CN101738486B - Fully-automatic analyzer and analysis method of urea in milk and milk products - Google Patents
Fully-automatic analyzer and analysis method of urea in milk and milk products Download PDFInfo
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Abstract
The invention discloses a fully-automatic analyzer and an analysis method of urea in milk and milk products. The fully-automatic analyzer comprises an automatic sampling device, a peristaltic pump, a detector, a computer processing system and an online processing assembly; wherein the detector is connected with the computer processing system through a signal wire; the online processing assembly comprises a sample injection valve, a knitting reactor, a tee joint, an online dialysis module, a sampling ring, a capillary connecting tube, a peristaltic pump pipe, a current-carrying container bottle, an acidic reagent solution container bottle, a color reagent container bottle, a backpressure regulator, a heating module, a condensing module and a waste liquid tank. The analysis method is used for analyzing the urea content in the milk and milk products by using the fully-automatic analyzer. The fully-automatic analyzer and the analysis method of the urea in the milk and milk products can test a sample continuously and automatically and are accurate and rapid in the test.
Description
Technical field
The present invention relates to a kind of flow injection fully-automatic analyzer and analytical approach, relate in particular to fully-automatic analyzer and the analytical approach of urea in a kind of Milk and milk products.
Background technology
Urea is easy to enter mammary glandular cell and discharges with breast in mammal, so urea is the conventional component of Milk and milk products and a part that consists of nonprotein nitrogen, it is generally acknowledged that urea content is the normal contents scope of milk between 200～300mg/kg.The phenomenon that the urea content superelevation is arranged in the at present commercially available milk, mostly extra urea content is to come from illegal retailer and adds urea to improve total nitrogen content in fresh milk, reach the purpose of adulterating, earn illegal profit, consequently directly be detrimental to health, cause poisoning or potential hazard, cause huge economic loss for simultaneously Dairy Processing enterprise.
Flow Injection Analysis is simple, convenient with it, easily realize robotization and the characteristics that can carry out online pre-treatment to sample being widely used at present (Ruzicka J, Hansen E H in the chemical analysis, Flow Injection Analysis, Wiley, New York, 1981; Fang Zhaolun, flow injection analysis, Beijing: Science Press, 1999).Use the method for flow injection (FI) to measure urea, method (Anal.Chim.Acta, 1996,323:109～113 of great majority employing and Electrochemical Detection coupling; J.Pharm.Bio.Anal.1999,21:51～57; Sensors and Actuators, 2003, B91 (1～3): 5～10); Urea (Analyst, 1994,19 (8): 1829～33 of adopting in the chemiluminescent method human body urine are also arranged; Sichuan Teachers University journal (natural science edition), 2004,27 (3): 288～291); Detect (J.Flow.Injection.Anal in the beverage with the photometry coupling, 2002,133～136), (trace elements and health research in the swimming pool 19 (2):, 2008,66～67), (Anal.Lett.1987,20 (12): 1977～1994) mensuration of urea content in the blood 25 (4):.The mensuration that is used for the milk urea content, the method of report also is to adopt the method (J.Agric of flow injection and galvanochemistry coupling, Food.Chem., 1998,46 (4): 1386～1389), and electrochemical method easily is subject to the interference of extraneous factor, is not easy to obtain reliable and stable numerical value.
At present, the measurement of the urea content in the Milk and milk products there is no national standard, and the mensuration of urea content in international standard ISO 14637～2004 milk is mainly the enzyme process of measuring urea degradation products---utilize the difference of pH value.Because the method has specific (special) requirements to reagent and instrument, common laboratory is difficult to realize.The direct detecting method of urea, be generally based on urea and the complex structure of reagent place's generation and the colorimetric method of quantity, such as AOAC (2000 editions) assay method, 967.07 the mensuration of urea content in the mensuration of the urea content in the animal feed and ISO 6654～1991 animal feeds, all adopt the method, the principle of method is that the interfering materials such as the protein in the raw material milk and fat are removed, under acid condition, urea in the test solution and paradime thylaminobenzaldehyde reaction generate yellow compound, the depth of its color is directly proportional with urea content, but the method complex pretreatment, developing time is long, and stability is slightly poor.
Summary of the invention
The purpose of this invention is to provide and a kind ofly continuously and automatically sample is tested, test fully-automatic analyzer and the analytical approach of urea in the Milk and milk products quickly and accurately.
The fully-automatic analyzer of urea in the Milk and milk products provided by the present invention comprises automatic sampling apparatus, peristaltic pump, detecting device, computer processing system and online processing components; Described detecting device is connected with computer processing system by signal wire; Described online processing components comprises sample fillup valve, the first knitting reactor, the second knitting reactor, the first threeway, the second threeway, online dialyse module, sampling ring, capillary connecting pipe, peristaltic pump pump line, current-carrying container bottle, sour reagent solution container bottle, reagent container bottle, the first back pressure regulator, the second back pressure regulator, heating module, condensation module and waste liquid tank;
Described sample fillup valve is multiport valve, has at least A, B, C, D, E, six interfaces of F; Described interface B is connected with the two ends of sampling ring respectively with interface E; The two ends of described the second peristaltic pump pump line are communicated with the capillary connecting pipe with described interface D and described current-carrying container bottle respectively; The port A of described interface C, described online dialysis module is connected with the capillary connecting pipe; The port C of described current-carrying container bottle, described the 3rd peristaltic pump pump line and described online dialysis module is connected with the capillary connecting pipe successively; Described interface, described the first back pressure regulator and described waste liquid tank are connected with the capillary connecting pipe successively; The port B of described online dialysis module, described the second back pressure regulator and described waste liquid tank are connected with the capillary connecting pipe successively; The port D of described online dialysis module is communicated with the capillary connecting pipe with an import of described the first threeway; Another import of described sour reagent solution container bottle, described the 4th peristaltic pump pump line, described the first threeway is connected with the capillary connecting pipe successively; An import of the outlet of described the first threeway, described knitting reactor, described the second threeway is connected with the capillary connecting pipe successively; Another import of described reagent container bottle, described the 5th peristaltic pump pump line, described the second threeway is connected with the capillary connecting pipe successively; The outlet of described the second threeway, described heating module, described condensation module, described knitting reactor, described flow cell and described waste liquid tank are connected with the capillary connecting pipe successively; Described automatic sampling apparatus, described peristaltic pump, described interface F connect with the capillary connecting pipe successively.
The fully-automatic analyzer of urea in the Milk and milk products of the present invention, wherein, described online dialysis module comprises fixed block, in described fixed block, be disposed with from lower to upper lower lock block, dialysis membrane, upper holder block and briquetting, wing plate at described fixed block is equipped with bolt, described bolt is fixed described briquetting, described lower lock block, the contacted side of described upper holder block and described dialysis membrane is respectively equipped with groove, described lower lock block, the symmetrical formation of the groove of described upper holder block stream, end face at described lower lock block and described upper holder block is respectively equipped with the threaded hole that communicates with groove, and described screw thread mouth is respectively described port A, B, C and D.
The fully-automatic analyzer of urea in the Milk and milk products of the present invention, wherein, described heating module comprises heating rod, is sleeved on the outer aluminium body of heating rod, is wrapped in heated capillary, the thermometric thermal resistance on the described aluminium body and is coated on the external muff of described aluminium; The outlet of described the second threeway is communicated with an end of described heated capillary, and the other end of described heated capillary is connected with described condensation module.
The fully-automatic analyzer of urea in the Milk and milk products of the present invention, wherein, described condensation module comprises weeping out, cool storage container, the first support and the second support, main refrigerator, auxiliary refrigerator, the first heating radiator and the second heating radiator, the first fan and the second fan and a controller; Described the first support is fixed on the relative side of cool storage container with the second support, described weeping out is around on the surface that is installed in described cool storage container remainder, described main refrigerator is between described cool storage container and the first support, described auxiliary refrigerator is between described cool storage container and the second support, the chill surface of described main refrigerator is fitted and is fixed on the described cool storage container right flank, and the chill surface of described auxiliary refrigerator is fitted and is fixed on the described cool storage container left surface; A side of the first heating radiator is fixed together by the right flank of described the first support and the hot side of described main refrigerator, and another side of described the first heating radiator is provided with the first heat radiator, and the first fan is fixedly mounted on the outside of described the first heat radiator; A side of the second heating radiator is fixed together by the left surface of described the second support and the hot side of described auxiliary refrigerator, and another side of described the second heating radiator is provided with the second heat radiator, and the second fan is fixedly mounted on the outside of described the second heat radiator; Described controller is provided with temperature sensor, and described temperature sensor is fixedly mounted in the inner chamber of described cool storage container, and described controller links to each other with the auxiliary refrigerator electricity with described temperature sensor; The other end of described heated capillary is connected with described weeping out.
The fully-automatic analyzer of urea in the Milk and milk products of the present invention, wherein, described automatic sampling apparatus comprises sample introduction needle, sample disc, sample introduction needle service sink and pipeline-cleaning pond; The upper end of described sample introduction needle is connected with the effective capillary connecting pipe of described the first peristaltic pump.
The fully-automatic analyzer of urea in the Milk and milk products of the present invention, wherein, the molecular cut off of described dialysis membrane is 3500～25000.
Fully-automatic analyzer provided by the present invention is analyzed the method for urea content in the Milk and milk products, comprises the steps:
The precipitation method are removed the protein in the Milk and milk products sample, filter, and filtrate enters described fully-automatic analyzer;
By online dialysis module dialysis;
The solution of dialysing and sour reagent mix;
Mixed solution and developer reaction;
Reacted solution carries out colorimetric estimation through on-line heating, the online condensation pond that circulates at 500～600nm place; Calculate the content of urea at typical curve according to absorbance peak height value or peak area value.
Fully-automatic analyzer of the present invention is analyzed the method for urea content in the Milk and milk products, and wherein, the volumetric molar concentration of sulfuric acid is 2～5mol/L in the described sour reagent, and the volumetric molar concentration of phosphoric acid is 0.5～3mol/L, Fe
3+Or Cd
2+Volumetric molar concentration be 0.1～0.5mmol/L.
Fully-automatic analyzer of the present invention is analyzed the method for urea content in the Milk and milk products, and wherein, the mass concentration of Diacetylmonoxime is 5～25g/L in the described developer, and the mass concentration of thiosemicarbazide is 0.05～0.3g/L.
The fully-automatic analyzer of urea in the Milk and milk products of the present invention, sample determination frequency be 22 samples/hour; The range of linearity of method is 10.0～400.0mg/kg, and linearly dependent coefficient r 〉=0.999 detects and is limited to 0.115mg/kg, and the recovery of standard addition of actual sample is 90%～110%; Precision is high, and the relative standard deviation of different sample tests (n=7) is 0.68～2.0%.
Further the present invention will be described below by embodiment.
Description of drawings
Fig. 1 is the structure diagram of the fully-automatic analyzer of urea in the Milk and milk products of the present invention.
Fig. 2 a is online dialysis modular structure schematic diagram;
Fig. 2 b is the stream form of upper lower lock block in the online dialysis module.
Fig. 3 is the heating module structural representation.
Fig. 4 is the main pseudosection of condensation module.
Fig. 5 is the vertical view of Fig. 4.
Embodiment
The fully-automatic analyzer of urea in the Milk and milk products as shown in Figure 1 comprises automatic sampling apparatus 1, peristaltic pump 23, detecting device 22, computer processing system 11 and online processing components.
Be provided with flow cell 21 in the detecting device 22, detecting device 22 is connected with computer processing system 11 by signal wire 8.
Automatic sampling apparatus 1 comprises sample introduction needle 2, sample disc 25, sample hose 6, sample introduction needle service sink 26, pipeline-cleaning pond 27; The lower end of sample introduction needle 2 can be stretched in the sample hose 6 of sample disc 25, draws sample from sample hose 6, sample of every taking-up, and sample introduction needle sequentially enters sample introduction needle service sink 26 and pipeline-cleaning pond 27, carries out respectively the cleaning of sample introduction needle and the cleaning of sample introduction pipeline.
Online processing components comprises sample fillup valve 19, two knitting reactor 14 and 15, two threeways 12 and 13, online dialysis modules 18, sampling ring 20, some capillary connecting pipes, some peristaltic pump pump lines, current-carrying container bottle 3, sour reagent solution container bottle 4, reagent container bottle 5, back pressure regulator 9, heating module 16 and condensation modules 17.
Shown in Fig. 2 a, online dialysis module 18 comprises] fixed block 32 of shape, in the fixed block groove, be disposed with from lower to upper lower lock block 28, dialysis membrane 29, upper holder block 30 and briquetting 31, a wing plate at fixed block 32 is equipped with bolt 33, bolt 33 withstands briquetting 31, has groove at lower lock block 28 and upper holder block 30 with dialysis membrane 29 contacted sides, the groove symmetry of two pressing plates is offered the stream that consists of fluid, both ends of the surface at lower lock block 28 and upper holder block 30 are provided with the threaded hole that communicates with groove, are respectively upper left mouthful of A, upper right mouthful of B, lower-left mouth C, bottom right mouth D.The height of described stream is 0.5～3mm, and width is 0.5～3mm, and the length of stream is 0.1～10m.The material of lower lock block 28 and upper holder block 30 is chemically inert fluorine material.The molecular cut off of dialysis membrane is 3500～25000.The stream form of online dialysis module 18 can be linear pattern, broken line type or shaped form.Shown in Fig. 2 b, the stream form of the module of dialysing online 18 is broken line type.
The interface F of sample fillup valve 19 links to each other with the end of the first peristaltic pump pump line 24-1, the other end of the first peristaltic pump pump line 24-1 is communicated with the upper end of sample introduction needle 2 by the capillary connecting pipe; Sample fillup valve 19 is six-way valves, has A, B, C, D, E, six interfaces of F, two states is arranged: sample introduction state and detected state.When A interface and B interface connection, C interface and D interface connection, E interface and F interface are communicated with, be the sample introduction state; When A interface and F interface connection, B interface and C interface connection, D interface and E interface are communicated with, be detected state.The interface B of sample fillup valve 19 is connected with the two ends of sampling ring 20 respectively with interface E; The interface D of sample fillup valve 19 is communicated with the capillary connecting pipe with the end of the second peristaltic pump pump line 24-2, and the other end of the second peristaltic pump pump line 24-2 is communicated with current-carrying container bottle 3 usefulness capillary connecting pipes;
The interface C of sample fillup valve 19 is communicated with the capillary connecting pipe with upper left mouthful of A of online dialysis module 18, the lower-left mouth C of online dialysis module 18 is communicated with the capillary connecting pipe with the end of the 3rd peristaltic pump pump line 24-3, and the other end of the 3rd peristaltic pump pump line 24-3 is communicated with current-carrying container bottle 3 usefulness capillary connecting pipes;
The interface A of sample fillup valve 19 is communicated with the import of back pressure regulator 9 with the capillary connecting pipe, and the outlet of back pressure regulator 9 is communicated with waste liquid tank 7 usefulness capillary connecting pipes;
Upper right mouthful of B of online dialysis module 18 is communicated with the import of back pressure regulator 10 with the capillary connecting pipe, and the outlet of back pressure regulator 10 is communicated with waste liquid tank 7 usefulness capillary connecting pipes;
The bottom right mouth D of online dialysis module 18 is communicated with one of them import of the first threeway 12, another import of the first threeway 12 is communicated with the capillary connecting pipe with the end of the 4th peristaltic pump pump line 24-4, and the other end of the 4th peristaltic pump pump line 24-4 is communicated with sour reagent solution container bottle 4 usefulness capillary connecting pipes; The outlet of the first threeway 12 is communicated with the capillary connecting pipe with an end of the first knitting reactor 14, the other end of the first knitting reactor 14 is communicated with one of them import of the second threeway 13, another import of the second threeway 13 is communicated with the capillary connecting pipe with the end of the 5th peristaltic pump pump line 24-5, and the other end of the 5th peristaltic pump pump line 24-5 is communicated with reagent container bottle 5 usefulness capillary connecting pipes; The outlet of the second threeway 13 is communicated with the capillary connecting pipe with the import of heating module 16, and the outlet of heating module 16 is communicated with the capillary connecting pipe with the import of condensation module 17; The outlet of condensation module 17 is communicated with the capillary connecting pipe with an end of the second knitting reactor 15, and the other end of the second knitting reactor 15 is communicated with the capillary connecting pipe with the import of flow cell 21, and the outlet of flow cell 21 is communicated with waste liquid tank 7 with the capillary connecting pipe.
The light path of flow cell (21) is 10～50mm.
The capillary pipe length of the first knitting reactor 14 is 1～10m, and the capillary pipe length of the second knitting reactor 15 is 1～9m.The length of sampling ring (20) is 1～4m.
Condensation module 17 comprises weeping out 41, the first supports 39, the second support 40 with reference to Figure 4 and 5, cool storage container 43, main refrigerator 42, auxiliary refrigerator 48, the first heating radiator 44, the second heating radiator 49, the first fans 50, the second fan 55, temperature sensor 46 and controller 47.Wherein, cool storage container 43 adopts metal material to make.Main refrigerator 42 and auxiliary refrigerator 48 adopt semiconductor cooler.The first heating radiator 44, the second heating radiator 49 are the red copper heating radiator.The first fan 50, the second fan 55 are the low noise fan.Main refrigerator 42, auxiliary refrigerator 48, the first heating radiator 44, the second heating radiator 49, the first fan 50, the second fan 55, temperature sensor 46 and controller 47 are commercially available product.The first support 39, the second support 40 are fixed on the relative side of cool storage container 43, and weeping out 41 is around on the surface that is installed in cool storage container 43 remainders.Be equipped with between the first support 39 and the second support 40 for the fixing web joint 53 of weeping out 41.Cool storage container 43 is provided with and weeping out 41 close-fitting grooves, and groove is distributed on the surface of cool storage container 43 around mode with multi-turn.Weeping out 41 embeds in the grooves, is wrapped on the cool storage container 43, by to cool storage container 43 refrigeration, thereby realizes cooling, the condensation of test substance.The groove size of cool storage container 43 is through accurate Calculation so that weeping out 41 when twining cool storage container 43, can embed groove fully, can with the metal part close contact of groove both sides and bottom, guarantee efficient heat interchange.Main refrigerator 42 is between cool storage container 43 and the first support 39, and auxiliary refrigerator 48 is between cool storage container 43 and the second support 40.The chill surface of main refrigerator 42 is fitted and is fixed on cool storage container 43 right flanks, and the chill surface of auxiliary refrigerator 48 is fitted and is fixed on cool storage container 43 left surfaces.Cool storage container 43 can not have steam by the time cold stored, released cold quantity again when needs freeze, to improve condensation efficiency, and balance heat to a certain extent, make temperature be in a metastable state, avoid instrument moving continuously or arrheaing a period of time when reruning, the temperature fluctuation of condensing unit is excessive.A side of the first heating radiator 44 is fixed together by the right flank of the first support 39 and the hot side of main refrigerator 42, another side of the first heating radiator 44 is provided with the first heat radiator, the first fan 45 is fixedly mounted on the outside of the first heat radiator, and acting in conjunction dissipates the heat that main refrigerator 42 produces rapidly.A side of the second heating radiator 49 is fixed together by the left surface of the second support 40 and the hot side of auxiliary refrigerator 48, another side of the second heating radiator 49 is provided with the second heat radiator, the second fan 55 is fixedly mounted on the outside of the second heat radiator, and acting in conjunction dissipates the heat that auxiliary refrigerator 48 produces rapidly.
The course of work of the automatic analyzer of urea is in the milk:
Draw sample in the sample hose 6 of sample introduction needle 2 from be inserted in sample disc 25, whenever get a kind of sample, sample introduction needle sequentially enters sample introduction needle service sink 26 and pipeline-cleaning pond 27, carries out respectively the cleaning of sample introduction needle 2 and the cleaning of sample introduction pipeline.Sample pumps into sample fillup valve 19 by peristaltic pump, after sampling ring 20 is full of, enters waste liquid tank 7 through interface A and back pressure regulator 9; 19 dislocations of sample fillup valve, current-carrying is released the sample that is full of in the sampling ring 20, enter upper left mouthful of A of online dialysis module, dialysis enters the stream that presses down the fluid in fast 28 to sample liquid through dialysis membrane, current-carrying in the current-carrying container bottle 3 enters online dialysis module from online dialysis module lower-left mouth C sample is released from line dialysis module 18 bottom right mouth D, mix in the first threeway 12 with sour reagent from online dialysis module 18 bottom right mouth D outflow, then first knitting reactor 14 of flowing through is further mixed, the test solution through the dialysis membrane dialysis does not enter waste liquid tank 7 from 18 upper right mouthfuls of B of online dialysis module through back pressure regulator 10, mix with developer in the second threeway 13 with the test solution after the sour reagent mix, through heating module 16, condensation module 17, further mix in the second knitting reactor 15, the pond 21 that circulates is detected, and the spectrogram of generation can be surveyed and drawn.Absorbance peak height value or the peak area value of standard solution according to record done typical curve, calculates the content of urea in the test fluid according to the absorbance peak height value of sample or peak area value at typical curve.
The below describes the method for using urea in the automatic analyzer test milk of the present invention in detail:
Adopt automatic analyzer of the present invention to test, the sample fillup valve is six-way valve, online dialysis module adopts broken line type, and the mechanical dimension head of stream * wide * height is 5m * 0.003m * 0.002m, and its material is PTFE, the dialysis membrane that it is used, molecular cut off is 14000, and the capillary inner diameter of stream is 0.8mm, and two knitting reactor 14 and 15 capillary pipe length are respectively 2m and 3m in the analyzing and testing stream, the length of other capillary connecting pipe is 0.5m, and the length of sampling ring 20 is 1m.The light path of flow cell 21 is 10mm, and capillary pipe length is 15m in the heating module 16, and length capillaceous is 3m in the condensation module 17, measures at the 540nm place.
1, the preparation of standard specimen
Preparation of standard sample: take by weighing 1.0000g urea (H
2NCONH
2) be dissolved in the 1000ml volumetric flask, the urea storing solution that is mixed with 1000mg/L is for subsequent use.
The urea storing solution of 1000mg/L with 15% trichloroacetic acid solution stepwise dilution, is configured to 0.0,10.0,20.0,50.0,100.0,200.0, the 400.0mg/L standard series.
In the present embodiment, the volumetric molar concentration of sulfuric acid is 3.3mol/L in the sour reagent, and the volumetric molar concentration of phosphoric acid is 1.gmol/L, catalyst Fe
3+Volumetric molar concentration be 0.4mmol/L.
In the developer, the mass concentration of Diacetylmonoxime is 13.5g/L, and the mass concentration of thiosemicarbazide is 0.2g/L.
Current-carrying is deionized water.
Agents useful for same all adopts domestic reagent, and the purity of reagent is minimum pure for analyzing.
2, determination
Take by weighing milk sample 20g, mix with 30% trichloroacetic acid solution equal-volume, under 4000 rev/mins centrifugal condition centrifugal 20 minutes, get supernatant to be measured after syringe filters.
3, sample introduction
Draw sample in the sample hose 6 of sample introduction needle 2 from be inserted in sample disc 25, sample pumps into sample fillup valve 19 by peristaltic pump, and sample is pumped to sampling ring 20, after sampling ring 20 is full of, enters waste liquid tank 7.
4, response measurement
19 dislocations of sample fillup valve, current-carrying is released the sample in the sampling ring 20, enter upper left mouthful of A of online dialysis module, the sample liquid of process flows out from online dialysis module 18 bottom right mouth D and mixes in the first threeway 12 with sour reagent, then first knitting reactor 14 of flowing through is further mixed, the test solution through the dialysis membrane dialysis does not enter waste liquid tank 7 from 18 upper right mouthfuls of B of online dialysis module through back pressure regulator 10, mix with developer in the second threeway 13 with the test solution after the sour reagent mix, through heating module 16, condensation module 17, further mix in the second knitting reactor 15, the pond 21 that circulates is detected, and the spectrogram of generation can be surveyed and drawn.Absorbance peak height value or the peak area value of standard model according to record done typical curve, the content that calculates urea at typical curve according to absorbance peak height value or the peak area value of milk sample.
Table 1 is the test result of standard model, and table 2 is the test result of milk sample, and table 3 is the Precision test result that urea content is measured in the milk sample.
The test result of table 1. standard model
| Concentration (mg/L) | Absorbance (peak height) | Absorbance (peak area) | Return and calculate concentration (mg/L) |
| 0 | 0.0002 | 0.0075 | 0 |
| 10 | 0.0121 | 5.0764 | 8.5058 |
| 20 | 0.0255 | 10.6597 | 19.2613 |
| 50 | 0.0641 | 26.9765 | 50.6933 |
| 100 | 0.1253 | 53.2033 | 101.2154 |
| 200 | 0.2485 | 106.5266 | 203.9352 |
| 400 | 0.4866 | 207.0855 | 397.6478 |
The test result of table 2. milk sample (n=3)
| Milk sample 1 | Milk sample 2 | Milk sample 3 | |
| Milk sample concentration (mg/kg) | 306.8 | 299.7 | 336.2 |
| Milk sample adds standard sample 100mg/kg | 408.94 | 397.06 | 438 |
| The recovery (%) | 102.1 | 97.3 | 101.8 |
| Milk sample adds standard sample 200mg/kg | 506.7 | 491.65 | 527.15 |
| The recovery (%) | 100 | 96 | 95.5 |
| Milk sample adds standard sample 400mg/kg | 688.73 | 666.31 | 78.63 |
| The recovery (%) | 95.5 | 91.6 | 91.1 |
| Milk sample adds standard sample 10mg/kg | 316.4 | 310.2 | 346.4 |
| The recovery (%) | 96 | 105 | 102 |
The Precision test result that urea content is measured in table 3. milk sample
| The sample repeated number | Milk sample 1 urea content (mg/kg) | Milk sample 2 urea contents (mg/kg) |
| 1 | 321.71 | 313.12 |
| 2 | 306.74 | 313.76 |
| 3 | 307.09 | 306.97 |
| 4 | 311.41 | 307.32 |
| 5 | 306.08 | 310.42 |
| 6 | 314.46 | 310.66 |
| Mean value (mg/kg) | 311.25 | 310.38 |
| Standard deviation (mg/kg) | 6.07 | 2.83 |
| Relative standard deviation RSD (%) | 1.95 | 0.91 |
The range of linearity of method is 10.0～400.0mg/kg, and linearly dependent coefficient r 〉=0.999 detects and is limited to 0.115mg/kg, and the recovery of standard addition of actual water sample is 90%～110%; Precision is high, and the relative standard deviation of different sample tests is 0.68～2.0%.
Embodiment recited above is described preferred implementation of the present invention; be not that the spirit and scope of the present invention are limited; do not breaking away under the design proposal prerequisite of the present invention; common engineering technical personnel make technical scheme of the present invention in this area various modification and improvement; all should fall into protection scope of the present invention; the technology contents that the present invention asks for protection all is documented in claims.
Claims (9)
1. the fully-automatic analyzer of urea in the Milk and milk products comprises automatic sampling apparatus (1), detecting device (22), computer processing system (11) and online processing components; Described detecting device (22) is connected with computer processing system (11) by signal wire (8), and it is characterized in that: described online processing components comprises sample fillup valve (19), the first knitting reactor (14), the second knitting reactor (15), the first threeway (12), the second threeway (13), online dialysis module (18), sampling ring (20), the capillary connecting pipe, peristaltic pump (23), the peristaltic pump pump line, current-carrying container bottle (3), acid reagent solution container bottle (4), reagent container bottle (5), the first back pressure regulator (9), the second back pressure regulator (10), heating module (16), condensation module (17) and waste liquid tank (7);
Described sample fillup valve (19) is multiport valve, has at least A, B, C, D, E, six interfaces of F; Described interface B is connected with the two ends of sampling ring (20) respectively with interface E; The two ends of the second peristaltic pump pump line (24-2) are communicated with the capillary connecting pipe with described interface D and described current-carrying container bottle (3) respectively; The port A of described interface C, described online dialysis module (18) is connected with the capillary connecting pipe; The port C of described current-carrying container bottle (3), the 3rd peristaltic pump pump line (24-3) and described online dialysis module (18) is connected with the capillary connecting pipe successively; Described interface A, described the first back pressure regulator (9) and described waste liquid tank (7) are connected with the capillary connecting pipe successively; The port B of described online dialysis module (18), described the second back pressure regulator (10) and described waste liquid tank (7) are connected with the capillary connecting pipe successively; The port D of described online dialysis module (18) is communicated with the capillary connecting pipe with an import of described the first threeway (12); Another import of described sour reagent solution container bottle (4), the 4th peristaltic pump pump line (24-4), described the first threeway (12) is connected with the capillary connecting pipe successively; An import of the outlet of described the first threeway (12), described the first knitting reactor (14), described the second threeway (13) is connected with the capillary connecting pipe successively; Another import of described reagent container bottle (5), the 5th peristaltic pump pump line (24-5), described the second threeway (13) is connected with the capillary connecting pipe successively; The outlet of described the second threeway (13), described heating module (16), described condensation module (17), described the second knitting reactor (15), flow cell (21) and described waste liquid tank (7) are connected with the capillary connecting pipe successively; Described automatic sampling apparatus (1), the first peristaltic pump pump line (24-1), described interface F connect with the capillary connecting pipe successively.
2. fully-automatic analyzer according to claim 1, it is characterized in that: described online dialysis module (18) comprises fixed block (32), in described fixed block (32), be disposed with from lower to upper the first briquetting (28), dialysis membrane (29), the second briquetting (30) and the 3rd briquetting (31), wing plate at described fixed block (32) is equipped with bolt (33), described bolt (33) is fixed described the 3rd briquetting (31), described the first briquetting (28), described the second briquetting (30) is respectively equipped with groove with the contacted side of described dialysis membrane (29), described the first briquetting (28), the symmetrical formation of the groove of described the second briquetting (30) stream, end face at described the first briquetting (28) and described the second briquetting (30) is respectively equipped with the threaded hole that communicates with groove, and described threaded hole is respectively described port A, B, C and D.
3. fully-automatic analyzer according to claim 1 and 2 is characterized in that: described heating module (16) comprises heating rod (36), is sleeved on the outer aluminium body (34) of heating rod (36), is wrapped in heated capillary (38), the thermometric thermal resistance (35) on the described aluminium body (34) and is coated on the outer muff (37) of described aluminium body (34); The outlet of described the second threeway (13) is communicated with an end of described heated capillary (38), and the other end of described heated capillary (38) is connected with described condensation module (17).
4. fully-automatic analyzer according to claim 3, it is characterized in that: described condensation module (17) comprises weeping out (41), cool storage container (43), the first support (39) and the second support (40), main refrigerator (42), auxiliary refrigerator (48), the first heating radiator (44) and the second heating radiator (49), the first fan (45) and the second fan (50) and a controller (47); Described the first support (39)) is fixed on the relative side of cool storage container (43) with the second support (40), described weeping out (41) is around being installed on the remaining surface of described cool storage container (43), described main refrigerator (42) is positioned between described cool storage container (43) and the first support (39), described auxiliary refrigerator (48) is positioned between described cool storage container (43) and the second support (40), the chill surface of described main refrigerator (42) is fitted and is fixed on described cool storage container (43) right flank, and the chill surface of described auxiliary refrigerator (48) is fitted and is fixed on described cool storage container (43) left surface; A side of the first heating radiator (44) is fixed together by the right flank of described the first support (39) and the hot side of described main refrigerator (42), another side of described the first heating radiator (44) is provided with the first heat radiator, and the first fan (45) is fixedly mounted on the outside of described the first heat radiator; A side of the second heating radiator (49) is fixed together by the left surface of described the second support (40) and the hot side of described auxiliary refrigerator (48), another side of described the second heating radiator (49) is provided with the second heat radiator, and the second fan (50) is fixedly mounted on the outside of described the second heat radiator; Described controller (47) is provided with temperature sensor (46), described temperature sensor (46) is fixedly mounted in the inner chamber of described cool storage container (43), and described controller (47) links to each other with auxiliary refrigerator (48) electricity with described temperature sensor (46); The other end of described heated capillary (38) is connected with described weeping out (41).
5. fully-automatic analyzer according to claim 4 is characterized in that: described automatic sampling apparatus (1) comprises sample introduction needle (2), sample disc (25), sample introduction needle service sink (26) and pipeline-cleaning pond (27); The upper end of described sample introduction needle (2) is connected with the capillary connecting pipe with described the first peristaltic pump pump line (24-1).
6. fully-automatic analyzer according to claim 5, it is characterized in that: the molecular cut off of described dialysis membrane is 3500～25000.
7. analyze the method for urea content in the Milk and milk products with arbitrary described fully-automatic analyzer in the claim 1 to 6, comprise the steps:
The precipitation method are removed the protein in the Milk and milk products, filter, and filtrate enters described fully-automatic analyzer;
By online dialysis module dialysis;
The solution of dialysing and sour reagent mix;
Mixed solution and developer reaction;
Reacted solution carries out colorimetric estimation through on-line heating, the online condensation pond that circulates at 500～600nm place;
Calculate the content of urea at typical curve according to absorbance peak height value or peak area value.
8. method according to claim 7, it is characterized in that: the volumetric molar concentration of sulfuric acid is 2～5mol/L in the described sour reagent, the volumetric molar concentration of phosphoric acid is 0.5～3mol/L, Fe
3+Or Cd
2+Volumetric molar concentration be 0.1～0.5mmol/L.
9. method according to claim 8, it is characterized in that: the mass concentration of Diacetylmonoxime is 5～25g/L in the described developer, the mass concentration of thiosemicarbazide is 0.05～0.3g/L.
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| CN102375073B (en) * | 2010-08-13 | 2013-12-04 | 北京吉天仪器有限公司 | Fully automatic fluorine analyzer and analytical method thereof |
| CN101975864B (en) * | 2010-11-03 | 2013-01-23 | 四川大学 | Automatic analyzer and automatic analysis method for various nutritive salts |
| CN102520190B (en) * | 2011-12-15 | 2014-03-05 | 中国人民解放军总医院 | Enzyme-linked immunoassay detection reagent kit for human insulin-like growth factor II |
| CN103499701B (en) * | 2013-09-04 | 2015-09-23 | 深圳市锦瑞电子有限公司 | Specific protein analyser and analytical approach thereof |
| CN107703124A (en) * | 2016-08-08 | 2018-02-16 | 安恒环境科技（北京）股份有限公司 | Urea concentration detection method and urea concentration on-line monitoring equipment |
| CN106405133B (en) * | 2016-08-30 | 2017-12-15 | 北京吉天仪器有限公司 | Suitable for the Ammonia-nitrogen analysis method of multi-field sample detection |
| JP6866211B2 (en) * | 2017-04-04 | 2021-04-28 | オルガノ株式会社 | Urea quantification method and analyzer |
| WO2018236272A1 (en) * | 2017-06-20 | 2018-12-27 | Delaval Holding Ab | Arrangement, method and measurement indicator for urea determination |
| CN108444994B (en) * | 2018-03-18 | 2021-11-05 | 北京宝德仪器有限公司 | Automatic analysis device and method for formaldehyde in water |
| CN110261628A (en) * | 2019-07-08 | 2019-09-20 | 东华理工大学 | A kind of online Absorbency Test platform and its test method of adsorbent material |
| CN112881724A (en) * | 2019-11-30 | 2021-06-01 | 深圳市帝迈生物技术有限公司 | Blood analyzer and detection device |
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