WO2021109079A1 - Intelligent chemical reaction device and sampling method - Google Patents

Abstract

An intelligent chemical reaction device and a sampling method, comprising: a sampling temporary storage chamber (3) and a reaction stirring chamber (4). A peristaltic pump (32) is mounted at the top of the sampling temporary storage chamber (3); a placing rack (34) is placed in a cavity under the peristaltic pump (32); a liquid level sensor (33) is mounted on the placing rack (34); a light source (43) is mounted at the top of the reaction stirring chamber (4); an automatic stirrer (5) is placed in a cavity under the light source (43); the peristaltic pump (32) is connected to a sampling test tube (35) and a reaction container (53) by means of hoses, separately. The method comprises the steps: S1. sampling parameter obtaining: according to a fit curve, determining that a reaction type R in sampling parameters is a zero-level or first-level reaction; S. sampling of the zero-level reaction; S3. sampling of the first-level reaction; S4. sampling time adjustment. According to the device, the peristaltic pump (32) is configured to take a sample, and the sampling precision is high; the automatic stirrer (5), a timer, and the liquid level sensor (33) are used for automatic sampling and storage, and labor and material resources are saved. By means of the method, sampling time is controllable and reasonable.

Description

Intelligent chemical reaction device and sampling method Technical field

The invention relates to an intelligent chemical reaction device and a sampling method, and belongs to the technical field of experimental appliances.

Background technique

At present, most of the sampling methods in chemical experiments are manual sampling, which will increase the workload of researchers and even fail to complete the experiment. For example, the time required for sampling in the experiment is too long (for example, a reaction process exceeds 24 hours), and the sampling interval is relatively long. Short (for example, the sampling interval is required to be shorter than 10 seconds) or the interval is continuous but less uniform time points (for example, the chemical reaction speed changes with time), etc. In addition, there are some reaction conditions of chemical experiments that are obviously harmful to the human body, such as harmful rays and radiation, ultraviolet light irradiation, strong light irradiation, microwave radiation and other conditions, so there is an urgent need for automated chemical experiment equipment. However, the current equipment is still unable to achieve this goal. The main reason is that the chemical experiment device does not couple the chemical experiment principle with the model. In addition, due to lack of understanding of chemical experiments, it is impossible to develop corresponding experimental devices, as follows:

(1) Chemical reactions generally follow a certain reaction kinetics law. If the entire reaction process needs to be investigated during the experiment, certain reaction conditions need to be controlled, and samples should be obtained at a reasonable time point, so that the subsequent detection can obtain The data points are uniform and reasonable and can reflect the entire chemical process, and these need the assistance of theoretical models, but so far, no relevant equipment has been seen.

(2) The existing experimental device generally adopts a sampling needle method. The sample is drawn in the reactor and transferred to a certain container. In addition, the purpose of sampling can be achieved by switching the multi-channel valve. However, no matter which method is used, there is a problem of sample residue in the sampler, which leads to contamination of the sample during re-sampling, which directly affects the accuracy of the experiment. Even if the cleaning solution is used for cleaning after sampling, it cannot be completely guaranteed that there is neither residual reaction sample nor residual cleaning solution in the entire pipeline.

(3) The sample transfer process or the sample receiving device adopts more complicated mechanical devices such as a turntable or a three-dimensional moving mechanism, which increases the dead time of sample sampling, that is, the time that is used for the movement of the mechanical device and cannot be used to monitor the reaction, making the reaction process The sampling interval becomes longer, which is not conducive to investigating the initial and most critical stage of the chemical reaction.

(4) The sampling volume in the experiment is difficult to control. At present, plunger pumps or quantitative loops can be used, which are more susceptible to contamination by residual liquid. In addition, the volume of the quantitative loop is generally small, which is not conducive to experiments with larger sample volumes.

(5) Samples need to be preserved under certain conditions after collection, especially the conditions such as protection from light, temperature, and atmosphere. Currently, there are few corresponding equipment.

Summary of the invention

In view of the above-mentioned defects in the prior art, the present invention proposes an intelligent chemical reaction device and a sampling method, which can realize the effects of timing sampling, high sampling accuracy, automatic placement after sampling, and reasonable sampling time.

The intelligent chemical reaction device of the present invention includes a housing, a sampling temporary storage chamber and a reaction stirring chamber which are located in the housing and are divided by partitions. A number of regularly arranged peristaltic pumps are installed on the top of the sampling temporary storage chamber. At least one placement rack is placed in the cavity under the pump, and a number of liquid level sensors are installed on the placement rack to detect the liquid level of the sampling test tube. The side of the sampling temporary storage room is provided with a sealed door I, which is provided on the sealed door I There is an observation window I; the top of the reaction mixing chamber is equipped with a light source composed of several UV lamps and several fluorescent lamps, and an automatic stirrer is placed in the cavity below the light source. The automatic stirrer includes a water bath container, and a heating tube and a heating tube located in the water bath container. Temperature sensor, a reaction vessel is placed in the water bath container, a sealed door II is arranged on the side of the reaction mixing chamber, an observation window II is arranged on the sealed door II, and an elastic valve for easy pipette insertion; the peristaltic pumps are respectively connected by hoses The sampling test tube and the reaction container, and the hose is fixed above the reaction container by a pipe clamp on the side wall of the sampling temporary storage chamber; the outer surface of the shell is provided with a timing display board.

Preferably, the timing display board includes a controller and a timer, the controller is respectively connected to an automatic stirrer, a light source, a peristaltic pump, a timer and a liquid level sensor, the controller controls the stirring speed and duration of the automatic stirrer, and controls the light source Switching time and duration; the controller turns on the peristaltic pump in turn through the timer, and feeds back the peristaltic pump to the controller through the liquid level sensor to turn off the peristaltic pump.

Preferably, the side of the housing is provided with a gas pipe I and a gas pipe II, the gas pipe I is connected to the outer joint I of the sampling temporary storage chamber, the gas pipe II is connected to the outer joint II of the reaction stirring chamber, and the gas pipe I and the gas pipe II are connected to the gas The air inlet pipeline is connected, and a one-way valve is opened between the air pipe I, the air pipe II and the air inlet pipe.

Preferably, the side wall of the water bath container of the automatic stirrer is further provided with a circulation port I and a circulation port II, and the water bath container is connected to the thermostat through the circulation port I and the circulation port II.

Preferably, the peristaltic pump includes a pump body, a liquid inlet and a liquid outlet. The pump body makes the tube sample move along the liquid inlet to the liquid outlet by squeezing; each peristaltic pump corresponds to one sampling test tube, at least one The peristaltic pump corresponds to a timer.

The sampling method of the intelligent chemical reaction device of the present invention includes the following steps:

S1: Acquisition of sampling parameters: sampling parameters include reaction type R, reaction time length T, reaction degree P, and sampling point N, including the following small steps:

S11: Before the experiment, the sampling point N is selected as n, and the sampling time (t1, t2,..., tn) of the above n sampling points, where the value of tn is required to meet the requirements of the degree of reaction P;

S12: Construct an experimental result graph with concentration on the ordinate and time on the abscissa, mark the measured concentrations corresponding to tn sampling points in the experimental result graph, and fit the tn values;

S13: According to the fitted curve, use the values of time and concentration to obtain the slope Slope, thereby inferring the reaction time T:

S14: According to the fitted curve, judge whether the reaction type R is a zero-order reaction or a first-order reaction;

If the curve is a straight line, the reaction type R is a zero-order reaction, and step S2 is entered. At this time, the reaction time is T:

If the curve is a curve, the reaction type R is a first-order reaction, and step S3 is entered. At this time, the reaction time T:

S2: Sampling of the zero-order reaction: the reaction time T is obtained from S1, the reaction degree P is usually selected as the sampling concentration of 70%-99%, and the sampling point N is not less than 8, then the sampling time T0 of the zero-order reaction is:

S3: Sampling of the first-level reaction: the reaction time T is obtained from S1, the reaction degree P is usually selected as the sampling concentration of 70%-99%, and the sampling point N is not less than 8, then the sampling time T1 of the first-level reaction is:

S4: Sampling time adjustment: The chemical reaction automatically generates the sampling time according to formula (3) and formula (4). When the sampling time does not meet the specifications, it is adjusted by increasing or decreasing the sampling point and actively modifying the sampling time.

7. The sampling method of an intelligent chemical reaction device according to claim 6, wherein in the step S1, the reaction type R is divided into a zero-order reaction and a first-order reaction, wherein:

The zero-order reaction has the following relationship between _{the concentration C t} at the sampling time t and the initial concentration C _0:

The first-order reaction has the following relationship between _{the concentration C t} at the sampling time t and the initial concentration C _0:

Preferably, in the step S11, the sampling point N is selected as n, and the value of n is at least 3, so that theoretical fitting can be performed during data processing.

Preferably, in the step S11, the reaction degree P is required, and at least P is required to reach a sampling concentration of 70%.

Preferably, in the step S4, that the sampling time does not meet the specification means that the sampling time is a time value less than the minimum sampling accuracy, and reasonable sampling is performed by adjusting it to a correction value.

The beneficial effects of the present invention are: the intelligent chemical reaction device of the present invention uses a peristaltic pump to sample samples with high sampling accuracy; uses an automatic stirrer, a timer, and a liquid level sensor to save energy in the stirring, sampling, and storage links, respectively. Manpower and material resources; using the intelligent chemical reaction sampling method of the present invention, the sampling time is controllable and the sampling time is reasonable.

Description of the drawings

Figure 1 is a cross-sectional view of the device of the present invention.

Fig. 2 is a left side view of the sampling temporary storage chamber in an open state.

Fig. 3 is a left side view of the sampling temporary storage chamber in a closed state.

Fig. 4 is a front view of the open state of the reaction stirring chamber.

Fig. 5 is a front view of the closed state of the reaction stirring chamber.

Fig. 6 is a schematic connection diagram of the device of the present invention.

Figure 7 is a cross-sectional view of the peristaltic pump of the device of the present invention.

Figures 8(a)-8(d) are fitted curve diagrams of each stage of the zero-order reaction of the method of the present invention.

Figures 9(a)-9(d) are fitted curve diagrams of each stage of the first-order reaction of the method of the present invention.

In the picture: 1. Shell; 11. Timing display board; 12. Trachea I; 13, Trachea II; 2. Partition; 3. Sampling temporary storage room; 31, External connector I; 32, Peristaltic pump; 321, Pump body 322. Liquid inlet; 323. Liquid outlet; 33. Liquid level sensor; 34. Place rack; 35. Sampling test tube; 36. Observation window Ⅰ; 37. Sealed door Ⅰ; 4. Reaction stirring chamber; 41. Outside Connector II; 42, tube clamp; 43, light source; 44, elastic valve; 45, pipette; 46, observation window II; 47, sealed door II; 48, hook; 5. automatic stirrer; 51, heating tube and Temperature sensor; 52, water bath container; 53, reaction container; 6, thermostat; 61, circulation port I; 62, circulation port II.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

Example 1:

As shown in Figures 1 to 7, the intelligent chemical reaction device, the intelligent chemical reaction device of the present invention, includes a housing 1, and a sampling temporary storage chamber 3 and reaction stirring located in the housing 1 and divided by partitions 2 Room 4, a number of regularly arranged peristaltic pumps 32 are installed on the top of the sampling temporary storage room 3, at least one placing rack 34 is placed in the cavity below the peristaltic pump 32, and several test tubes 35 for testing and sampling are installed on the placing rack 34 For the liquid level sensor 33, a sealed door I 37 is arranged on the side of the sampling temporary storage chamber 3, and an observation window I 36 is arranged on the sealed door I 37; a light source composed of a number of UV lamps and a number of fluorescent lamps is installed on the top of the reaction stirring chamber 4 43. An automatic stirrer 5 is placed in the cavity under the light source 43. The automatic stirrer 5 includes a water bath container 52, a heating tube and a temperature sensor 51 located in the water bath container 52, and a reaction container 53 is placed in the water bath container 52 for reaction stirring. The side of the chamber 4 is provided with a sealed door Ⅱ47, and an observation window Ⅱ46 is provided on the sealed door Ⅱ47, and an elastic valve 44 that facilitates the insertion of the pipette 45; the peristaltic pump 32 is connected to the sampling test tube 35 and the reaction container 53 through a flexible hose. The tube is fixed above the reaction vessel 53 by a tube clamp 42 located on the side wall of the sampling temporary storage chamber 3; the outer surface of the housing 1 is provided with a timing display panel 11.

The principle of the present invention is: the timing display board 11 includes a controller and a timer, the controller is respectively connected to the automatic stirrer 5, the light source 43, the peristaltic pump 32, the timer and the liquid level sensor 33, and the controller controls the automatic stirrer 5. The stirring speed and duration of the light source 43 are controlled by the on-off time and duration of the light source 43; the controller turns on the peristaltic pump 32 sequentially through a timer, and feeds back the peristaltic pump 32 through the liquid level sensor 33 to the controller to turn off the peristaltic pump 32.

First of all, regarding the housing 1, as shown in FIG. 1. The housing 1 is arranged in a rectangular parallelepiped as a whole, and a timing display board 11 is installed on the top of the rectangular parallelepiped, and the timing display board 11 has a built-in controller and a timer. The housing 1 is provided with a partition 2 which is divided into multiple parts by the partition 2 and includes at least two cavities, that is, at least a sampling temporary storage chamber 3 and a reaction stirring chamber 4. A number of holes are opened on the partition plate 2 for placing a number of hoses connecting the sampling temporary storage chamber 3 and the reaction stirring chamber 4. A gas pipe Ⅰ12 and a gas pipe Ⅱ13 are provided on the side wall of the housing 1 to pass gas. The gas pipe Ⅰ12 is connected to the external joint Ⅰ31 of the sampling temporary storage chamber 3, and the gas pipe Ⅱ13 is connected to the external joint Ⅱ41 of the reaction stirring chamber 4; The gas can be an inert gas such as nitrogen and argon to protect the reaction from being affected by oxygen, or a reactive gas such as oxygen and chlorine to control specific reaction conditions.

Secondly, regarding the sampling temporary storage room 3, as shown in Figs. 2 to 3. The sampling temporary storage chamber 3 is located at the rear of the housing 1 and mainly includes a peristaltic pump 32 and a placing rack 34. The advantage of the peristaltic pump 32 is that it can avoid the problem of sample residue during the sampling process. It includes a pump body 321, a liquid inlet 322, and a liquid outlet 323. As shown in FIG. 7, the pump body 321 squeezes the sample along the tube. The liquid inlet 322 moves in the direction of the liquid outlet 323. In fact, the sample does not make too much contact with the peristaltic pump 32, which is obviously different from other driven pumps. The placing rack 34 is divided into two rows, each row is provided with a number of sampling test tubes 35, and a liquid level sensor 33 is installed in the middle of the placing rack 34 corresponding to each sampling test tube 35, that is, the number of the liquid level sensor 33 and the number of sampling test tubes 35 are the same. . The number of peristaltic pumps 32 is also consistent with the number of sampling test tubes 35, and one peristaltic pump 32 is required to be connected to one sampling test tube 35 for one-to-one correspondence. Through one-to-one correspondence, the sampling peristaltic pump 32 stops using the sample after placing the sample in the sampling test tube 35, so as to prevent the sample remaining in the hose from contaminating the next sampling immediately. On the side of the sampling temporary storage room 3 is opened a sealed door I 37 that is larger in size than the rack 34 on which the sampling test tube 35 is placed. In order to facilitate the observation of the sampling state from the outside, a brown door is also opened on the sealed door I 37. Transparent viewing window. The reason for the brown color is to prevent the external light source 43 from affecting the sample in the sampling test tube 35.

Again, regarding the reaction stirring chamber 4, as shown in Figs. 4 to 5. The reaction stirring chamber 4 is located at the front of the housing 1 and mainly includes a light source 43 and an automatic stirrer 5. The light source 43 is a composite structure, including at least UV lamps and fluorescent lamps, to meet the requirements of different experimental environments; the light source 43 is located directly above the reaction vessel 53 of the automatic stirrer 5. A sealed door Ⅱ47 is opened in the front of the reaction stirring chamber 4, when a test reaction is required, a sealed environment is created by closing the sealed door Ⅱ47 to avoid external interference. The automatic stirrer 5 usually adopts a common magnetic stirrer. The automatic stirrer 5 includes a bottom plate with a temperature sensor and a heater, and a water bath container 52 is provided on the bottom plate. When the reaction requires different reaction temperatures, it can be achieved by controlling the heating time of the heater through the controller. A reaction container 53 is placed in the water bath container 52, and a hose connected to the peristaltic pump 32 is placed in the reaction container 53. The hose connecting the peristaltic pump 32 needs to be fixed above the reaction vessel 53, so two hooks 48 are provided on the side wall of the reaction stirring chamber 4, and a horizontal pipe clamp 42 is fixed by the hooks 48, and the pipe clamp 42 is provided with There are several grooves. Through the fixing effect of the grooves, the direction of the horizontal extension of the partition plate 2 is changed to face the inside of the reaction vessel 53. The above-mentioned sealed door II 47 is also provided with an observation window II 46, and the observation window II 46 is also made of brown transparent glass to reduce the influence of the external light source 43 on the reaction. At the same time, due to the need to add a specific catalyst through the pipette gun 45 during the experiment, an elastic valve 44 is provided on the observation window or the sealed door Ⅱ 47, which is tilted downwards, and the elastic valve 44 is pushed inward by the pipette gun 45. Turn it on, and reset under the action of a spring after the pipette gun 45 is withdrawn. The inclination direction of the elastic valve 44 satisfies that the pipette gun 45 can extend directly above the reaction container 53 along the inclined channel.

Finally, regarding the thermostat 6, as shown in Fig. 6. In the case that the heating tube of the automatic stirrer 5 itself cannot meet the requirements, the temperature controller 6 is used to achieve precise adjustment of the temperature. Especially when low temperature is achieved quickly. A circulation port I 61 and a circulation port II 62 are opened on the side of the water bath container 52 of the automatic stirrer 5, and the water bath container 52 is connected to the thermostat 6 through the circulation port I 61 and the circulation port II 62. The thermostat 6 can be connected to the controller via a serial port as required, and the temperature can be adjusted by the controller.

The use process of the intelligent chemical reaction device of the present invention is as follows: According to the reaction type R, the reaction time T, the reaction degree P and the sampling point N, set the stirring time of the automatic stirrer and the corresponding temperature, and set the sampling of the timer Time and sampling times, the sampling test tube 35 on the placing rack 34 moves to the corresponding peristaltic pump 32 through the movable platform. For example, when the first sampling time t1 arrives, the timer controls the corresponding peristaltic pump 32 to start, and one end of the peristaltic pump 32 extends into the reaction container 53 to sample the sample into the sampling test tube 35 through the liquid inlet 322 until all sampling is completed. ; At this time, the sampling test tube 35 on the placing rack 34 stores the samples of each sampling time, which are temporarily stored inside the device for personnel to take.

It should be noted:

The automatic stirrer 5 can choose a common mechanical stirrer. The reaction vessel 53 is usually selected as a beaker. The timer, in conjunction with the peristaltic pump 32, delivers the sample to be sampled into the sampling test tube 35 at regular intervals; the timer is selected as a time relay. Timed sampling by timer, the sampling time is controllable and the sampling time is reasonable, saving manpower and material resources in the sampling process.

When the experiment is completed, open the sealed door I and sealed door II at the same time, pull the two ends of the hose out of the cavity respectively, put all the ends in clean water or a specific cleaning solution, such as acid-base solution, and turn on the peristaltic pump to repeatedly cycle and rinse The cleaning work can be completed, which is simple and convenient.

Example 2:

The sampling method of the intelligent chemical reaction device of the present invention includes the following steps:

S1: Acquisition of sampling parameters: sampling parameters include reaction type R, reaction time length T, reaction degree P, and sampling point N, including the following small steps:

S11: Before the experiment, the sampling point N is selected as n, and the sampling time (t1, t2,..., tn) of the above n sampling points, where the value of tn is required to meet the requirements of the degree of reaction P;

S12: Construct an experimental result graph with concentration on the ordinate and time on the abscissa, mark the measured concentrations corresponding to tn sampling points in the experimental result graph, and fit the tn values;

S13: According to the fitted curve, use the values of time and concentration to obtain the slope Slope, thereby inferring the reaction time T:

S14: According to the fitted curve, judge whether the reaction type R is a zero-order reaction or a first-order reaction;

If the curve is a straight line, the reaction type R is a zero-order reaction, and step S2 is entered. At this time, the reaction time is T:

If the curve is a curve, the reaction type R is a first-order reaction, and step S3 is entered. At this time, the reaction time T:

S2: Sampling of the zero-order reaction: the reaction time T is obtained from S1, the reaction degree P is usually selected as the sampling concentration of 70%-99%, and the sampling point N is not less than 8, then the sampling time T0 of the zero-order reaction is:

S3: Sampling of the first-level reaction: the reaction time T is obtained from S1, the reaction degree P is usually selected as the sampling concentration of 70%-99%, and the sampling point N is not less than 8, then the sampling time T1 of the first-level reaction is:

S4: Sampling time adjustment: The chemical reaction automatically generates the sampling time according to formula (3) and formula (4). When the sampling time does not meet the specifications, it is adjusted by increasing or decreasing the sampling point and actively modifying the sampling time.

Preferably, in the step S1, the reaction type R is divided into zero-order reaction and first-order reaction, wherein:

The zero-order reaction has the following relationship between _{the concentration C t} at the sampling time t and the initial concentration C _0:

The first-order reaction has the following relationship between _{the concentration C t} at the sampling time t and the initial concentration C _0:

It should be noted:

Response time Time T: An initial assumption is required for an unknown response, for example, it is assumed to be 1h=60min=3600s. Note the unit here, and it can be adjusted to s.

Percentage P: Generally, it can be considered that when the reaction reaches 70%, the entire reaction process can be reflected, and when it reaches 90%, the entire reaction will be monitored; if you need to more accurately examine the changes in the late stage of the reaction, you can set it to 95%, 98 %, 99%, or even 100%, etc.

Data Density Number N: The density of the sampling points, such as 8 or 10 samplings in the entire reaction; note that the theoretical sampling number of the sampling points is at least 3 times, so that the theoretical fitting process can be performed in the later data processing; but the theoretical sampling number is actual There are still few applications, and it is difficult to achieve accurate experimental results. It is generally considered that at least 8 times.

Example 3:

As shown in Fig. 8(a) to Fig. 9(d), the sampling method of the smart chemical reaction device according to the present invention will be described below through specific cases.

1. Zero-order reaction:

In the initial reaction, that is, the pre-experiment, use manual correction of the sampling point. For the above reaction, set N to 4. At this time, the default value of the sampling point is (0min, 840s, 1680s, 2520s), so you can reduce the sampling point , Thereby reducing the number of subsequent analysis and testing. Although reducing the sampling points reduces the accuracy of monitoring the reaction process, the important parameters T and P of the reaction can be estimated at a lower cost, so as to facilitate manual correction and setting of more accurate sampling points in subsequent experiments. As shown in Figure 8(a), only 4 points are needed to get an overview of the reaction. In particular, when the results reflected by the experimental data exceed 50% of the total reaction progress, the total reaction time T can be more positively estimated from the slope Slope in Figure 8(a). The specific formula is as follows:

It can be seen from the above that the manual correction sampling point described here is limited to operators who fully understand the performance and principle of the equipment under specific circumstances. Generally, manual settings are not required. The required values can be obtained only by the default values of the instrument itself. The sampling points are shown in Figure 8(b). When performing an experiment, through the same experimental process as in Figure 4, T can be determined preliminarily, so as to set parameters as needed to obtain data results similar to those in Figure 8(b) or Figure 8(d).

Through the determination of the above parameters, the default value of the sampling point can be calculated by the following formula:

As mentioned above, suppose (T=3600s, P=70%, N=8), as shown in Table 1.

Table 1 Sampling parameter table of zero-order reaction

The sampling time is (0s, 360s, 720s, 1080s, 1440s, 1800s, 2160s, 2520s), if converted to minutes, it is (0min, 6min, 12min, 18min, 24min, 30min, 36min, 42min), and the default The value automatically obtains the sampling time through the pre-set formula, and the equipment can operate accordingly, as shown in Table 2. As shown in Figure 8(b), the photolysis process of tetracycline, an organic pollutant in the environment, can be tested using this equipment and method.

Table 2 Automatic sampling parameter table for zero-order reaction

Sampling point N	Sampling time
Sampling point 1	0min
Sampling point 2	6min
Sampling point 3	12min
Sampling point 4	18min
Sampling point 5	24min
Sampling point 6	30min
Sampling point 7	36min
Sampling point 8	42min

However, for technicians with rich work experience and skilled equipment use, the sampling time can be manually corrected, so that on the basis of basically not affecting the experimental results, the sampling time that is more familiar to humans rather than the calculation in pure formula is relatively non-integer point. The sampling time can be modified to (0min, 5min, 10min, 20min, 25min, 30min, 35min, 40min), as shown in Table 3. The experimental results are shown in Figure 8(c).

Table 3 Correction value-parameter table of zero-order reaction

Sampling point N	Sampling time	Correction value one
Sampling point 1	0min	0min
Sampling point 2	6min	5min

Sampling point 3	12min	10min
Sampling point 4	18min	20min
Sampling point 5	24min	25min
Sampling point 6	30min	30min
Sampling point 7	36min	35min
Sampling point 8	42min	40min

It can be seen that the correction is closer to the human habit of using time, but there are also shortcomings, that is, the 15min sampling point is missing when all the steps are 5min. In addition, the total reaction time is also reduced from 42min to 40min, which may cause The reaction did not reach 70%. Therefore, you can continue to modify the parameter N=10, and then manually modify the sampling time to (0min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min), by adding 15min, 45min two points to make the sampling time more Reasonable, as shown in Table 4. The experimental results are shown in Figure 8(d).

Table 4 Two-parameter table of correction values for zero-order reaction

Sampling point N	Sampling time	Correction value one	Correction value two
Sampling point 1	0min	0min	0min
Sampling point 2	6min	5min	5min
Sampling point 3	12min	10min	10min
Sampling point 4	18min	20min	15min
Sampling point 5	24min	25min	20min
Sampling point 6	30min	30min	25min
Sampling point 7	36min	35min	30min
Sampling point 8	42min	40min	35min
Sampling point 9	-	-	40min
Sampling point 10	-	-	45min

Second, the first reaction:

Also for the initial reaction, you can manually modify the sampling time during the preliminary experiment. For the above reaction, you can set N to 4. At this time, the default value of the sampling time is (0min, 30min, 60min), so you can reduce the sampling point , Thereby reducing the number of subsequent analysis and testing. Although reducing the sampling point reduces the accuracy of monitoring the reaction process, the important parameters T and P of the reaction can be estimated at a lower cost, so as to facilitate manual correction and set more accurate sampling time in subsequent experiments. As shown in Figure 8, only 4 points need to be taken to get an overview of the reaction. In particular, when the results reflected by the experimental data exceed 50% of the total reaction progress, the half-life t of the reaction can be estimated from Figure 9(a), so that the total reaction time T can be more accurately estimated (e.g., by the degree of completion of the reaction). P=90% is the standard), the specific formula is as follows:

It can be seen from the above that the manual correction sampling time described here is limited to operators who fully understand the performance and principle of the equipment under specific conditions. Generally, manual settings are not required. The required value can be obtained only by the default value of the instrument itself. The sampling time is shown in Figure 9(b). When performing an experiment, through the same experimental process as in Figure 9(a), T can be determined preliminarily, so as to set parameters as needed to obtain data results similar to Figures 9(b)-6(d).

As mentioned above, suppose (T=3600s, P=70%, N=8), as shown in Table 5.

Table 5 Sampling parameter table of the first-level reaction

The sampling time is (0s, 220s, 467s, 746s, 1069s, 1450s, 1917s, 2520s), as shown in Table 6. At this time, the default value automatically obtains the sampling time through the pre-set formula, and the device can operate accordingly. As shown in Figure 9(b), the oxidative degradation process of Quinclorac, an organic pollutant in the environment, can be tested using this equipment and method.

Table 6 Automatic sampling parameter list for the first-level reaction

Sampling point N	Sampling time
Sampling point 1	0s
Sampling point 2	220s
Sampling point 3	467s
Sampling point 4	746s
Sampling point 5	1069s
Sampling point 6	1450s
Sampling point 7	1917s
Sampling point 8	2520s

Similar to the situation of zero-order reaction, for technicians with rich work experience and skilled equipment use, the sampling time can be manually corrected, so that the sampling time that is more familiar to humans is used instead of pure formula calculations on the basis of basically not affecting the experimental results. The obtained sampling time relative to non-integer points can be modified to (0min, 5min, 10min, 15min, 20min, 25min, 30min, 40min), as shown in Table 7. The experimental results are shown in Figure 9(c).

Table 7: Correction value-parameter table for the first-order reaction

Sampling point N	Sampling time	Correction value one
Sampling point 1	0s	0min
Sampling point 2	220s	5min
Sampling point 3	467s	10min
Sampling point 4	746s	20min
Sampling point 5	1069s	25min
Sampling point 6	1450s	30min
Sampling point 7	1917s	35min
Sampling point 8	2520s	40min

It can be seen that the corrected time is closer to the human habits of using time, but there are also disadvantages, that is, the 35min sampling time is missing in the case of 5min progression, and the total reaction time is also reduced from 42min to 40min, which may cause The reaction did not reach 70%, and more importantly, the sample concentration at the initial sampling point was already less than 90%. As for the first-order reaction, the initial stage of the reaction is relatively fast, so the concentration of the sample at the initial sampling point should be 90% and above. At this time, in addition to modifying the parameter N like the zero-order reaction, and then manually modifying the sampling time, you can also manually modify the sampling time (0min, 3min, 8min, 12min, 18min, 25min, 35min, 42min) to make the sampling time more Reasonable, as shown in Figure 9(d). Of course, no matter how to manually modify the parameters, there is still a gap between the reasonableness of sampling and the default value.

Table 8: Correction value of the first-order reaction and two-parameter table

Sampling point N	Sampling time	Correction value one	Correction value two
Sampling point 1	0s	0min	0min
Sampling point 2	220s	5min	3min
Sampling point 3	467s	10min	8min
Sampling point 4	746s	20min	12min
Sampling point 5	1069s	25min	18min
Sampling point 6	1450s	30min	25min
Sampling point 7	1917s	35min	35min
Sampling point 8	2520s	40min	42min

It should be noted that the zero-order reaction and the first-order reaction described in the present invention are the most common chemical reactions. Therefore, they can be easily set by the theoretical formula proposed in the present invention, that is, the user only needs to provide the reaction type, The reaction time, reaction degree, data density and other requirements are sufficient, and there is no need to worry about the rationality of sampling in the experiment.

When encountering individual situations, that is, other types of reactions that are not common in chemical reactions, you can also change the sampling time by first selecting a close model and then manually correcting the sampling time, which is suitable for personalized experimental procedures.

The invention can be widely used in the occasion of experimental equipment, especially suitable for the occasion of chemical reaction experiment equipment.

It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply one of these entities or operations. There is any such actual relationship or order between. Moreover, the terms "include", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes those that are not explicitly listed Other elements of, or also include elements inherent to this process, method, article or equipment.

Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. And variations, the scope of the present invention is defined by the appended claims and their equivalents.

Claims (10)

1. An intelligent chemical reaction device, which is characterized by comprising a housing (1), a sampling temporary storage chamber (3) and a reaction stirring chamber (4) located in the housing (1) and divided by partitions (2), A number of regularly arranged peristaltic pumps (32) are installed on the top of the sampling temporary storage room (3). At least one placement rack (34) is placed in the cavity below the peristaltic pump (32), and a number of placement racks (34) are installed on the placement rack (34). A liquid level sensor (33) for detecting the liquid level of the sampling test tube (35), a sealed door I (37) is arranged on the side of the sampling temporary storage room (3), and an observation window I is arranged on the sealed door I (37) (36); The top of the reaction stirring chamber (4) is equipped with a light source (43) composed of a number of UV lamps and a number of fluorescent lamps, and an automatic stirrer (5) is placed in the cavity below the light source (43), and an automatic stirrer ( 5) Including a water bath container (52), a heating tube and a temperature sensor (51) located in the water bath container (52), a reaction container (53) is placed in the water bath container (52), and the reaction stirring chamber (4) is arranged on the side There is a sealed door II (47), an observation window II (46) is provided on the sealed door II (47), and an elastic valve (44) that is convenient for the insertion of the pipette gun (45); the peristaltic pumps (32) are respectively connected by hoses Sampling test tube (35) and reaction container (53), the hose is fixed above the reaction container (53) by a tube clamp (42) located on the side wall of the sampling temporary storage chamber (3); the outer surface of the housing (1) is provided with Timing display board (11).
2. The intelligent chemical reaction device according to claim 1, wherein the timing display board (11) includes a controller and a timer, and the controller is respectively connected to an automatic stirrer (5), a light source (43), and a peristaltic pump ( 32), timer and liquid level sensor (33), the controller controls the stirring speed and duration of the automatic stirrer (5), and controls the switching time and duration of the light source (43); the controller sequentially makes the peristaltic pump (32) through the timer ) Is turned on, and the peristaltic pump (32) is turned off by feedback of the liquid level sensor (33) to the controller.
3. The intelligent chemical reaction device according to claim 1, characterized in that the side of the housing (1) is provided with a trachea I (12) and a trachea II (13), and the trachea I (12) is connected to the sampling temporary storage chamber ( 3) The outer joint I (31) and the gas pipe II (13) are connected to the outer joint II (41) of the reaction stirring chamber (4), and the gas pipe I (12) and the gas pipe II (13) are respectively connected to the gas inlet pipe , One-way valves are opened between the air pipe I (12), the air pipe II (13) and the air inlet pipe.
4. The intelligent chemical reaction device according to claim 1, characterized in that the side wall of the water bath container (52) of the automatic stirrer (5) is also provided with a circulation port I (61) and a circulation port II (62) , The water bath container (52) is connected to the temperature controller (6) through the circulation port I (61) and the circulation port II (62).
5. The intelligent chemical reaction device according to claim 1, wherein the peristaltic pump (32) comprises a pump body (321), a liquid inlet (322) and a liquid outlet (323), and the pump body (321) passes Squeezing makes the tube sample move in the direction of the liquid inlet (322) to the liquid outlet (323); each peristaltic pump (32) corresponds to a sampling test tube (35), and at least one peristaltic pump (32) corresponds to a timer.
6. A sampling method based on the intelligent chemical reaction device according to any one of claims 1-5, characterized in that it comprises the following steps:

   S1: Acquisition of sampling parameters: sampling parameters include reaction type R, reaction time length T, reaction degree P, and sampling point N, including the following small steps:

   S11: Before the experiment, the sampling point N is selected as n, and the sampling time (t1, t2,..., tn) of the above n sampling points, where the value of tn is required to meet the requirements of the degree of reaction P;

   S12: Construct an experimental result graph with concentration on the ordinate and time on the abscissa, mark the measured concentrations corresponding to tn sampling points in the experimental result graph, and fit the tn values;

   S13: According to the fitted curve, use the values of time and concentration to obtain the slope Slope, thereby inferring the reaction time T:

   S14: According to the fitted curve, judge whether the reaction type R is a zero-order reaction or a first-order reaction;

   If the curve is a straight line, the reaction type R is a zero-order reaction, and step S2 is entered. At this time, the reaction time is T:

   

   If the curve is a curve, the reaction type R is a first-order reaction, and step S3 is entered. At this time, the reaction time T:

   

   S2: Sampling of the zero-order reaction: the reaction time T is obtained from S1, the reaction degree P is usually selected as the sampling concentration of 70%-99%, and the sampling point N is not less than 8, then the sampling time T0 of the zero-order reaction is:

   

   Where N is an integer greater than 1 (3)

   S3: Sampling of the first-level reaction: the reaction time T is obtained from S1, the reaction degree P is usually selected as the sampling concentration of 70%-99%, and the sampling point N is not less than 8, then the sampling time T1 of the first-level reaction is:

   

   Where N is an integer greater than 1 (4)

   S4: Sampling time adjustment: The chemical reaction automatically generates the sampling time according to formula (3) and formula (4). When the sampling time does not meet the specifications, it is adjusted by increasing or decreasing the sampling point and actively modifying the sampling time.
7. The sampling method for a smart chemical reaction device according to claim 6, wherein in the step S1, the reaction type R is divided into zero-order reaction and first-order reaction, wherein:

   The zero-order reaction has the following relationship between _{the concentration C t} at the sampling time t and the initial concentration C _0:

   

   The first-order reaction has the following relationship between _{the concentration C t} at the sampling time t and the initial concentration C _0:

   
8. The sampling method of the intelligent chemical reaction device according to claim 6, wherein in the step S11, the sampling point N is selected as n, and the value of n is at least 3, so that theoretical fitting can be performed during data processing.
9. The sampling method of the intelligent chemical reaction device according to claim 6, characterized in that, in the step S11, the reaction degree P is required, and at least P is required to reach a sampling concentration of 70%.
10. The sampling method of the intelligent chemical reaction device according to claim 6, wherein in the step S4, the sampling time does not meet the specification means that the sampling time is less than the minimum sampling accuracy time value, which is adjusted to a correction value Take reasonable sampling.

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