, prevents excessive temperature heating from damaging material, and to reaction container after the gas in installation cavity 65 is heated
66 heating is uniform, it is therefore prevented that the situation of local heating.
Preferably, reactor 1 is additionally provided with the oscillation component for rocking reaction container 66, oscillation component include oscillating plate 72,
One spring 73, second spring 74, motor 2 75 and moving block 76, specifically, oscillating plate 72 is arranged on the bottom of installation cavity 65, shakes
The size for being smaller in size than installation cavity 65 of dynamic plate 72, oscillating plate 72 can be fixed in transverse shakiness in installation cavity 65, motor 2 75
In the base plate 64 of reactor one, motor 2 75 prejudicially connects moving block 76 by shaft coupling;Oscillating plate 72 is in reaction container
66 lower section, and there is between reaction container 66 interval, the upper surface of oscillating plate 72 is by the first spring 73 and reaction container 66
Bottom is connected, and base plate 64 offers mounting groove, and second spring 74 is located in mounting groove, and under second spring 74 and oscillating plate 72
End face is connected.The lower surface of oscillating plate 72 is concaved with receiving slit, and moving block 76 is placed in receiving slit, and motor 2 75 starts
When, drive moving block 76 prejudicially to rotate, moving block 76 can collide the inwall of receiving slit, in the presence of second spring 74,
When oscillating plate 72 is subject to the horizontal impact force of moving block 76, transverse shifting back and forth, the transverse shifting power of oscillating plate 72 can be produced
Reaction container 66 is passed to by the first spring 73, wherein, connection rib 67 uses elastomeric material, and therefore reaction container 66 is subject to back and forth
Cross force after can be with transverse shakiness, so as to the mixture to reacting intracavity produces oscillation action.The oscillation component can also be applied
On reactor two and reactor four.
The liquid outlet of reactor 1 is opened in position of the reaction container 66 near bottom, after sample liquid is formed, outside from liquid outlet
Discharge, liquid outlet is provided with filter screen, for stopping solid sample.
The fruit and vegerable for needing detection are cut into particle of the particle diameter less than 2mm, are put in reactor 1, then from feeding mouth
Organic solvent and buffer are inwardly added from inlet, distilled water, organic solvent can be added as needed to be preferably acetonitrile, be used for
The pesticide in fruit and vegerable is extracted, buffer is preferably 0.1~0.5mol/L phosphate buffers, for adjusting the pH value of solution, reaction
The quick stirring of one 1 pairs of mixture of device, after fruit and vegerable sample soaks a period of time in mixed solution, the pesticide in fruit and vegerable sample is carried
Get in solution, form sample liquid.
Sample liquid purifier includes reactor 25, drug tube 6 and fluid reservoir 7, and reactor 25 has feed pathway 8, anti-
Chamber 9 and liquid outlet channel 10, the liquid outlet of reactor 1 is answered to be connected with the feed pathway 8 of reactor 25, feed pathway 8 is in anti-
The top in chamber 9, drug tube 6 is answered obliquely to penetrate reaction chamber 9, the outlet of drug tube 6 is located at the lower section of the outlet of feed pathway 8;
Solid absorbent is put into by drug tube 6 and purify in reaction chamber 9 sample liquid, and the sample liquid after purification is expelled to fluid reservoir by liquid outlet channel 10
7.
After the sample liquid that sample liquid extraction element is generated is discharged from the liquid outlet of reactor 1, the feed liquor for entering reactor 25 leads to
Road 8, the liquid outlet of reactor 1 can arrange delivery pump (not shown), and sample liquid is delivered into reactor 25 by delivery pump.
Meanwhile, solid absorbent is put into from drug tube 6, sample liquid from the outlet of feed pathway 8 flow into reaction chamber 9 when, be just struck against solid
Body adsorbent, sample liquid are fully contacted with solid absorbent, and sample liquid is when being input into by delivery pump, and flow velocity is big, and impulsive force is big, can be with
Solid absorbent is made fully to spread in sample liquid.Solid absorbent is preferably Graphon and C18 bonded silica gel mixture, energy
Pigment enough in absorption sample liquid.Reactor 25 is provided with oscillation component to promote being fully contacted for adsorbent and sample liquid.
The feed pathway 8 of reactor 25 is in bending, to increase the time that sample liquid passes through, while making the granule in sample liquid
Thing is attached on the inwall of feed pathway 8.At least two-layer filter membrane 1 has been positioned apart from feed pathway 8, and filter membrane 1 is used
Reaction chamber 9 is entered in the residual sample particulate matter in sample liquid is intercepted, compartment of terrain is provided with least one of which filter membrane two in liquid outlet channel 10
60, filter membrane 2 60 is used for intercepting solid absorbent, and further removes the fine particle in sample liquid, the aperture of filter membrane 2 60
Less than the aperture of filter membrane 1, the aperture of filter membrane 2 60 is 0.2um.
Chromogenic reaction device includes reactor 3 11, washing device 12, substrate solution tank 13, reaction enzymes tank 14 and nitrite ion
Tank 15, colour developing ware 1 and colour developing ware 2 17, washing device 12 contain flushing liquor, and it is molten that substrate solution tank 13 contains acetylcholine
Liquid, reaction enzymes tank 14 contain acetylcholinesterase, and colour developing flow container 15 contains nitrite ion.Reactor 3 11 has inlet and goes out liquid
Mouthful, the sample liquid in flushing liquor, acetylcholine solution, acetylcholinesterase and fluid reservoir 7 is respectively by inlet input reaction
Device 3 11.Washing device 12, substrate solution tank 13, reaction enzymes tank 14 are respectively at the top of reactor 3 11, washing device 12,
After substrate solution tank 13, the liquid outlet of reaction enzymes tank 14 are opened, washing device, substrate solution tank and reaction enzymes tank can be to whereabouts
Enter the inlet of reactor 3 11.The liquid outlet of reactor 3 11 is provided with three-way valve, the one outlet connecting passage one of three-way valve
18, another outlet connecting passage 2 19 of three-way valve, the mixed liquor being made up of sample liquid, acetylcholine is passed through aobvious by runner 1
The mixed liquor being made up of sample liquid, acetylcholine, acetylcholinesterase is passed through colour developing ware 2 17 by color ware 1, runner 2 19;Instead
Answer, by delivery pump to mixed liquor conveying
Power is provided.Top of the colour developing flow container 15 in colour developing ware 2 17, after colour developing flow container 15 is opened, nitrite ion is put into colour developing downwards
Ware 2 17.
Chromogenic reaction device also includes gathering the ccd cameras 1 of solution colour and collection colour developing ware two in colour developing ware 1
The ccd cameras 2 21 of solution colour in 17, ccd cameras 1 are fixed on the top of colour developing ware 1 by camera support 1,
Ccd cameras 2 21 are fixed on the top of colour developing ware 2 17 by camera support 2 23;2 21 points of ccd cameras 1 and ccd cameras
Control device 24 is not electrically connected to.
The inlet of reactor 3 11 is opened, and a certain amount of sample liquid is taken from fluid reservoir 7 and is passed through reactor 3 11, fluid reservoir 7
Liquid outlet delivery pump can be set.Acetylcholine solution is simultaneously introduced, after sample liquid is sufficiently mixed with acetylcholine solution, is opened anti-
The three-way valve of the liquid outlet of device 3 11 is answered, liquid outlet is connected with runner 1, if reactor 3 11 is provided with delivery pump, is also opened
Delivery pump, take a certain amount of sample liquid-acetylcholine mixed liquor in colour developing ware 1 in.It is then shut off the liquid outlet of reactor 3 11
Delivery pump, three-way valve, open reactor 3 11 inlet, into reactor 3 11 add acetylcholinesterase, stand one
Delivery pump, the three-way valve of the liquid outlet of reactor 3 11 after the section time, is opened, liquid outlet is connected with runner 2 19, taken certain
The mixed liquor of the sample liquid-acetylcholine of amount-acetylcholinesterase composition is in colour developing ware 2 17, and adds in colour developing ware 2 17
Nitrite ion.
Solution in colour developing ware 1 as a control group, i.e., gathers the color of matched group, for excluding with ccd cameras 1
The color interference of solution itself, the solution developed the color in ware 2 17 is used as experimental group, if containing organophosphors or amino first in sample liquid
Esters of gallic acid pesticide, will acetylcholine esterase inhibition activity, add nitrite ion after qualitative judgement can be made by color, wherein
The content difference of organophosphors or carbamate chemicals for agriculture can cause shown color different, therefore can make rough
Rational judgment.The image information of the reaction solution color for collecting is fed back to control dress by ccd cameras 1 and ccd cameras 2 21
24 are put, and the comparison for color being carried out by control device 24 is compared with the mode of artificial contrast, high precision, and improves detection efficiency.
Extractive analysis device includes reactor 4 25, gas chromatograph 26, inner mark solution tank 27, extractant tank 28, dispersion
Agent tank 29, demulsifier tank 30, liquid valve 1, liquid valve 2 32, liquid valve 3 33, liquid valve 4 34, drain pipe 1, go out liquid
Pipe 2 44, drain pipe 3 45, drain pipe 4 46.Inner mark solution tank 27 contains inner mark solution, and extractant tank 28 contains extractant, extraction
Take the one kind of agent in 1 one undecyl alcohols, 1 one lauryl alcohols, 2 one lauryl alcohols, hexadecane or the hexamethylene, selected extractant
Density ratio water is little.Dispersant tank 29 contains dispersant, and dispersant selects methanol, acetonitrile or acetone.Demulsifier tank 30 contains breakdown of emulsion
Agent, demulsifier is from methanol or acetonitrile.
Reactor 4 25 has inlet and liquid outlet, inner mark solution tank 27, extractant tank 28, dispersant tank 29 and breakdown of emulsion
Top of the agent tank 30 in reactor 4 25, inner mark solution tank 27, extractant tank 28, dispersant tank 29 and demulsifier tank 30 go out
After mouth is opened, inner mark solution, extractant, dispersant and demulsifier are able to the inlet for dropping downward into reactor 4 25.Tool
Body ground, the import of the outlet connection liquid valve 1 of inner mark solution tank 27, the outlet connection drain pipe 1 of liquid valve 1;Extraction
Take the import of the outlet connection liquid valve 2 32 of agent tank 28, the outlet connection drain pipe 2 44 of liquid valve 2 32;Dispersant tank 29
Outlet connection liquid valve 3 33 import, the outlet connection drain pipe 3 45 of liquid valve 3 33, the outlet of demulsifier tank 30 connect
Connect the import of liquid valve 4 34, the outlet connection drain pipe 4 46 of liquid valve 4 34;Fluid reservoir 7 is connected with liquid valve 5 35, goes out
The outlet connection drain pipe 5 47 of liquid valve 5 35, drain pipe 1, drain pipe 2 44, drain pipe 3 45, drain pipe 4 46 and goes out
Liquid pipe 5 47 is connected with the inlet of reactor 4 25;The extraction phase that reactor 4 25 is generated is discharged and noted by its liquid outlet
Enter to gas chromatographicanalyzer.
The extractive analysis device uses dispersive liquid-liquid microextraction-gas chromatogram combination technology to determine the residual content of agriculture
Amount analysis, the bottom of reactor 4 25 is provided with oscillation component extractant and dispersant and sample liquid is all added in reactor 4 25
Afterwards, open oscillation component and rock reactor 4 25, in reactor 4 25, form emulsion, backward emulsion in addition breakdown of emulsion
Agent, is layered after standing, and upper solution is extraction phase, and extraction phase is from after the liquid outlet discharge of reactor 4 25 for gas chromatogram point
Analysis, the liquid outlet of wherein reactor 4 25 are opened in the top of reactor 4 25.
Control device 24 has central processing unit, image analysis module, valve pump control module, display module and typing mould
Block, central processing unit use existing programmable processor, will herein be described in detail.2 21 electricity of ccd cameras 1 and ccd cameras
Control device 24 is connected to, the image of collection is transferred to image by image converter by ccd cameras 1 and ccd cameras 2 21
Analysis module, image analysis module combine the colour developing ware that the default colorimetric card color image of typing module, ccd cameras 1 feed back
The solution colour image of the colour developing ware 2 17 that one 16 solution colour image is fed back with ccd cameras 2 21 is made and being compared, and draws
The analysis result of persticide residue rough range.Liquid valve 1, liquid valve 2 32, liquid valve 3 33, liquid valve 4 34, go out liquid
Valve 5 35 is controlled by valve pump control module, and visual comparison's result is fed back to valve pump control module, typing by image analysis module
Module preset dose information and related extractive analysis conditional parameter, preset dose information of the valve pump control module according to typing module
With the feedback information of image analysis module control liquid valve 1, liquid valve 2 32, liquid valve 3 33, liquid valve 4 34, go out liquid
The keying of valve 5 35, controls liquid outlet quantity with this, and display module is display, and display module is used for the numerical value letter for showing liquid outlet quantity
Breath.
It is noted that being extracted before the pesticide in sample liquid using extractant, can be estimated in advance by chromogenic reaction device
Go out the residual substantially content of agriculture, according to this substantially content, the valve pump control module of control device 24 correspondingly opens liquid valve one
31st, liquid valve 2 32, liquid valve 3 33, liquid valve 4 34, liquid valve 5 35, relatively precisely and automatically control sample liquid, internal standard,
The liquid outlet quantity of extractant, dispersant and demulsifier, is conducive to the automaticity for improving the accuracy rate of detection and detection, and reduces
Experiment number.Common detection mode adopt manual type, and due to the agriculture residual to being detected be in unknown state, therefore
The accuracy of the consumptions such as the extractant that added, dispersant is low, and consumption is wasted or the not enough feelings for being not up to optimum condition of consumption
Condition can all occur, and need repeated detection just to can guarantee that the accuracy of detection, so as to cause detection efficiency low.
Specifically, drain pipe 1, drain pipe 2 44, drain pipe 3 45, drain pipe 4 46, drain pipe 5 47 are equipped with stream
Gauge quantity sensor 57, each flow sensor 57 are communicatively coupled to valve pump control module, flow sensor respectively
57 are used for sensing liquid outlet quantity, and give valve pump control module by liquid outlet quantity feedback of the information, and when reaching default liquid outlet quantity, valve pump is controlled
Module can correspondingly close liquid valve 1, liquid valve 2 32, liquid valve 3 33, liquid valve 4 34, liquid valve 5 35.
Preferably, liquid valve 5 35 is three-way valve, the primary outlet connection drain pipe 5 47 of liquid valve 5 35, liquid valve
5 35 second outlet connection drain pipe 6 48, drain pipe 6 48 are provided with the flow measurement being connected with the communication of valve pump control module
Sensor 57.Delivery pump can be set between the liquid outlet of fluid reservoir 7 and liquid valve 5 35, and delivery pump is communicatively coupled to the control of valve pump
Module, when sampling liquid is added to reactor 3 11, valve pump control module opens its delivery pump and liquid valve 5 35, fluid reservoir 7
Liquid outlet is connected with drain pipe 6 48, and sample liquid is added in reactor 3 11 by drain pipe 6 48, flow sensor
Sample liquid liquid outlet quantity feedback of the information is given valve pump control module by 57, and when reaching default liquid outlet quantity, valve pump control module closes conveying
Pump and liquid valve 5 35.
Preferably, chromogenic reaction device also include liquid valve 6 36, liquid valve 7 37, liquid valve 8 38, liquid valve 9 39,
Drain pipe 7 49, drain pipe 8 50, drain pipe 9 51 and drain pipe 10, the outlet connection liquid valve 6 36 of washing device 12
Import, the outlet connection drain pipe 7 49 of liquid valve 6 36, the import of the outlet connection liquid valve 7 37 of substrate solution tank 13 go out
The outlet connection drain pipe 8 50 of liquid valve 7 37, the import of the outlet connection liquid valve 8 38 of reaction enzymes tank 14, liquid valve 8 38
Outlet connection drain pipe 9 51, the import of the outlet connection liquid valve 9 39 of the flow container 15 that develops the color, the outlet of liquid valve 9 39 connect
Liquid pipe 10 is picked out, drain pipe 7 49, drain pipe 8 50 are connected with the inlet of reactor 3 11 with drain pipe 9 51, go out liquid
Pipe 10 is arranged on the top of colour developing ware 2 17, and nitrite ion is dropped in colour developing ware 2 17 from drain pipe 10;Liquid valve 6 36,
Delivery pump at liquid valve 7 37, liquid valve 8 38,3 11 liquid outlet of liquid valve 9 39 and reactor is controlled by valve pump control
Molding block.Drain pipe 7 49, drain pipe 8 50, drain pipe 9 51 and drain pipe 10 are equipped with flow sensor 57, per
Individual flow sensor 57 is communicatively coupled to valve pump control module respectively.
During chromogenic reaction, the valve pump control module of control device 24 is correspondingly successively opened out according to default time interval
Liquid valve 5 35, liquid valve 7 37, liquid valve 8 38, liquid valve 9 39 and delivery pump, are accurately controlled sample liquid, substrate molten relatively
The liquid outlet quantity of liquid, reaction enzymes and nitrite ion, corresponding flow sensor 57 is by corresponding liquid outlet quantity feedback of the information to valve
Pump control module, valve pump control module accordingly close liquid valve 5 35, liquid valve 7 37, liquid valve 8 38, liquid valve 9 39
And delivery pump.
Additionally, the three-way valve at the liquid outlet of reactor 3 11 is also controlled by valve pump control module, runner 1 and runner
The flow sensor 57 being connected with the communication of valve pump control module also is provided with 2 19, is passed through colour developing ware 1 and colour developing ware two
Amount of solution in 17 is controlled by valve pump control module.
The chromogenic reaction device also carries cleaning function, and develop the color ware 1 and the leakage fluid dram of colour developing ware 2 17 connect useless respectively
Liquid bucket 58, after the test of sample liquid chromogenic reaction, opens the leakage fluid dram of colour developing ware 1 and colour developing ware 2 17, and opens reactor
The delivery pump of 3 11 liquid outlet, three-way valve, make the liquid outlet of reactor 3 11 be connected with runner 2 19, in reactor 3 11
Mixed liquor through runner 2 19 flow to colour developing ware 2 17, and from colour developing ware 2 17 be expelled to waste liquid barrel 58.After liquid to be mixed is discharged,
Liquid valve 6 36 is opened, flushing liquor is passed through reactor 3 11, rinsed inside reactor 3 11, flushing liquor successively flows through runner one
18 and runner 2 19, when the liquid outlet of reactor 3 11 is communicated with runner 2 19, flushing liquor flow to colour developing ware two from runner 2 19
17 and waste liquid barrel 58 is drained into, to clean reactor 3 11, runner 2 19 and colour developing ware 2 17.The liquid outlet and stream of reactor 3 11
When road 1 is communicated, flushing liquor flow to colour developing ware 1 from runner 1 and drains into waste liquid barrel 58, to clean reactor 3 11, stream
Road 1 and colour developing ware 1.
Selectively, sample liquid extraction element also includes liquid valve 10, liquid valve 11, liquid valve 12, goes out liquid
Guan Shiyi 53, drain pipe 12 and drain pipe 13, the import of the outlet connection liquid valve 10 of organic solvent tank 2, go out
The outlet connection drain pipe 11 of liquid valve 10, buffers the import of the outlet connection liquid valve 11 of flow container 3, liquid valve ten
One 41 outlet connection drain pipe 12, distills the import of the outlet connection liquid valve 12 of water pot 4, liquid valve 12
Outlet connection drain pipe 13;Drain pipe 11, drain pipe 12 and drain pipe 13 with reactor 1
Inlet is connected.May also set up delivery pump between the outlet of distillation water pot 4 and liquid valve 12, delivery pump, liquid valve 10,
Liquid valve 11, liquid valve 12 are controlled by valve pump control module.
Liquid valve 12 is three-way valve, the primary outlet connection drain pipe 13 of liquid valve 12, liquid valve
12 second outlet connection drain pipe 14, drain pipe 14 are connected with the inlet of reactor 4 25;Go out liquid
Guan Shiyi 53, drain pipe 12, drain pipe 13 and drain pipe 14 are equipped with flow sensor 57, each stream
Gauge quantity sensor 57 is communicatively coupled to valve pump control module respectively.
Selectively, the upper surface of lid 61 is additionally provided with shielding plate 77 and drainage plate 78, and shielding plate 77 is rotationally connected with lid
Body 61, shielding plate 77 can cover feeding mouth.Drainage plate 78 is used for and drain pipe 11, drain pipe 12 and drain pipe ten
3 55 are connected, and drainage plate 78 is connected with inlet, and drain pipe 11, drain pipe 12 and drain pipe 13 flow out
Liquid is first converged in drainage plate 78, then flows into inlet.
When extracting sample liquid, the valve pump control module of control device 24 correspondingly open liquid valve 10, liquid valve 11,
Liquid valve 12, delivery pump, the relative liquid outlet quantity for being accurately controlled organic solvent, buffer and distilled water, each flow measurement
Corresponding liquid outlet quantity feedback of the information is given valve pump control module by sensor 57, when reaching default liquid outlet quantity, valve pump control module
Liquid valve ten 40, liquid valve ten one 41, liquid valve ten two 42, delivery pump are correspondingly closed.Wherein, due to extractant used
Density ratio water is little, the solution in reactor 4 25 be divided into biphase after, for ease of taking out extraction phase, liquid valve 12 can be opened
42, make the outlet of distillation water pot 4 be connected with drain pipe 14, distilled water is passed through reactor four by drain pipe 14
In 25, extraction phase rises to the liquid outlet position of reactor 4 25, and discharges from the liquid outlet.
Selectively, it is the automaticity that improves the preprocessing system, the preprocessing system also includes pretreating device,
Pretreating device includes for sample shredding the Material disintegrator of granulating and collects the sample collection bucket of particle sample, and Material disintegrator has pan feeding
Mouth and discharging opening, are provided with the blade of rotation inside Material disintegrator, bulk sample puts into Material disintegrator by feeding mouth, and sample collection bucket is arranged
Filter screen is provided with the lower section of discharging opening, sample collection bucket, filter screen is removably attached to above drum head.
Selectively, pretreating device also includes that treatment trough, sparge pipe and liquid injection valve, sparge pipe are located at the upper for the treatment of trough
Side, sparge pipe connect liquid injection valve, and liquid injection valve is controlled by valve pump control module;Treatment trough is connected by ramp way with Material disintegrator,
Bulk sample after cleaning is slipped into the feeding mouth of Material disintegrator by ramp way.
The process of the first step is carried out in treatment trough to sample, and valve pump control module opens liquid injection valve, the water in sparge pipe
Spray in treatment trough, cleaning sample, remove the soil and dust impurity of sample surfaces, or remove peel, take sarcocarp, tentatively
After process, plunge the sample in ramp way, sample is fallen in Material disintegrator with the guiding of ramp way, the knife in Material disintegrator
Sample is shredded granulating by piece, and particle sample is fallen in sample collection bucket from discharging opening, and wherein produced liquid portion is through filter
Net, accumulates in the bottom of sample collection bucket.
It is noted that each liquid valve and delivery pump of the preprocessing system are the valve pumps in control device 24
Open and close under the control of control module, and display module has record to the liquid outlet quantity of each liquid valve, using before this
Processing system carries out the automaticity that the residual detection of agriculture improves the residual detection of agriculture, while also improving detection efficiency.
The present invention is applied to the detection of Organophosphorus and carbamate pesticides class pesticide.
Specific embodiment described herein is only to the spiritual explanation for example of the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement or replaced using similar mode to described specific embodiment
Generation, but without departing from the spiritual of the present invention or surmount scope defined in appended claims.
Although more having used reactor 1 herein;Organic solvent tank 2;Buffering flow container 3;Distillation water pot 4;Reactor
25;Drug tube 6;Fluid reservoir 7;Feed pathway 8;Reaction chamber 9;Liquid outlet channel 10;Reactor 3 11;Washing device 12;Substrate is molten
Flow container 13;Reaction enzymes tank 14;Colour developing flow container 15;Colour developing ware 1;Colour developing ware 2 17;Runner 1;Runner 2 19;Ccd cameras
One 20;Ccd cameras 2 21;Camera support 1;Camera support 2 23;Control device 24;Reactor 4 25;Gas chromatograph
26;Inner mark solution tank 27;Extractant tank 28;Dispersant tank 29;Demulsifier tank 30;Liquid valve 1;Liquid valve 2 32;Liquid valve
3 33;Liquid valve 4 34;Liquid valve 5 35;Liquid valve 6 36;Liquid valve 7 37;Liquid valve 8 38;Liquid valve 9 39;Liquid valve
10;Liquid valve 11;Liquid valve 12;Drain pipe 1;Drain pipe 2 44;Drain pipe 3 45;Drain pipe 4 46;
47th, drain pipe 5 47;Drain pipe 6 48;Drain pipe 7 49;Drain pipe 8 50;Drain pipe 9 51;Drain pipe 10;Drain pipe ten
One 53;Drain pipe 12;Drain pipe 13;Drain pipe 14;Flow sensor 57;Waste liquid barrel 58;Filter membrane one
59;Filter membrane 2 60;Lid 61;Outer casing plate 62;Internal layer shell plate 63;Base plate 64;Installation cavity 65;Reaction container 66;Connection rib
67;Agitating roller 68;Motor 1;Heating chamber 70;Electric heating piece 71;Oscillating plate 72;First spring 73;Second spring 74;Motor two
75;Moving block 76;Shielding plate 77;78 grade term of drainage plate, but it is not precluded from the probability using other terms.Using these arts
Language is used for the purpose of the essence for more easily describing and explaining the present invention;Being construed as any additional restriction is all
Contrary with spirit of the invention.
Claims (10)
1. the residual detection method of agriculture based on automatization's preprocessing system, it is characterised in that comprise the following steps:
1) sample liquid is extracted:The solid fruit-vegetable sample of chopping is put in sample liquid extraction element, and one is added to sample liquid extraction element
Quantitative organic solvent and buffer, the pesticide after stirring in fruit and vegerable sample are extracted in solution, form sample liquid;
2) sample liquid is purified:Sample liquid extraction element discharges sample liquid, and sample liquid is transported in sample liquid purifier, and purifies dress to sample liquid
Put the middle pigment and particulate matter for adding a certain amount of solid absorbent, removing in sample liquid;
3) chromogenic assay:A part of sample liquid after by purification is delivered in the reactor three of chromogenic reaction device, first to reactor
In three add acetylcholine solution, take a certain amount of sample liquid-acetylcholine mixed liquor in colour developing ware one in;Then to reactor three
Middle addition acetylcholinesterase, after standing a period of time, takes a certain amount of sample liquid-acetylcholine-acetylcholinesterase composition
Mixed liquor is in colour developing ware two, and in colour developing ware two adds nitrite ion;The solution colour that colour developing ware one is gathered with ccd cameras one
Image, the solution colour image for gathering colour developing ware two with ccd cameras two, ccd cameras one and ccd cameras two are by the solution for collecting
Color image information feeds back to the image analysis module of control device, and image analysis module combines the default colorimetric card of typing module
Color image, the solution colour image of the feedback of ccd cameras one and the feedback solution colour image of ccd cameras two are made and being compared, and calculate
Draw the scope value of persticide residue, and condition according to needed for the scope exploitation of the persticide residue obtains extractive analysis
And consumption;
4) extractive analysis:Take a certain amount of sample liquid to be passed in extractive analysis device, in extractive analysis device, first add internal standard
Mixed solution, extractant and dispersant, form into emulsion after vibration, then add demulsifier in emulsion, divide after standing
Layer, takes upper strata extraction phase for gas chromatographic analysiss, and extractive analysis adopt above-mentioned steps 3) calculated condition and consumption.
2. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 1, it is characterised in that solid is inhaled
Attached dose is Graphon and C18 bonded silica gel mixture, and organic solvent is acetonitrile, and buffer is 0.1~0.5mol/L phosphoric acid
Buffer, the one kind of extractant in 1 one undecyl alcohols, 1 one lauryl alcohols, 2 one lauryl alcohols, hexadecane or hexamethylene, dispersant
From methanol, acetonitrile or acetone, demulsifier is from methanol or acetonitrile.
3. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 1, it is characterised in that sample liquid is carried
Taking device includes that reactor one, organic solvent tank, buffering flow container and distillation water pot, organic solvent tank contain organic solvent, buffering
Flow container contains buffer, and distillation water pot contains distilled water;Reactor one has feeding mouth, inlet and liquid outlet, solid sample
Reactor one is put into by feeding mouth, organic solvent, buffer or distilled water put into reactor one, one shape of reactor by inlet
Into sample liquid sample liquid purifier is expelled to by liquid outlet, be provided with the agitating roller of stirring inside reactor one.
4. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 3, it is characterised in that reactor
One includes that housing and lid, cover cap are located on housing, and housing includes outer casing plate, internal layer shell plate and base plate, inner layer case
Body plate defines installation cavity, and reactor one also includes that open-topped reaction container, reaction container have installed in intracavity, reaction container is installed
There are reaction chamber, the perisporium of reaction container to be connected by several connection ribs being spaced with inner panel shell plates;The feeding mouth of reactor one
It is opened on lid with inlet, feeding mouth and inlet are in the overthe openings of reaction container, and agitating roller is by shaft coupling and electricity
The transmission of machine one is connected, and motor one is arranged in lid, and agitating roller extend into reaction intracavity;Outer casing plate and internal layer shell plate are
Gap is arranged, and outer casing plate is enclosed in the outside of internal layer shell plate, forms heating between outer casing plate and internal layer shell plate
Chamber, heating intracavity are inoculated with water, and heating intracavity is installed with electric heating piece, and electric heating piece is heated to the water for heating intracavity after being powered,
The heat diffusion produced after water heating enters to install intracavity, will install the gas heating of intracavity, and finally reaction container be carried out by gas
Heating.
5. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 4, it is characterised in that reactor
One is additionally provided with the oscillation component for rocking reaction container, and oscillation component includes oscillating plate, the first spring, second spring, motor two and turns
Motion block, oscillating plate are arranged on the bottom of installation cavity, and the size for being smaller in size than installation cavity of oscillating plate, motor two are fixed on reactor
In one base plate, motor two prejudicially connects moving block by shaft coupling;Oscillating plate is in the lower section of reaction container, and and reaction container
Between there is interval, the upper surface of oscillating plate is connected with the bottom of reaction container by the first spring, and base plate offers mounting groove, the
Two springs are in mounting groove, and second spring is connected with the lower surface of oscillating plate;The lower surface of oscillating plate is concaved with and connects
Groove is received, moving block is placed in receiving slit, when motor two starts, moving block can be driven prejudicially to rotate and collide receiving slit, even
Rib adopts elastomeric material.
6. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 1, it is characterised in that sample liquid is net
Makeup is put including reactor two, drug tube and fluid reservoir, and reactor two has feed pathway, reaction chamber and liquid outlet channel, reaction
The liquid outlet of device one is connected with the feed pathway of reactor two, and top of the feed pathway in reaction chamber, drug tube are obliquely worn
Enter reaction chamber, the outlet of drug tube is located at the lower section of the outlet of feed pathway;Solid absorbent is by drug tube input reaction intracavity
Sample liquid is purified, the sample liquid after purification is expelled to fluid reservoir by liquid outlet channel.
7. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 6, it is characterised in that reactor
Two feed pathway has been positioned apart from least two-layer filter membrane one in bending in feed pathway, in liquid outlet channel, compartment of terrain sets
There are at least one of which filter membrane two, the aperture of filter membrane two to be less than the aperture of filter membrane one.
8. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 1, it is characterised in that colour developing is anti-
Device is answered to include reactor three, washing device, substrate solution tank, reaction enzymes tank and the flow container that develops the color, colour developing ware one and colour developing ware two,
Washing device contains flushing liquor, and substrate solution tank contains acetylcholine solution, and reaction enzymes tank contains acetylcholinesterase, nitrite ion
Tank contains nitrite ion, and reactor three has inlet and a liquid outlet, flushing liquor, acetylcholine solution, acetylcholinesterase and
Sample liquid in fluid reservoir puts into reactor three by inlet respectively, and the liquid outlet of reactor three is provided with three-way valve, three-way valve
One outlet connecting passage one, another outlet connecting passage two of three-way valve, runner one will be made up of sample liquid, acetylcholine
Mixed liquor is passed through colour developing ware one, and the mixed liquor being made up of sample liquid, acetylcholine, acetylcholinesterase is passed through colour developing ware by runner two
Two;Nitrite ion is fed into colour developing ware two;Chromogenic reaction device also includes the ccd cameras one for gathering solution colour in colour developing ware one
With collection colour developing ware two in solution colour ccd cameras two, ccd cameras one by camera support one be fixed on colour developing ware one upper
Side, ccd cameras two are fixed on the top of colour developing ware two by camera support two;Ccd cameras one and ccd cameras two are electrically connected
In control device.
9. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 1, it is characterised in that extraction point
Analysis apparatus include reactor four, gas chromatograph, inner mark solution tank, extractant tank, dispersant tank, demulsifier tank, liquid valve one,
Liquid valve two, liquid valve three, liquid valve four, drain pipe one, drain pipe two, drain pipe three, drain pipe four;Inner mark solution tank is contained
Inner mark solution, extractant tank contain extractant, and dispersant tank contains dispersant, and demulsifier tank contains demulsifier, and reactor four has
There are inlet and liquid outlet, the import of the outlet connection liquid valve one of inner mark solution tank, the outlet connection drain pipe of liquid valve one
One;The import of the outlet connection liquid valve two of extractant tank, the outlet connection drain pipe two of liquid valve two;The outlet of dispersant tank
The import of connection liquid valve three, the outlet connection drain pipe three of liquid valve three, the outlet of demulsifier tank connect entering for liquid valve four
Mouthful, the outlet connection drain pipe four of liquid valve four;Fluid reservoir is connected with liquid valve five, the outlet connection drain pipe of liquid valve five
Five, drain pipe one, drain pipe two, drain pipe three, drain pipe four are connected with the inlet of reactor four with drain pipe five;Reaction
The extraction phase that device four is generated is discharged by its liquid outlet and is injected into gas chromatographicanalyzer.
10. the residual detection method of the agriculture based on automatization's preprocessing system according to claim 9, it is characterised in that control
Device has central processing unit, image analysis module, valve pump control module, display module and typing module, one He of ccd cameras
Ccd cameras two by the image transmitting for gathering to image analysis module, liquid valve one, liquid valve two, liquid valve three, liquid valve four,
Liquid valve five is controlled by valve pump control module, and drain pipe one, drain pipe two, drain pipe three, drain pipe four, drain pipe five are all provided with
There is flow sensor, each flow sensor is communicatively coupled to valve pump control module respectively;Image analysis module will
Visual comparison's result feeds back to valve pump control module, typing module preset dose information, and valve pump control module is according to typing module
Preset dose information and image analysis module feedback information control liquid valve one, liquid valve two, liquid valve three, liquid valve
4th, the keying of liquid valve five, display module are used for the numerical information for showing liquid outlet quantity.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610988208.8A CN106501424A (en) | 2016-11-10 | 2016-11-10 | The residual detection method of agriculture based on automatization's preprocessing system |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610988208.8A CN106501424A (en) | 2016-11-10 | 2016-11-10 | The residual detection method of agriculture based on automatization's preprocessing system |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106501424A true CN106501424A (en) | 2017-03-15 |
Family
ID=58323804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610988208.8A Pending CN106501424A (en) | 2016-11-10 | 2016-11-10 | The residual detection method of agriculture based on automatization's preprocessing system |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106501424A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107525803A (en) * | 2017-09-20 | 2017-12-29 | 昆明理工大学 | A kind of embedded food inspection device of view-based access control model identification |
CN107727822A (en) * | 2017-12-07 | 2018-02-23 | 河北华厚天成环保技术有限公司 | One kind is used for Water Test Kits reagent dosage supervising device |
CN107807123A (en) * | 2017-12-04 | 2018-03-16 | 重庆市合川区农产品质量安全监督检验检测站 | A kind of agricultural product heavy metal analysis mechanism |
CN107817241A (en) * | 2017-10-31 | 2018-03-20 | 安徽师范大学 | A kind of biology sensor, the application of preparation method and detection acetylcholinesterase, a kind of method for detecting organophosphorus pesticide |
CN109030382A (en) * | 2018-08-21 | 2018-12-18 | 温州职业技术学院 | Food nutrient composition detection device |
CN109270033A (en) * | 2018-09-10 | 2019-01-25 | 南京市产品质量监督检验院 | The rapid detection method of Hazard factor in a kind of food |
CN109724925A (en) * | 2017-10-30 | 2019-05-07 | 爱科来株式会社 | Analytical equipment |
CN110530861A (en) * | 2019-09-10 | 2019-12-03 | 佛山科学技术学院 | A kind of measuring method of soil acidity or alkalinity |
CN111220602A (en) * | 2018-11-27 | 2020-06-02 | 上海尚湾信息技术有限公司 | Quick detection device of carbamate pesticide residue |
CN112946105A (en) * | 2021-01-27 | 2021-06-11 | 延吉海关综合技术服务中心 | Pesticide residue rapid detection system and detection method |
CN115112647A (en) * | 2022-08-25 | 2022-09-27 | 济南市食品药品检验检测中心 | Detection system based on pesticide residue food |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102445552A (en) * | 2010-10-09 | 2012-05-09 | 武汉森济生物科技有限责任公司 | Automatic online multifunctional sample pretreatment equipment |
CN202921320U (en) * | 2012-12-05 | 2013-05-08 | 潍坊乐多收生物工程有限公司 | Reaction kettle for experiment |
CN104374723A (en) * | 2014-11-21 | 2015-02-25 | 长春长光思博光谱技术有限公司 | Pesticide residue detector |
CN105107452A (en) * | 2015-08-12 | 2015-12-02 | 安徽苏乐医药材料有限公司 | Vibrating reaction kettle |
CN105116064A (en) * | 2015-07-17 | 2015-12-02 | 中国农业科学院茶叶研究所 | Automatic sample pretreatment and detection method for detecting residual of multiple pesticides in tea leaves |
CN204891853U (en) * | 2015-06-17 | 2015-12-23 | 南通沃兰化工有限公司 | Spiral cover formula reation kettle |
CN205269676U (en) * | 2015-12-03 | 2016-06-01 | 重庆智寰传动科技发展有限公司 | Vibrating chemical industry reation kettle |
CN205413025U (en) * | 2016-03-19 | 2016-08-03 | 吴进春 | Reactor mixing device of ration pan feeding |
CN106053631A (en) * | 2016-05-19 | 2016-10-26 | 电子科技大学 | Automatic dispersed liquid-liquid micro-extraction system and applications thereof |
-
2016
- 2016-11-10 CN CN201610988208.8A patent/CN106501424A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102445552A (en) * | 2010-10-09 | 2012-05-09 | 武汉森济生物科技有限责任公司 | Automatic online multifunctional sample pretreatment equipment |
CN202921320U (en) * | 2012-12-05 | 2013-05-08 | 潍坊乐多收生物工程有限公司 | Reaction kettle for experiment |
CN104374723A (en) * | 2014-11-21 | 2015-02-25 | 长春长光思博光谱技术有限公司 | Pesticide residue detector |
CN204891853U (en) * | 2015-06-17 | 2015-12-23 | 南通沃兰化工有限公司 | Spiral cover formula reation kettle |
CN105116064A (en) * | 2015-07-17 | 2015-12-02 | 中国农业科学院茶叶研究所 | Automatic sample pretreatment and detection method for detecting residual of multiple pesticides in tea leaves |
CN105107452A (en) * | 2015-08-12 | 2015-12-02 | 安徽苏乐医药材料有限公司 | Vibrating reaction kettle |
CN205269676U (en) * | 2015-12-03 | 2016-06-01 | 重庆智寰传动科技发展有限公司 | Vibrating chemical industry reation kettle |
CN205413025U (en) * | 2016-03-19 | 2016-08-03 | 吴进春 | Reactor mixing device of ration pan feeding |
CN106053631A (en) * | 2016-05-19 | 2016-10-26 | 电子科技大学 | Automatic dispersed liquid-liquid micro-extraction system and applications thereof |
Non-Patent Citations (1)
Title |
---|
周敏等: "分散液相微萃取-气相色谱-串联质谱法快速测定蔬菜中8种亲脂类农药残留", 《色谱》 * |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107525803A (en) * | 2017-09-20 | 2017-12-29 | 昆明理工大学 | A kind of embedded food inspection device of view-based access control model identification |
CN109724925B (en) * | 2017-10-30 | 2023-07-14 | 爱科来株式会社 | Analysis device |
CN109724925A (en) * | 2017-10-30 | 2019-05-07 | 爱科来株式会社 | Analytical equipment |
CN107817241A (en) * | 2017-10-31 | 2018-03-20 | 安徽师范大学 | A kind of biology sensor, the application of preparation method and detection acetylcholinesterase, a kind of method for detecting organophosphorus pesticide |
CN107817241B (en) * | 2017-10-31 | 2020-09-11 | 安徽师范大学 | Biosensor, preparation method, application of biosensor in detection of acetylcholinesterase, and method for detecting organophosphorus pesticide |
CN107807123A (en) * | 2017-12-04 | 2018-03-16 | 重庆市合川区农产品质量安全监督检验检测站 | A kind of agricultural product heavy metal analysis mechanism |
CN107807123B (en) * | 2017-12-04 | 2024-01-19 | 重庆市合川区农产品质量安全监督检验检测站 | Agricultural product heavy metal detection mechanism |
CN107727822A (en) * | 2017-12-07 | 2018-02-23 | 河北华厚天成环保技术有限公司 | One kind is used for Water Test Kits reagent dosage supervising device |
CN107727822B (en) * | 2017-12-07 | 2024-04-16 | 河北华厚天成环保技术有限公司 | Reagent dosage monitoring device for water quality analyzer |
CN109030382A (en) * | 2018-08-21 | 2018-12-18 | 温州职业技术学院 | Food nutrient composition detection device |
CN109270033A (en) * | 2018-09-10 | 2019-01-25 | 南京市产品质量监督检验院 | The rapid detection method of Hazard factor in a kind of food |
CN111220602A (en) * | 2018-11-27 | 2020-06-02 | 上海尚湾信息技术有限公司 | Quick detection device of carbamate pesticide residue |
CN110530861A (en) * | 2019-09-10 | 2019-12-03 | 佛山科学技术学院 | A kind of measuring method of soil acidity or alkalinity |
CN112946105A (en) * | 2021-01-27 | 2021-06-11 | 延吉海关综合技术服务中心 | Pesticide residue rapid detection system and detection method |
CN115112647B (en) * | 2022-08-25 | 2022-12-09 | 济南市食品药品检验检测中心 | Detection system based on pesticide residue food |
CN115112647A (en) * | 2022-08-25 | 2022-09-27 | 济南市食品药品检验检测中心 | Detection system based on pesticide residue food |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106501424A (en) | The residual detection method of agriculture based on automatization's preprocessing system | |
CN106770699A (en) | A kind of fruit and vegetable residual pesticide detecting system | |
CN101665523B (en) | The production method of L-arabinose and D-xylose pref | |
CN206671204U (en) | A kind of detecting system for fruits and vegetables pesticide residues | |
RU2315721C1 (en) | Method of the anaerobic reprocessing of the organic wastes and the installation for the method realization | |
CN106501061B (en) | On-line automatic monitoring system and method for anionic surfactant in water | |
CN106383189A (en) | Dispersive liquid-liquid microextraction gas chromatograph mass spectrometry pesticide residue detection method | |
SE430171B (en) | CONTINUOUS PROCEDURE FOR THE PRODUCTION OF ETHANOL IN A FERMENTOR ADDED TO A SUBSTRATE WITH HIGH CARBOHYDRATE CONCENTRATION, WHICH DISPOSES FERMENTATION LIQUID AFTER COMPOUNDING A FRENCH PREPARED FLUID ... | |
CN206081739U (en) | Nicotine extraction tower | |
CN101665524B (en) | Method for producing L-arabinose | |
CN205463564U (en) | Device for treating kitchen waste | |
CN105457991A (en) | Kitchen waste centralized treatment device | |
CN106932259A (en) | A kind of device for extracting soil hydrophobic DOM | |
KR100780384B1 (en) | Organic Waste Treatment System | |
CN107354105A (en) | A kind of complex microbial inoculum and preparation method thereof and the system for administering sewage | |
CN102093099B (en) | Device for preparing organic liquid fertilizer by using restaurant kitchen garbage | |
CN202865044U (en) | Reaction device for wastewater treatment | |
CN201313848Y (en) | Overhead jet aeration biochemical tower | |
CN109601437A (en) | The method that Mucilage of loach stress is secreted and collected | |
CN205463563U (en) | Kitchen garbage's concentrated processing apparatus | |
Hovorukha et al. | Increase in efficiency of hydrogen production by optimization of food waste fermentation parameters | |
CN210394113U (en) | Combined device for producing carbon source by medium-temperature alkaline hydrolysis sludge | |
CN106552593A (en) | Mycelium pellet biological adsorption and renovation process | |
CN101227831A (en) | Method for enriching lignocellulose residues with yeast protein | |
CN206051690U (en) | Based on the water purifying device that microorganism is decomposed |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170315 |