CN211043144U

CN211043144U - Water-borne flow infusion system

Info

Publication number: CN211043144U
Application number: CN201921741333.4U
Authority: CN
Inventors: 龚治湘; 杨梅; 龚晖
Original assignee: Chongqing Mintai New Agrotech Development Group Co ltd
Current assignee: Chongqing Mintai New Agrotech Development Group Co ltd
Priority date: 2018-10-29
Filing date: 2018-10-29
Publication date: 2020-07-17
Anticipated expiration: 2028-10-29
Also published as: CN209656565U

Abstract

The utility model discloses water year class infusion system belongs to the analytical chemistry field, and this water year class infusion system includes: the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a sample inlet pipe; the reagent bottle is used for containing a reducing agent and is communicated with the reactor through a reagent inlet pipe; the water outlet of the water bottle is communicated with the inlet of the sample inlet pipe and the inlet of the reagent inlet pipe respectively through the water inlet pipe, and the water inlet is controlled by switching the water inlet pipe. The water-carrying flow transfusion system is simplified and clean, so that the instrument is not corroded by acid, and the detection operation environment is free from pollution; can be used in combination with an analytical instrument, and can effectively overcome the memory effect.

Description

Water-borne flow infusion system

The application is a divisional application of an application with the application number of 201821763422.4 and the name of an atomic fluorescence analysis device using water as a current carrier, which is submitted to the national intellectual property office of the people's republic of China in 2018, 10 and 29.

Technical Field

The utility model belongs to the analytical chemistry field relates to atomic fluorescence analysis. The method breaks through the traditional infusion mode and the corresponding technology in the atomic fluorescence analysis method, and particularly relates to the improvement of the existing infusion mode.

Background

Atomic fluorescence analysis has been widely used for the determination of trace amounts of As, Sb, Bi, Hg, Se, and the like. The basic principle is that ions of an element to be detected in an acidic medium (usually hydrochloric acid) react with a strong reducing agent (usually potassium borohydride or sodium borohydride) to be reduced into gaseous hydride or atoms, and a large amount of hydrogen is generated. The hydride molecules are dissociated into ground state atoms in the high-temperature hydrogen flame and excited to a high energy state by radiation of a specific frequency of an excitation light source, and the excited state atoms emit fluorescence of a characteristic wavelength in the form of light radiation in the de-excitation process due to extreme instability of the high energy level. The fluorescence intensity is correlated with the concentration of the element to be detected, and the concentration of the element to be detected is obtained by measuring the fluorescence signal of the element to be detected by a detector (usually a photomultiplier).

The atomic fluorescence analysis device (also called atomic fluorescence instrument and atomic fluorescence photometer) designed according to the principle mainly comprises a transfusion system, a steam generation system (or called reactor), an atomizer, an excitation light source and a detection system. The test solution and the reducing agent are conveyed through the liquid conveying system and are carried by a carrier liquid (also called carrier liquid) to be fed into the reactor to carry out chemical reaction to generate gaseous atoms or hydride molecules (generally called vapor) and hydrogen, and the gaseous atoms or hydride molecules and the hydrogen enter the atomizer under the carrying of the carrier gas (usually argon).

The reagent solution and reagent are carried by HCl and NaBH4 (or KBH4), and the technology has the following defects: the infusion system has serious memory effect, particularly after a high-concentration mercury sample is measured, the next sample can be measured only by cleaning the sample for many times by using blank liquid, the time consumption is long, and even the infusion system needs to be completely replaced. The continuous use of a large amount of acid carrying liquid not only causes pollution to the operating environment, but also corrodes the instrument, and meanwhile, the detection cost is increased due to the consumption of a large amount of high-purity HCl and a more expensive reduction reagent in the current carrying process.

SUMMERY OF THE UTILITY MODEL

An object of the utility model is to provide a water current-carrying transfusion system to effectively solve the above-mentioned problem among the atomic fluorescence analysis.

The utility model provides a water current-carrying transfusion system for infusion in to chemical analysis instrument's reactor, include: the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a sample inlet pipe; the reagent bottle is used for containing a reducing agent and is communicated with the reactor through a reagent inlet pipe; the water outlet of the water bottle is respectively communicated with the inlet of the sample inlet pipe and the inlet of the reagent inlet pipe through a water inlet pipe, and the water inlet is controlled by switching the water inlet pipe; and, the switching is a bidirectional switch.

Furthermore, in the water-borne flow transfusion system, the sample inlet pipe, the reagent inlet pipe and the water inlet pipe are capillary tubes.

The water-carrying flow transfusion system also comprises a peristaltic pump, wherein the sample inlet pipe and the reagent inlet pipe are arranged in the peristaltic pump, and liquid is conveyed into the reactor through the peristaltic pump.

The water-borne flow transfusion system also comprises sample storage rings, and the sample inlet pipe and the reagent inlet pipe are respectively provided with the sample storage rings at the extension part at the rear end of the peristaltic pump.

The utility model discloses still provide another kind of water current carrying transfusion system who simplifies, include: the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a liquid inlet capillary; the reagent bottle is used for containing a reducing agent and is communicated with the reactor through another liquid inlet capillary; the two water cups are used for containing purified water, one water cup is used for containing cleaning water, the other water cup is used for containing carrier water, and the liquid inlet capillary can be replaced and inserted in the two water cups.

The simplified water-borne flow transfusion system also comprises a peristaltic pump, wherein the two liquid inlet capillary tubes are connected into the reactor through the peristaltic pump, and the peristaltic pump is used for controlling the conveying speed and the transfusion quantity of the liquid inlet capillary tubes for feeding test liquid, reagent, cleaning water and current-borne water.

The simplified water-borne flow transfusion system also comprises a sample storage ring, and the extension parts of the two liquid inlet capillary tubes at the rear end of the peristaltic pump are respectively the sample storage rings.

Scheme more than adopting, utilize the utility model discloses a water year flows infusion system can creatively use water as the current-carrying in the atomic fluorescence analysis process, has ended the history that uses HCl and NaBH4 as the current-carrying for more than 30 years, and infusion system simplifies and is clean, and the instrument is not corroded by acid, detects the operating environment and is pollution-free. Experiments prove that: the transfusion technology using water to replace HCl and reducing agent As current-carrying is used in atomic fluorescence analysis, not only can detect trace or trace As, Sb, Bi, Pb, Se, Cd, Hg, etc. in test solution, but also overcomes the technical prejudice that the atomic fluorescence analysis can not use water As current-carrying in common understanding, and at the same time, unlike HCl and NaBH4 As current-carrying, the ultrapure water does not contain the component to be measured, and does not have any chemical reaction with the test solution or reducing agent in the transfusion process, and does not have a large amount of bubbles (caused by hydrogen generated by acid and reducing agent) adhered to the tube wall of the flow path, so that all the transfusion flow paths can be washed thoroughly. Therefore, the atomic fluorescence instrument taking water as a current-carrying material effectively overcomes the memory effect, improves the sensitivity and accuracy of the determination, saves a large amount of high-purity HCl and a reducing agent NaBH4, greatly reduces the analysis cost, and obviously improves the operation environment.

The present invention will be described in detail with reference to the accompanying drawings and examples.

Drawings

FIG. 1 is a schematic diagram showing the construction of an atomic fluorescence analysis apparatus using a water-borne flow infusion system;

FIG. 2 is a schematic view of the simplified water-borne infusion system and infusion of the present invention;

FIGS. 3A and 3B are the peak curve (fluorescence value-time) and the standard curve (fluorescence value-concentration) of 0.1-0.5ng/m L of Cd measured by the atomic fluorescence analyzer using water as carrier in example 1;

FIGS. 4A and 4B are graphs showing the peak value of Hg/As (fluorescence value-time) measured simultaneously with a mixed solution of 0.1 to 0.5ng/ml Hg and 10 to 50ng/ml As (fluorescence value-concentration) in an atomic fluorescence analyzer using water As a carrier in example 2.

Detailed Description

The utility model discloses a water carrier flow transfusion system can be used to among the atomic fluorescence analysis, and conventional atomic fluorescence analysis device includes infusion system, reactor, atomizer, excitation light source and detector (see that fig. 1 shows), wherein introduces test solution and reductant (reagent) respectively in to the reactor by infusion system, and the introduction in-process will use hydrochloric acid and reductant respectively to do the current-carrying.

The utility model discloses a design is at conventional atomic fluorescence analysis infusion in-process, utilizes water to replace HCl and reductant (reagent) to do the current-carrying, is inputing test solution and reagent to separately preserving appearance ring from the imbibition capillary respectively after, and two capillaries all do the current-carrying with the pure water, and test solution and reagent in separately preserving appearance ring are reacted in being pushed into the reactor under the carrier band of water, and simultaneously, the pure water of current-carrying also washs the pipeline of infusion system.

According to the above design, referring to the infusion system part shown in fig. 1, the water-based flow infusion system provided by the utility model comprises: the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a sample inlet pipe; the reagent bottle is used for containing a reducing agent and is communicated with the reactor through a reagent inlet pipe; the water outlet of the water bottle is communicated with the inlet of the sample inlet pipe and the inlet of the reagent inlet pipe respectively through the water inlet pipe, and the water inlet is controlled by switching the water inlet pipe. The infusion system is unique in design that the infusion system does not comprise a matched device for infusing hydrochloric acid, and is obviously distinguished and obviously different from the known infusion system. The liquid conveying system and a conventional atomic fluorescence instrument comprising a reactor, an atomizer, an excitation light source, a detector and the like form an atomic fluorescence analysis device taking water as a carrier.

According to above design, utilize the utility model discloses a water carries a class transfusion system, the test solution of introducing certain acidity and reagent (feed liquor) of certain concentration respectively simultaneously earlier at the infusion process, use the pure water to get into the reactor reaction as current-carrying propelling movement respectively (carrier band propelling movement) test solution and reagent again, utilize the atomizer to make the reaction back vapour atomization, the concentration of the element that awaits measuring in the rethread laser source and detector acquire the fluorescence signal (survey) of the element that awaits measuring and then the calculation obtains the test solution. The infusion process completely does not use hydrochloric acid as a current carrier, and the current carrier of a reagent is changed into pure water, so that the infusion system is obviously different from a known infusion system and exceeds the conventional imagination.

The concentration ranges and acidity (HCl) of the main elements measured by an atomic fluorescence analyzer using water as a carrier are shown in table 1.

TABLE 1 concentration and acidity of the element solutions

Element(s)	As	Sb	Bi	Se	Hg	Pb	Cd
								Concentration/ng/ml	1-50	1-10	1-10	1-50	0.1-2	2-25	0.05-2
HCl/％	10	10	10	10	5-10	10	4

Reducing agent NaBH for determining main elements₄(or KBH₄) The concentrations are given in Table 2.

TABLE 2 concentrations of the customary reagents

Element(s)	As	Sb	Bi	Hg	As-Hg	Pb	Cd
								NaBH₄/％	1	1	1	0.2	1	2	2.5

Specifically, referring to fig. 1, the atomic fluorescence analysis method using water as a carrier may include the following specific steps:

step 1, preparing series of standard solutions, sample solutions and NaBH of elements to be detected with different concentrations₄Putting the solution, the standard solution and the sample solution into a test solution bottle, and adding NaBH₄Putting the solution into a reagent bottle; purified water is put into a water bottle.

Step 2, making a standard curve: 1) connecting a sample inlet pipe to a test solution bottle interface filled with standard blank liquid (acid liquid with element concentration to be measured being 0), connecting a reagent inlet pipe to a reagent bottle interface, and feeding liquid (4-5 seconds); 2) switching the sample inlet pipe and the reagent inlet pipe to be communicated with the water inlet pipe, sucking water into the sample inlet pipe and the reagent inlet pipe, and carrying the blank liquid and the reagent by a carrier belt (until the detection is finished for 8-10 seconds); 3) the reactor, the atomizer and the excitation light source work, and the detector records a blank fluorescence value; 4) replacing the test solution bottles filled with standard solutions with different concentrations in sequence from low to high, and repeating the steps 1) -3), and sequentially measuring and obtaining the fluorescence value corresponding to each solution in the standard series; 5) and (4) drawing a fluorescence value-concentration standard curve.

Step 3, sample determination: and (3) after the sample inlet pipe is cleaned by water, replacing the sample solution bottle filled with the sample solution, repeating the steps 1) -3) to measure and obtain the fluorescence value corresponding to the sample solution, and converting the fluorescence value-concentration standard curve to obtain the concentration value of the element to be measured in the sample solution.

The simplified water-carrying transfusion system of the utility model is shown in figure 2, comprising: the device comprises a test solution bottle for containing a sample solution to be tested and a reagent bottle for containing a reducing agent, wherein the test solution bottle and the reagent bottle are communicated with a reactor through a liquid inlet capillary; the two water bottles are used for containing purified water, one water bottle (water cup 1) contains cleaning water for cleaning a capillary tube, and the other water bottle (water cup 2) contains carrier flow water as a carrier flow. In the atomic fluorescence analysis transfusion process, a peristaltic pump can be used, after a test solution and a reagent are respectively input into a sample storage ring (called as sampling) through two capillaries under the action of the peristaltic pump, the front sections of the two capillaries near the head ends are transferred into cleaning purified water of a water cup 1 to be cleaned (shown by a dotted line in figure 2), then the head ends of the two capillaries are transferred into a water cup 2 (shown by a dotted line in figure 2 to be called as plug-in change), and the test solution and the reagent in the sample storage ring are carried by carrier purified water to be pushed into a reactor. Similarly, atomic or molecular vapor generated by the chemical reaction is atomized after being input into the atomizer and is excited by radiation of the excitation light source. And detecting the emitted fluorescent signal to obtain the concentration of the element to be detected in the test solution.

The time control in the atomic fluorescence analysis with water as a carrier is as follows: sample/delay/add/drop (capillary)/assay: 4-5/0/2-3/8-10 (seconds). That is, the time for sucking in the sample solution and the reagent (sampling) is 4-5 seconds, the time delay is usually zero seconds, the capillary tube is taken out of the sample solution and the reagent, and the time for transferring the sample solution and the reagent into the water cup 2 (changing and inserting) after placing the sample solution and the reagent in the water cup 1 for a moment is usually 2-3 seconds. The time for pushing the test solution and the reagent in the sample storage ring by the carrier water in the water cup 2 until the determination is finished is 8-10 seconds, and the fluorescence signal of the element is measured in the time.

The specific operation of the detection example is as follows:

operation 1, preparing standard series solution of elements to be detected and NaBH according to requirements₄Solutions and related reagents, sample solutions need to be prepared in advance. A sample pan was placed with NaBH4 solution and two cups of purified water.

And 2, switching on a power supply of the atomic fluorescence instrument, selecting a single channel or a double channel on a setting page of the desktop system, confirming conditions required by the test, lighting a light source of the element to be tested, and preheating for 5-10 minutes. And opening the valve of the Ar gas steel cylinder, adjusting the pressure of the Ar gas to be 0.3MPA, and opening an exhaust device of the atomizer.

Operation 3, standard curve preparation:

1) sampling: inserting the ends of two liquid inlet capillary tubes into standard blank liquid and NaBH respectively₄In solution, clickWhen the desktop standard page is blank, the infusion system automatically executes an infusion program, and the peristaltic pump stops working after sampling for 4-5 seconds;

2) immediately taking out the two capillaries, putting the capillaries into the cleaning water of the water cup 1 for cleaning, immediately transferring the capillaries into the purified water of the water cup 2 (the time of the replacement is 2-3 seconds), and restarting the peristaltic pump;

3) carrying test solution and reagent into a reactor respectively by carrier water in a water cup 2, simultaneously measuring a blank fluorescence signal by an instrument and recording a blank fluorescence value (the time from the carrier to the end of measurement is 8-10 seconds);

4) after the blank fluorescent signal is stable, sequentially measuring the fluorescent signals of the standard series solutions according to the concentration from low to high, and recording the fluorescent value; the peak curves of the fluorescence signals (fluorescence value-time) can be generated synchronously;

5) the concentration of the standard solution is input into a desktop system, and the average value of the measurement of each concentration standard solution is taken to prepare a fluorescence value-concentration standard curve.

Run 4. measurement of samples: after a liquid inlet capillary inserted into a test solution bottle is cleaned by water, a sample blank is firstly measured to be stable on a sample test page of a desktop system, then the fluorescence signal of each sample solution is sequentially measured according to the test method of the operation 3 standard solution, the concentration of an element to be measured in the sample solution is obtained from a fluorescence value-concentration standard curve according to the fluorescence value of the sample, and the content of the element to be measured in the sample is calculated after relevant parameters are input.

The above method can measure a single element or two elements simultaneously. When the multi-element is measured, standard mixed solutions with different elements and different concentrations are prepared, standard curves of corresponding elements are made, and the content of the element to be measured in each sample is measured according to the steps and the operation. The following is further described with reference to specific examples, which are given by way of illustration and not by way of limitation. In the examples, "%" means mass percent concentration.

Example 1: analysis of Cd

Testing a sample: rice, soybean

And (3) manufacturing a cadmium standard curve: preparing 10ng/ml cadmium standard solution (prepared now), then respectively putting 0, 0.5, 1.0, 1.5, 2.0 and 2.5ml of the standard solution into a 50ml plastic quantitative bottle, respectively adding 4ml of 50% HCl solution and 5ml of 5% thiourea into each solution, diluting the solutions to a scale with water, wherein the concentrations of the standard series solutions are 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng/ml Cd. After shaking up, the fluorescence signals of the blank and standard series solutions were measured according to the procedure to prepare a standard curve (see FIG. 3B, FIG. 3A is the peak curve of Cd).

Preparation and determination of test solutions:

weighing 0.1-0.2g of rice or soybean sample, placing the rice or soybean sample in a 50ml plastic quantitative bottle, adding 50% HCl4ml and 5% thiourea respectively, shaking for 5-10min, diluting with water to scale, shaking uniformly, measuring the fluorescence signal of the sample solution by using the sample solution as a test solution according to the operation process, and obtaining the concentration of Cd from a standard curve and converting the concentration of Cd into the content of Cd in the sample. The results of the determination of Cd in the food samples are shown in Table 3.

TABLE 3 test results (ng/g) for Cd in rice and soybean meal

As can be seen from the data in the table, under the conditions that the sample weighing (G) is greatly different and the HCl concentration is 4 percent, the test sample is not pretreated, cadmium in foods such as rice and the like can be rapidly measured by using the atomic fluorescence analysis of water carrying flow, and the content of Cd in the measured sample is consistent with the recommended value.

In the determination operation, only pure water (18.2M omega) is consumed without hydrochloric acid as a carrier, the sampling time is reduced by about 50 percent compared with the conventional method, and NaBH is reduced by about 50 percent₄The solution only needs to be used for participating in the reaction, and is saved by more than 75% compared with the conventional detection. The sample detection in table 3 is sequentially determined from left to right, and it can be seen that the determination of the concentration of cadmium in the solution can still be completed from high to low and the determination result is accurate, therefore, water is used as the carrier flow, the memory effect is eliminated, and even after the determination of the high-concentration standard solution, the determination of other concentration sample solutions is not affected because the infusion system is cleaned by the carrier flow water.

Example 2: simultaneous measurement of Hg/As

Testing a sample: soil(s)

Because the content of As in soil is much higher than Hg, the existing atomic fluorescence instrument can not simultaneously measure Hg and As in the sample. In the embodiment, water is used As a carrier flow to realize the simultaneous detection of two elements of Hg and As in the same sample.

And (3) preparing a standard curve: a mixed standard solution containing 500ng/ml As and 5ng/ml Hg was prepared in advance. Taking 0, 1, 2, 3, 4 and 5ml of the standard solution respectively, putting 5ml of 5% Vc-5% thiourea solution and 10ml of HCl with the concentration of 50% in 50ml plastic quantitative bottles, diluting the solutions to a scale with water, and obtaining series of standard solutions with the Hg concentration of 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng/ml and the As concentration of 0, 10, 20, 30, 40 and 50 ng/ml.

Selecting a double-channel method, simultaneously measuring the fluorescence signals of Hg and As in the blank and standard series solutions according to the operation process, and respectively making standard curves of 0.1-0.5ng/ml Hg and 10-50ng/ml As of the mixed standard solution. FIG. 4A is a peak curve of Hg/As and FIG. 4B is a standard curve of mixed standard solutions of Hg and As (the signal of the standard curve is calculated from the spectral area and the blank area has been subtracted).

Preparation and determination of test solutions: placing 0.1-0.2g of soil sample in a 50ml plastic quantitative bottle, adding 5ml of 5% Vc-5% thiourea solution and 10ml of HCl with the concentration of 50%, diluting with water to scale, shaking up, simultaneously measuring fluorescence signals of Hg and As of the sample solution by taking the sample solution As a test solution according to the operation process, and obtaining the concentrations of corresponding elements according to respective standard curves so As to calculate the respective contents in the sample. The results are shown in Table 4.

TABLE 4 results of simultaneous measurement of soil Hg/As

The data show that the difficulty of simultaneously measuring Hg and As in soil is solved using the above method and apparatus. Meanwhile, the Hg concentration in 6 samples (standard samples) has larger difference, and the results of the samples sequentially tested from top to bottom according to the table 4 are consistent with the recommended values, which shows that the fluorescence analysis method and the fluorescence analysis device using water as a current-carrying atom eliminate the serious memory effect of Hg determination.

In the embodiment, two elements coexist in the test solution, the conveying system only needs to finish the conveying of the test solution once, the detection of the double-channel detection system is also finished once, and water is used as a current-carrying agent in the determination operation without hydrochloric acid or NaBH₄The solution only needs 100ml to 250ml to participate in the reaction, and the time and the cost of the whole testing process are greatly reduced.

Claims

1. An aqueous carrier fluid infusion system for infusing fluid into a reactor of a chemical analysis instrument, comprising:

the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a sample inlet pipe;

the reagent bottle is used for containing a reducing agent and is communicated with the reactor through a reagent inlet pipe;

the water outlet of the water bottle is communicated with the inlet of the sample inlet pipe and the inlet of the reagent inlet pipe respectively through the water inlet pipe, and the water inlet is controlled by switching the water inlet pipe.

2. The water-borne fluid infusion system of claim 1, wherein the switch is a two-way switch.

3. The water-borne stream infusion system of claim 1, wherein the sample inlet tube, reagent inlet tube, and water inlet tube are capillary tubes.

4. The water-borne stream infusion system according to any one of claims 1 to 3, further comprising a peristaltic pump, wherein the sample inlet tube and the reagent inlet tube are arranged in the peristaltic pump, and liquid is conveyed into the reactor through the peristaltic pump.

5. The water-borne flow infusion system of claim 4, further comprising a sample ring, wherein the sample tube and the reagent tube extend from the rear end of the peristaltic pump to form respective sample rings.

6. An aqueous carrier fluid infusion system for infusing fluid into a reactor of a chemical analysis instrument, comprising:

the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a liquid inlet capillary;

the reagent bottle is used for containing a reducing agent and is communicated with the reactor through another liquid inlet capillary;

the two water cups are used for containing purified water, one water cup is used for containing cleaning water, the other water cup is used for containing carrier water, and the liquid inlet capillary can be replaced and inserted in the two water cups.

7. The water-borne flow transfusion system of claim 6, further comprising a peristaltic pump, wherein the two liquid inlet capillaries are connected into the reactor through the peristaltic pump, and the peristaltic pump is used for controlling the conveying speed and the conveying amount of the liquid inlet capillary, the reagent and the cleaning water, and the carrier flow water.

8. The aqueous carrier fluid infusion system of claim 7, further comprising a sample ring, wherein the two inlet capillaries extend into the respective sample rings at the rear end of the peristaltic pump.