Constant-temperature environment automatic dripping and heating device

Abstract

The invention discloses a constant-temperature environment automatic titration heat measuring device which comprises a constant-temperature temperature control system, a heat measuring system, an automatic titration system and a controller, and the constant-temperature temperature control system comprises a constant-temperature cavity for containing a constant-temperature solution and a temperature measuring device for detecting the temperature of the constant-temperature solution; the calorimetric system comprises a calorimetric cavity, a reaction container and a calorimeter, the calorimetric cavity is arranged in the constant-temperature cavity, the reaction container and the calorimeter are arranged in the calorimetric cavity, the calorimetric cavity is used for being wrapped by the constant-temperature solution, the reaction container is connected to the calorimetric cavity in a heat insulation mode and used for containing the reaction solution, and the calorimeter is used for measuring the temperature of the reaction solution; the automatic titration system comprises a titration container communicated with the reaction container, a liquid storage container communicated with the titration container, a control pump set arranged between the titration container and the liquid storage container, and a discharge pump set communicated with the reaction container and the outside.

Description

Technical Field

[0001] The invention relates to the field of microcalorimeters, in particular to an automatic titration calorimeter in a constant temperature environment. Background Art

[0002] Isothermal titration calorimetry (ITC) is an important method for studying biothermodynamics and biokinetics developed in the past three decades. It continuously and accurately monitors and records the calorimetric curve of a changing process through a highly sensitive and highly automated microcalorimeter, providing thermodynamic and kinetic information in situ, online and non-destructively. The complete thermodynamic parameters of biomolecular interactions can be obtained through isothermal titration calorimetry, including binding constant, number of binding sites, molar binding enthalpy, molar binding entropy, molar constant-pressure heat capacity and kinetic parameters (such as enzyme activity, enzymatic reaction Michaelis constant and enzyme turnover number), etc. Isothermal titration calorimetry has a wide range of applications and is suitable for physical chemistry, biochemistry, biophysics, chemical biology, life sciences, pharmacology, soil science, colloid chemistry and other disciplines.

[0003] In the related art, the mainstream isothermal titration calorimeters are all thermal conductivity differential calorimeters, whose constant temperature medium is a metal block and air, and a thermopile is used to measure the relationship curve between the temperature difference and time of the calorimeter. Its structure is complex, difficult to manufacture, and expensive. In addition, the constant temperature environment titration calorimeter device in the related art is a manual titration, which requires operators to operate, increasing the burden on operators, and the titration calorimetry efficiency is low. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides a constant temperature environment automatic titration calorimeter, which can improve the titration calorimetry efficiency.

[0005] The constant temperature environment automatic titration calorimeter according to an embodiment of the present invention comprises: A constant temperature control system, comprising a constant temperature cavity for containing a constant temperature solution and a temperature measuring device for detecting the temperature of the constant temperature solution; A calorimetric system, comprising a calorimetric cavity disposed in the constant temperature cavity, a reaction container and a calorimeter both disposed in the calorimetric cavity, wherein the calorimetric cavity is used to be coated with the constant temperature solution, the reaction container is thermally insulatedly connected to the calorimetric cavity and is used to contain the reaction solution, and the calorimeter is used to measure the temperature of the reaction solution; An automatic titration system, comprising a titration container connected to the reaction container, a liquid storage container connected to the titration container, a control pump group arranged between the titration container and the liquid storage container, and a discharge pump group connected to the reaction container and the outside, wherein the liquid storage container is used to store a solution, the titration container is used to suck out the solution in the liquid storage container or discharge the solution into the reaction container, the control pump group has an open state and a closed state, and the discharge pump group is used to discharge the solution in the reaction container; A controller, electrically connected to the control pump group; Wherein, the controller is configured to: when the control pump group is in the open state, control the control pump group to connect the liquid storage container and the titration container, and control the control pump group to transport the solution in the liquid storage container to the titration container; in the closed state, control the control pump group to disconnect the liquid storage container and the titration container.

[0006] The constant temperature environment automatic titration calorimeter according to the first embodiment of the present invention has at least the following beneficial effects: 1. The calorimetric cavity is coated with a constant temperature solution, which makes the calorimetric cavity more isolated from the outside temperature and the measurement more accurate; 2. Through the cooperation of the control pump group and the discharge pump group in the automatic titration system, the control pump group can automatically transport the solution in the liquid storage container to the titration container, and then cooperate with the suction method of the titration container itself to make the titration container full of solution, and the titration container then discharges the solution into the reaction container. When the solution is a cleaning liquid, the liquid in the reaction container can be extracted by the discharge pump group to achieve automatic cleaning of the titration container and the reaction container. When the solution is a reaction solution, the reaction solution is directly added to the reaction container. When the solution is a sample solution, the sample solution is titrated into the reaction solution through the titration container to complete the automatic titration. The sample solution reacts with the reaction solution to release or absorb heat, and the calorimeter can measure the changed calorific value to achieve automatic titration calorimetry and improve the efficiency of titration calorimetry. 3. After the sample solution reacts with the reaction solution, all the solutions are discharged through the discharge pump group, and then cleaned again with the cleaning solution to carry out the next titration calorimetry of the sample solution and the reaction solution, so as to realize continuous automatic titration calorimetry, which is more efficient and saves manpower.

[0007] According to some embodiments of the present invention, the liquid storage containers are provided in plurality, the control pump groups are provided in plurality, the plurality of liquid storage containers are capable of storing different solutions, one control pump group corresponds to one liquid storage container, and is used to control the connection between the corresponding liquid storage container and the titration container.

[0008] According to some embodiments of the present invention, the control pump group includes a delivery pipe connecting the liquid storage container and the titration container, a control valve and a delivery pump both arranged on the delivery pipe, the delivery pump is used to pump the solution in the liquid storage container, the control valve is used to control the on-off of the delivery pipe, and the control valve and the delivery pump are both electrically connected to the controller.

[0009] According to some embodiments of the present invention, the automatic titration system further comprises a transfer assembly, the transfer assembly comprising a bracket and a moving part connected to the bracket by transmission, the moving part can move along a first direction, the moving part is connected to the titration container, and can drive the titration container to move to a first position or a second position along the first direction, and the transfer assembly is electrically connected to the controller; Wherein, the controller is configured to: control the transfer component to drive the titration container to move along the first direction to the first position, the titration container is located above the reaction container and is separated from the calorimetric cavity; control the transfer component to drive the titration container to move along the first direction from the first position to the second position, a portion of the titration container is inserted into the reaction container, and the reaction container is sealed and insulated together with the calorimetric cavity.

[0010] According to some embodiments of the present invention, the automatic titration system further comprises a collection container, the moving part can rotate around the circumference of the bracket, and the transfer assembly can also drive the titration container to rotate from the first position to a third position along the circumference of the bracket; Wherein, the controller is configured to: control the transfer component to drive the titration container to rotate from the first position to the third position along the circumference of the bracket, and the titration container moves to the top of the collection container and communicates with the collection container.

[0011] According to some embodiments of the present invention, the titration container includes an outer shell, a syringe body partially disposed within the outer shell, a needle connected to the syringe body and extending out of the outer shell, a plunger disposed within the outer shell and partially located within the syringe body, an injection drive source disposed within the outer shell and transmission-connected to the plunger, and a valve group disposed between the syringe body and the needle, the valve group being connected to the liquid storage container, and the injection drive source being electrically connected to the controller.

[0012] According to some embodiments of the present invention, the valve group includes a third control valve disposed between the titration container and the control pump group and a fourth control valve disposed between the titration container and the reaction container; The automatic titration system is configured as follows: when the control pump group is in an on state and negative pressure is formed in the titration container, the third control valve is opened, the fourth control valve is closed, and the solution in the liquid storage container enters the titration container; when the control pump group is in a off state and the pressure in the titration container increases, the third control valve is closed, the fourth control valve is opened, and the solution in the titration container is injected into the reaction container.

[0013] According to some embodiments of the present invention, the automatic titration system further comprises an overflow control valve connected to an end of the injection tube body away from the needle, a collection container connected to the overflow control valve, and an overflow sensor; Wherein, the controller is configured to: when the overflow sensor detects that the water in the overflow control valve overflows into the collection container, control the overflow control valve to close; when the control pump group is in an on state, control the overflow control valve to open.

[0014] According to some embodiments of the present invention, the automatic titration system further comprises a first stopper and a second stopper which are arranged inside the outer shell and located at an end of the injection tube body away from the needle, the first stopper and the second stopper are arranged in sequence along a direction in which the injection tube body is away from the needle, the first stopper and the second stopper are both used to detect the end of the plunger away from the needle, and are both connected to the controller; Wherein, the controller is configured to: when the first stopper does not detect the plunger, control the plunger to stop moving toward the needle; when the second stopper detects the plunger, control the plunger to stop moving in a direction away from the needle.

[0015] According to some embodiments of the present invention, the titration container further includes a dry gas source, a dry pipe connected between the titration container and the dry gas source, and a dry valve provided on the dry pipe, the dry gas source is used to transport dry gas, the dry valve is electrically connected to the controller, and is used to control the on and off of the dry pipe.

[0016] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein: Figure 1 A schematic diagram of the structure of a constant temperature environment automatic titration calorimeter according to an embodiment of the present invention; Figure 2A schematic diagram of the structure of an automatic titration system in a constant temperature environment automatic titration calorimeter according to an embodiment of the present invention; Figure 3 It is a structural schematic diagram of the third control valve and the fourth control valve of the automatic titration system in the constant temperature environment automatic titration calorimeter according to one embodiment of the present invention; Figure 4 It is a structural schematic diagram of a calorimetric system in a constant temperature environment automatic titration calorimeter according to an embodiment of the present invention; Figure 5 A schematic diagram of the structure of a constant temperature control system in a constant temperature environment automatic titration calorimeter according to an embodiment of the present invention; Figure 6 The present invention is a schematic diagram of the structure of the cooling pipeline of the constant temperature control system in the constant temperature environment automatic titration calorimeter according to an embodiment of the present invention.

[0018] Figure Number: Constant temperature control system 100; constant temperature cavity 110; temperature measuring device 120; heating element 130; cooling pipeline 140; cooling source 141; cold end heat conducting element 142; cooling pipe 143; cooling pipe 144; stirring element 150; temperature controller 160; Calorimetric system 200; calorimetric chamber 210; exhaust control valve 211; reaction container 220; calorimeter 230; heat exchanger 240; first heat exchange pipe 241; first control valve 242; second control valve 243; drive pump 244; electric heating element 250; Automatic titration system 300; titration container 310; outer shell 311; injection tube 312; needle 313; plunger 314; injection drive source 315; sealing layer 316; liquid storage container 320; distilled water container 321; buffer container 322; reaction solution container 323; sample solution container 324; third control valve 330; first valve body 331; first spring 332; first movable plug 333; first joint 334; fourth control valve 340; second valve body 341; second spring 342; second movable plug 343 ; second connector 344; control pump group 350; distilled water control valve 351; distilled water delivery pump 352; buffer control valve 353; buffer delivery pump 354; reaction solution control valve 355; reaction solution delivery pump 356; sample solution control valve 357; sample solution delivery pump 358; first master control valve 359; second master control valve 35A; discharge pump group 360; discharge pipeline 361; transfer assembly 370; bracket 371; moving part 372; overflow control valve 380; collection container 390; dry gas source 3A0; Controller 400. DETAILED DESCRIPTION

[0019] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and cannot be understood as limiting the present invention.

[0020] In the description of the present invention, it should be understood that descriptions involving orientation, such as orientation or positional relationship indicated as up, down, etc., are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0021] In the description of the present invention, "a number" refers to one or more than one, and "a plurality" refers to two or more than two. If there is a description of "first" or "second", it is only used for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the order of the indicated technical features.

[0022] In the description of the present invention, unless otherwise clearly defined, terms such as setting, installing, connecting, etc. should be understood in a broad sense, and technicians in the relevant technical field can reasonably determine the specific meanings of the above terms in the present invention based on the specific content of the technical solution.

[0023] Reference Figures 1 to 6As shown, the first embodiment of the present invention proposes a constant temperature environment automatic titration calorimeter, the constant temperature environment automatic titration calorimeter, comprising: a constant temperature control system 100, a calorimetric system 200, an automatic titration system 300 and a controller 400, the constant temperature control system 100 comprises a constant temperature cavity 110 for holding a constant temperature solution and a thermometer 120 for detecting the temperature of the constant temperature solution; the calorimetric system 200 comprises a calorimetric cavity 210 disposed in the constant temperature cavity 110, a reaction container 220 and a calorimeter 230 both disposed in the calorimetric cavity 210, the calorimetric cavity 210 is used to be coated with the constant temperature solution, the reaction container 220 is thermally insulatedly connected to the calorimetric cavity 210, and is used to hold a reaction solution, and the calorimeter 230 is used to measure the temperature of the reaction solution; the automatic titration system 300 comprises a titration container 310 connected to the reaction container 220, and a liquid storage container 120 connected to the titration container 310. The container 320, the control pump group 350 arranged between the titration container 310 and the liquid storage container 320, and the discharge pump group 360 connecting the reaction container 220 and the outside, the liquid storage container 320 is used to store the solution, the titration container 310 is used to suck out the solution in the liquid storage container 320 or discharge the solution into the reaction container 220, the control pump group 350 has an open state and a closed state, and the discharge pump group 360 is used to discharge the solution in the reaction container 220; the controller 400 is electrically connected to the control pump group 350; wherein the controller 400 is configured to: when the control pump group 350 is in the open state, control the control pump group 350 to connect the liquid storage container 320 and the titration container 310, and control the control pump group 350 to transport the solution in the liquid storage container 320 to the titration container 310; in the closed state, control the control pump group 350 to disconnect the liquid storage container 320 and the titration container 310.

[0024] It is worth understanding that by coating the calorimetric cavity 210 with a constant temperature solution, the calorimetric cavity 210 is better isolated from the outside temperature, and the measurement is more accurate; by cooperating with the control pump group 350 and the discharge pump group 360 in the automatic titration system 300, the control pump group 350 can automatically transport the solution in the liquid storage container 320 to the titration container 310, and then cooperate with the suction method of the titration container 310 itself, so that the titration container 310 can be filled with the solution, and the titration container 310 then discharges the solution into the reaction container 220. When the solution is a cleaning solution, the liquid in the reaction container 220 can be extracted by the discharge pump group 360, so as to realize the titration container 310 and the reaction container 2 20 is an automatic cleaning method. When the solution is a reaction solution, the reaction solution is directly added into the reaction container 220. When the solution is a sample solution, the sample solution is titrated into the reaction solution through the titration container 310 to complete the automatic titration. The sample solution reacts with the reaction solution to release or absorb heat, and the calorimeter 230 can measure the changed calorific value to achieve automatic titration calorimetry and improve the efficiency of titration calorimetry. After the sample solution reacts with the reaction solution, all the solutions are discharged through the discharge pump group 360, and are cleaned again with the cleaning solution to perform the next titration calorimetry of the sample solution and the reaction solution, thereby achieving continuous automatic titration calorimetry, with higher titration calorimetry efficiency and labor saving.

[0025] In this embodiment, the constant temperature control system 100 includes a constant temperature cavity 110 and a thermometer 120. The constant temperature cavity 110 includes a constant temperature tank and a cover plate covered on the constant temperature tank. The side wall of the constant temperature tank has at least one air insulation layer, and the cover plate is thermally insulated and connected to the constant temperature tank. The thermometer 120 is a temperature control thermistor. Among them, the constant temperature control system 100 also includes a stirring member 150 and an inlet and outlet water dispenser. The stirring member 150 can quickly mix the constant temperature solution so that the constant temperature solution is evenly distributed. The inlet and outlet water dispenser can automatically add the constant temperature solution or discharge the constant temperature solution to control the liquid level of the constant temperature solution in the constant temperature tank, wherein the constant temperature solution can be water.

[0026] The calorimetric system 200 includes a calorimetric cavity 210, a reaction vessel 220, a calorimeter 230, and a heat exchanger 240. The calorimetric cavity 210 and the reaction vessel 220 form a Dewar flask and a Dewar flask cover. The reaction vessel 220 is the inner liner of the Dewar flask, and the calorimetric cavity 210 is the outer shell of the Dewar flask. There is a gap between the inner liner and the outer shell, and the gap forms a vacuum for heat insulation. The calorimetric cavity 210 and the reaction vessel 220 can also form other heat-insulating cavities. The Dewar flask is made of corrosion-resistant hard glass with an effective volume of 100 cm -3 or 50cm -3The Dewar flask cover is made of polytetrafluoroethylene with a low thermal conductivity and is shaped like an "I" to ensure that the Dewar flask is almost completely immersed in the constant temperature water bath and is always at a constant temperature. The inner wall of the Dewar flask cover is embedded with stainless steel high vacuum (vacuum degree reaches 10 -5 Pa) insulation layer to reduce heat exchange. The Dewar flask body uses a high vacuum silver-plated interlayer (vacuum degree reaches 10 -5 Pa), plus a layer of stainless steel protective layer filled with heat insulation material for double insulation to reduce the loss of heat radiation and heat exchange. Submersible magnetic stirring element 150 replaces traditional mechanical stirring to avoid heat leakage caused by heat conduction of the stirring rod. And the magnetic stirring element 150 is fixedly installed at the bottom of the Dewar flask to prevent the position of the magnetic stirring element 150 from moving. The glass stirring rod is driven by a synchronous motor, and the stirring speed is 360r / min (adjustable at will). The actual operation shows that its stirring speed can quickly make the temperature and concentration of the reaction system reach complete uniformity.

[0027] The calorimeter 230 includes a temperature measuring thermistor, which constitutes one of the four bridge arms of the temperature measuring Weston bridge, and generates a DC voltage signal. The signal change generated by the Weston bridge in the temperature range of about 0.8K is linearly related to the temperature change of the calorimetric solvent. The signal is collected by the computer after linear amplification. The fixed resistor of the temperature measuring Weston bridge, that is, the winding resistor used for electrical calibration and auxiliary heating, is a high-precision resistor wound with manganese copper wire, and its temperature coefficient is very small, so that the resistance value can basically remain unchanged during heating. The winding resistor is installed in a thin-walled glass tube filled with silicone oil with good thermal conductivity to ensure that the electrical energy is quickly transferred to the reaction system in the form of heat. The power supply of the temperature measuring Weston bridge is a precision regulated DC power supply. The precision constant current source is an electric energy calibration power supply, and its current accuracy is very high, which can ensure the precision of the supplied current. The time of electric heating is measured by an electronic timer in a computer, and the timing accuracy is 0.001s. The calorimeter 230 also includes a temperature sensing element, which is a bead-shaped thermistor with a resistance of about 50k at 298.15K. The thermistor itself has a very small heat capacity and reacts quickly to temperature. In order to minimize the thermal hysteresis of the temperature sensing element, the thermistor is installed in a thin-walled glass tube filled with silicone oil with good thermal conductivity. The time constant of the temperature measuring element is measured to be 3s, and the sensitivity of the temperature measuring system can reach 510 -5 K.

[0028] The titration container 310 includes an outer shell 311, an injection tube body 312 partially disposed within the outer shell 311, a needle 313 connected to the portion of the injection tube body 312 extending out of the outer shell 311, a plunger 314 disposed within the outer shell 311 and partially located within the injection tube body 312, an injection drive source 315 disposed within the outer shell 311 and transmission-connected to the plunger 314, and a valve group disposed between the injection tube body 312 and the needle 313, the valve group being connected to the liquid storage container 320, and the injection drive source 315 being electrically connected to the controller 400. The injection drive source 315 is transmission-connected to the plunger 314 to precisely control the moving distance of the plunger 314 so that the volume of the reaction solution titrated each time is basically the same. The injection drive source 315 can be a stepper motor. The outer peripheral surface of the plunger 314 has a thread and is spirally connected to the stepper motor. Under the rotation drive of the stepper motor, it moves axially along the injection tube body 312. The needle 313 has an injection port to inject the solution into the reaction container 220.

[0029] Among them, the discharge pump group 360 includes a discharge pipe 361 connecting the bottom of the reaction container 220 and the outside, a discharge control valve and a discharge pump both arranged on the discharge pipe 361, the discharge pump is used to pump the solution in the reaction container 220, the discharge control valve is used to control the on-off of the discharge pipe 361, and the discharge control valve and the discharge pump are both electrically connected to the controller 400.

[0030] Reference Figure 1 As shown, in some specific embodiments of the present invention, the valve group includes a third control valve 330 arranged between the titration container 310 and the control pump group 350 and a fourth control valve 340 arranged between the titration container 310 and the reaction container 220; the automatic titration system 300 is configured as follows: when the control pump group 350 is in an open state and a negative pressure is formed in the titration container 310, the third control valve 330 is opened, the fourth control valve 340 is closed, and the solution in the liquid storage container 320 enters the titration container 310; when the control pump group 350 is in a closed state and the pressure in the titration container 310 increases, the third control valve 330 is closed, the fourth control valve 340 is opened, and the solution in the titration container 310 is injected into the reaction container 220.

[0031] The titration container 310 is connected to the liquid storage container 320 through the third control valve 330 and the control pump group 350, or is connected to the liquid storage container 320 through the third control valve 330, the fifth control valve, and the control pump group 350, and the liquid storage container 320 is connected to the reaction container 220 through the fourth control valve 340 and the injection port; the third control valve 330 and the fourth control valve 340 are both spring valves. The liquid storage container 320 can be a container such as a liquid storage bottle or a liquid storage box that can hold a sample solution.

[0032] In this embodiment, refer to Figure 3As shown, the third control valve 330 includes a first valve body 331, a first spring 332, a first movable plug 333 and a first joint 334. The first valve body 331 is connected to the titration container 310, and is connected to the control pump group 350 through the first joint 334, and is further connected to the liquid storage container 320 through the control pump group 350. The first movable plug 333 can move from the first valve body 331 to the first joint 334, and can block the first joint 334. The first spring 332 is arranged on the side of the first movable plug 333 away from the first joint 334, and the first spring 33 The end away from the first joint 334 abuts against the first valve body 331. When the pressure in the titration container 310 is normal or increases, the first movable plug 333 blocks the first joint 334 through the first spring 332, so that the third control valve 330 remains closed. When the pressure in the titration container 310 is negative pressure, the first movable plug 333 compresses the first spring 332 under the action of the pressure difference, so that the first movable plug 333 opens the first joint 334, so that the third control valve 330 remains open, and the sample solution in the liquid storage container 320 enters the titration container 310. The solution delivered by the injection drive source 315 may also increase the pressure on the side of the first movable plug 333 away from the titration container 310 to form a pressure difference.

[0033] In this embodiment, refer to Figure 3 As shown, the fourth control valve 340 includes a second valve body 341, a second spring 342, a second movable plug 343 and a second joint 344. The second valve body 341 is connected to the titration container 310 and is connected to the reaction container 220 through the second joint 344. The second movable plug 343 can move from the second valve body 341 to the second joint 344 and can block the second valve body 341. The second spring 342 is arranged on a side of the second movable plug 343 away from the second valve body 341, and the second spring 342 is away from the second joint 344. One end of the second valve body 341 abuts against the second valve body 341. When the pressure in the titration container 310 is normal or negative, the second movable plug 343 blocks the second valve body 341 through the second spring 342, so that the fourth control valve 340 remains closed; when the pressure in the titration container 310 increases, the second movable plug 343 compresses the second spring 342 under the action of the pressure difference, so that the second movable plug 343 opens the second joint 344, so that the fourth control valve 340 remains open, and the sample solution in the titration container 310 drips into the reaction container 220. The first valve body 331 and the second valve body 341 can be provided separately, or they can be made together to form a three-way valve.

[0034] It is worth understanding that when negative pressure is formed in the titration container 310, the third control valve 330 is automatically opened and the fourth control valve 340 is closed, and the sample solution in the liquid storage container 320 automatically enters the titration container 310, so that the transportation of the sample solution is more convenient. When the pressure in the titration container 310 increases, the third control valve 330 is closed and the fourth control valve 340 is opened, and the sample solution in the titration container 310 enters the reaction container 220 for reaction. When the pressure in the titration container 310 remains unchanged, the third control valve 330 and the fourth control valve 340 remain closed. By controlling the change in pressure, the sample solution in the liquid storage container 320 is accurately absorbed into the titration container 310, and the sample solution in the titration container 310 is accurately transported to the reaction container 220, thereby improving the titration calorimetric efficiency, reducing costs and maintaining measurement accuracy.

[0035] Reference Figure 1 As shown, in some specific embodiments of the present invention, the liquid storage container 320 is provided in plurality, and the control pump group 350 is provided in plurality. The plurality of liquid storage containers 320 can store different solutions. One control pump group 350 corresponds to one liquid storage container 320, and is used to control the communication between the corresponding liquid storage container 320 and the titration container 310. The plurality of liquid storage containers 320 can contain different solutions, for example, some of the liquid storage containers 320 contain cleaning solutions, some of the liquid storage containers 320 contain reaction solutions, and some of the liquid storage containers 320 contain sample solutions. The cleaning solutions can be of various types, such as distilled water or concentrated solutions, which can be selected according to actual needs. The reaction solutions and sample solutions can also be of various types.

[0036] Reference Figure 1 As shown, in some specific embodiments of the present invention, the control pump group 350 includes a delivery pipeline connecting the liquid storage container 320 and the titration container 310, a control valve and a delivery pump both arranged on the delivery pipeline, the delivery pump is used to pump the solution in the liquid storage container 320, the control valve is used to control the on-off of the delivery pipeline, and the control valve and the delivery pump are both electrically connected to the controller 400.

[0037] In this embodiment, the control valve controls the on-off of the delivery pipeline under the action of the controller 400, and the delivery pump controls the delivery of the solution along the delivery pipeline under the action of the controller 400. When the number of liquid storage containers 320 is multiple, the number of delivery pipelines, control valves, and delivery pumps is also multiple, and corresponds to the multiple liquid storage containers 320. The control valve can control the on-off of the corresponding delivery pipeline under the control of the controller 400, and the controller 400 controls the corresponding delivery pump to deliver the solution stored in the corresponding liquid storage container 320.

[0038] Reference Figure 1As shown, in some specific embodiments of the present invention, the automatic titration system 300 also includes a transfer component 370, the transfer component 370 includes a bracket 371 and a moving part 372 that is transmission-connected to the bracket 371, the moving part 372 can move along a first direction, the moving part 372 is connected to the titration container 310, and can drive the titration container 310 to move to a first position or a second position along the first direction, and the transfer component 370 is electrically connected to the controller 400; wherein the controller 400 is configured to: control the transfer component 370 to drive the titration container 310 to move to a first position along the first direction, the titration container 310 is located above the reaction container 220, and is spaced apart from the calorimetric chamber 210; control the transfer component 370 to drive the titration container 310 to move from the first position to the second position along the first direction, a portion of the titration container 310 is inserted into the reaction container 220, and the reaction container 220 is sealed and insulated together with the calorimetric chamber 210.

[0039] In this embodiment, the moving portion 372 is lifted and lowered along the first direction, so that the titration container 310 can be moved from a first position outside the calorimetric cavity 210 to a second position partially inserted into the calorimetric cavity 210, and the titration container 310 is sealed and heat-insulated with the calorimetric cavity 210, so that the titration container 310 can be automatically moved and can be sealed and heat-insulated with the calorimetric cavity 210 or separated from the calorimetric cavity 210.

[0040] Specifically, the titration container 310 further includes a sealing layer 316, which surrounds the portion of the injection tube 312 extending from the outer shell 311 and is used to seal and thermally insulate with the calorimetric cavity 210. The sealing layer 316 enables the portion of the injection tube 312 inserted into the calorimetric cavity 210 to seal and thermally insulate with the calorimetric cavity 210.

[0041] Reference Figure 1 As shown, in some specific embodiments of the present invention, the automatic titration system 300 also includes a collecting container 390, the moving part 372 can rotate around the circumference of the bracket 371, and the transfer component 370 can also drive the titration container 310 to rotate from the first position to the third position along the circumference of the bracket 371; wherein, the controller 400 is configured to: control the transfer component 370 to drive the titration container 310 to rotate from the first position to the third position along the circumference of the bracket 371, and the titration container 310 moves to the top of the collecting container 390 and communicates with the collecting container 390.

[0042] It is worth understanding that the transfer assembly 370 moves to the third position to align with the collection container 390 and discharge the excess sample solution into the collection container 390. The sample solution will not be discharged into the reaction container 220 in advance, thereby effectively avoiding the premature reaction of the sample solution and the reaction solution. At the same time, the injection tube body 312 is filled with the sample solution, and the needle 313 is also filled with the sample solution after the sample solution flows out, thereby improving the titration accuracy of the sample solution and thus improving the measurement accuracy.

[0043] Reference Figure 1 As shown, in some specific embodiments of the present invention, the automatic titration system 300 also includes an overflow control valve 380 connected to the end of the injection tube body 312 away from the needle 313, a collecting container 390 connected to the overflow control valve 380, and an overflow sensor; wherein the controller 400 is configured to: when the overflow sensor detects that the water in the overflow control valve 380 overflows into the collecting container 390, control the overflow control valve 380 to close; when the control pump group 350 is in an open state, control the overflow control valve 380 to open.

[0044] It is worth understanding that when the overflow sensor detects that solution is flowing out of the overflow control valve 380, the injection tube body 312 is already filled with solution. When the solution is a cleaning solution, the injection tube body 312 is fully cleaned, and the cleaning of the injection tube body 312 is more thorough.

[0045] Reference Figure 1 As shown, in some specific embodiments of the present invention, the titration container 310 also includes a dry gas source 3A0, a dry pipe connected between the titration container 310 and the dry gas source 3A0, and a dry valve provided on the dry pipe, the dry gas source 3A0 is used to transport dry gas, the dry valve is electrically connected to the controller 400, and is used to control the on and off of the dry pipe.

[0046] It is worth understanding that the titration container 310 and the reaction container 220 are dried by the dry gas source 3A0, thereby reducing the influence of the residual liquid on the titration experiment and improving the calorimetric accuracy of the titration calorimetry.

[0047] For ease of understanding, a specific embodiment is used as an example below. The following description does not constitute a specific limitation to the present invention. The number and layout of the control pump group 350 and the liquid storage container 320 in the constant temperature environment automatic titration calorimeter are as follows: There are four liquid storage containers 320, namely a distilled water container 321, a buffer solution container 322, a reaction solution container 323, and a sample solution container 324; The control pump group 350 includes a distilled water pipeline, a distilled water control valve 351 and a distilled water delivery pump 352 corresponding to the distilled water pipeline, a buffer solution pipeline, a buffer solution control valve 353 and a buffer solution delivery pump 354 corresponding to the buffer solution pipeline, a reaction solution pipeline, a reaction solution control valve 355 and a reaction solution delivery pump 356 corresponding to the reaction solution pipeline, a sample solution pipeline, a sample solution control valve 357 and a sample solution delivery pump 358 corresponding to the sample solution pipeline, a first master control valve 359 connected to the distilled water pipeline and the buffer solution pipeline, and a second master control valve 35A connected to the first master control valve 359, the reaction solution pipeline and the sample solution pipeline. The distilled water control valve 351 is also connected to the outside, that is, the distilled water control valve 351 is equivalent to the discharge control valve, the distilled water delivery pump 352 is equivalent to the discharge pump, the second master control valve 35A is also connected to the dry gas source 3A0, the second master control valve 35A is equivalent to the dry valve, the second master control valve 35A is also connected to the third control valve 330 and the titration container 310 through the first connecting pipe, and the second master control valve 35A is also connected to the bottom of the reaction container 220 through the second connecting pipe. All control valves are electrically connected to the controller 400.

[0048] A stirring member 150 is disposed in the reaction container 220 for stirring the solution in the reaction container 220 . The stirring member 150 is electrically connected to the controller 400 .

[0049] The calorimetric chamber 210 further includes an exhaust control valve 211 connecting the reaction container 220 and the outside. The exhaust control valve 211 is electrically connected to the controller 400 .

[0050] The overall cleaning and loading process of the constant temperature environment automatic titration calorimeter is as follows: (I) Cleaning and loading of reaction vessel 220 1.1 Distilled water cleaning 1.1.1 Titration vessel 310 cleaning ① The controller 400 drives the rotating moving part 372 to move the titration container 310 to the second position, and the injection port of the needle 313 in the titration container 310 is inserted into the reaction container 220. The controller 400 controls the injection driving source 315 to drive the plunger 314 to move toward the needle 313, so that the plunger 314 moves down to the bottom of the injection tube body 312.

[0051] ② The controller 400 controls the distilled water control valve 351, the first main control valve 359, and the second main control valve 35A to connect the distilled water container 321 and the third control valve 330. The third control valve 330 is connected to the titration container 310. The controller 400 synchronously controls the injection drive source 315 to drive the plunger 314 to move in the direction away from the needle 313, and controls the distilled water delivery pump 352 to deliver the distilled water, so that the distilled water enters the injection tube body 312. The controller 400 also controls the overflow control valve 380 to be connected to the injection tube body 312. When the overflow sensor detects that distilled water overflows from the outlet of the overflow control valve 380, the controller 400 controls the injection drive source 315 and the distilled water delivery pump 352 to stop, and the overflow control valve 380 is closed.

[0052] ③ The controller 400 controls the injection drive source 315 to drive the plunger 314 to move toward the needle 313 to discharge all the distilled water in the injection tube body 312 into the reaction container 220.

[0053] ④ Repeat steps ② and ③ for 3 consecutive cleanings, or 1, 2, 4 or more times.

[0054] 1.1.2 Cleaning of reaction vessel 220 ⑤ The controller 400 controls the stirring element 150 in the reaction container 220 to stir and clean.

[0055] ⑥ The controller 400 controls the distilled water control valve 351, the first main control valve 359, and the second main control valve 35A to connect the reaction container 220 with the outside world. The controller 400 controls the distilled water delivery pump 352 to reversely extract the waste liquid in the reaction container 220 to discharge the waste liquid to the outside world.

[0056] ⑦ The controller 400 controls the distilled water control valve 351 , the first main control valve 359 , and the second main control valve 35A to connect the reaction container 220 and the distilled water container 321 , and the controller 400 controls the distilled water delivery pump 352 to deliver distilled water into the reaction container 220 .

[0057] ⑧ Repeat steps ⑥ and ⑦ for three consecutive cleanings, or once, twice, four times or more; repeat step ⑥ again to drain all the waste liquid in the reaction container 220.

[0058] 1.2 Buffer washing 1.2.1 Titration vessel 310 cleaning ① The controller 400 controls the buffer control valve 353, the first main control valve 359, and the second main control valve 35A to connect the buffer container 322 and the third control valve 330. The third control valve 330 is connected to the titration container 310. The controller 400 synchronously controls the injection drive source 315 to drive the plunger 314 to move in the direction away from the needle 313, and controls the buffer delivery pump 354 to deliver the buffer, so that the buffer enters the injection tube body 312. The controller 400 also controls the overflow control valve 380 to be connected to the injection tube body 312. When the overflow sensor detects that the buffer overflows from the outlet of the overflow control valve 380, the controller 400 controls the injection drive source 315 and the buffer delivery pump 354 to stop, and the overflow control valve 380 is closed.

[0059] ② The controller 400 controls the injection drive source 315 to drive the plunger 314 to move toward the needle 313 to discharge all the buffer solution in the injection tube body 312 into the reaction container 220.

[0060] ③Repeat steps ① and ② for 3 consecutive washes.

[0061] 1.2.2 Cleaning of reaction vessel 220 ④ The controller 400 controls the stirring member 150 in the reaction container 220 to stir and clean; ⑤ The controller 400 controls the distilled water control valve 351, the first main control valve 359, and the second main control valve 35A to connect the reaction container 220 and the outside world. The controller 400 controls the distilled water delivery pump 352 to reversely extract the waste liquid in the reaction container 220 to discharge the waste liquid to the outside world.

[0062] ⑥ The controller 400 controls the distilled water control valve 351 , the first main control valve 359 , and the second main control valve 35A to connect the reaction container 220 and the distilled water container 321 , and the controller 400 controls the distilled water delivery pump 352 to deliver distilled water into the reaction container 220 .

[0063] ⑦ Repeat steps ⑤ and ⑥ for 3 consecutive washes.

[0064] 1.3 Dry gas for purification ① The controller 400 controls the second main control valve 35A to connect the dry gas source 3A0 and the third control valve 330. The third control valve 330 is connected to the titration container 310. The controller 400 synchronously controls the injection drive source 315 to drive the plunger 314 to move in a direction away from the needle 313, and controls the dry gas source 3A0 to deliver the dry gas. The dry gas enters the injection tube body 312. The controller 400 also controls the overflow control valve 380 to connect with the injection tube body 312, so that the dry gas overflows from the overflow control valve 380. Then, the controller 400 controls the injection drive source 315 to drive the plunger 314 to move toward the needle 313 to discharge all the dry gas in the injection tube body 312 into the reaction container 220.

[0065] ② The controller 400 controls the second main control valve 35A to connect to the dry gas source 3A0 and the reaction container 220, and the controller 400 controls the exhaust control valve 211 to open.

[0066] ③ Repeat steps ① and ② for 3 consecutive times.

[0067] 1.4 Loading of reaction vessel 220 ① The controller 400 controls the reaction solution control valve 355, the reaction solution control valve 355, and the second main control valve 35A to connect the reaction solution container 323 and the third control valve 330. The third control valve 330 is connected to the titration container 310. The controller 400 synchronously controls the injection drive source 315 to drive the plunger 314 to move in the direction away from the needle 313, and controls the reaction solution delivery pump 356 to deliver the reaction solution. The reaction solution enters the injection tube body 312. The controller 400 also controls the overflow control valve 380 to be connected to the injection tube body 312. When the overflow sensor detects that the reaction solution overflows from the outlet of the overflow control valve 380, the controller 400 controls the injection drive source 315 and the reaction solution delivery pump 356 to stop, and the overflow control valve 380 is closed.

[0068] ② The controller 400 controls the injection driving source 315 to drive the plunger 314 to move toward the needle 313 to discharge the reaction solution in the injection tube body 312 into the reaction container 220 .

[0069] ③ Repeat steps ① and ② for 5 or 10 times, that is, fill the container with 50 mL or 100 mL of the substance to be tested.

[0070] (II) Cleaning and loading of titration vessel 310 2.1 Distilled water cleaning ① The controller 400 drives the rotating moving part 372 to move the titration container 310 to the third position, and the injection port of the needle 313 in the titration container 310 is aligned with the collection container 390. The controller 400 controls the injection driving source 315 to drive the plunger 314 to move toward the needle 313, so that the plunger 314 moves down to the bottom of the injection tube body 312.

[0071] ② The controller 400 controls the distilled water control valve 351, the first main control valve 359, and the second main control valve 35A to connect the distilled water container 321 and the third control valve 330. The third control valve 330 is connected to the titration container 310. The controller 400 synchronously controls the injection drive source 315 to drive the plunger 314 to move in the direction away from the needle 313, and controls the distilled water delivery pump 352 to deliver the distilled water, so that the distilled water enters the injection tube body 312. The controller 400 also controls the overflow control valve 380 to be connected to the injection tube body 312. When the overflow sensor detects that distilled water overflows from the outlet of the overflow control valve 380, the controller 400 controls the injection drive source 315 and the distilled water delivery pump 352 to stop, and the overflow control valve 380 is closed.

[0072] ③ The controller 400 controls the injection drive source 315 to drive the plunger 314 to move toward the needle 313 to discharge all the distilled water in the injection tube body 312 into the collection container 390.

[0073] ④ Repeat steps ② and ③ for 3 consecutive cleanings, or 1, 2, 4 or more times.

[0074] 2.2 Buffer washing ① The controller 400 controls the buffer control valve 353, the first main control valve 359, and the second main control valve 35A to connect the buffer container 322 and the third control valve 330. The third control valve 330 is connected to the titration container 310. The controller 400 synchronously controls the injection drive source 315 to drive the plunger 314 to move in the direction away from the needle 313, and controls the buffer delivery pump 354 to deliver the buffer, so that the buffer enters the injection tube body 312. The controller 400 also controls the overflow control valve 380 to be connected to the injection tube body 312. When the overflow sensor detects that the buffer overflows from the outlet of the overflow control valve 380, the controller 400 controls the injection drive source 315 and the buffer delivery pump 354 to stop, and the overflow control valve 380 is closed.

[0075] ② The controller 400 controls the injection drive source 315 to drive the plunger 314 to move toward the needle 313 to discharge all the buffer solution in the injection tube body 312 into the collection container 390.

[0076] ③Repeat steps ① and ② for 3 consecutive washes.

[0077] 2.3 Dry gas for purification ① The controller 400 controls the second main control valve 35A to connect the dry gas source 3A0 and the third control valve 330. The third control valve 330 is connected to the titration container 310. The controller 400 synchronously controls the injection drive source 315 to drive the plunger 314 to move in a direction away from the needle 313, and controls the dry gas source 3A0 to deliver the dry gas. The dry gas enters the injection tube body 312. The controller 400 also controls the overflow control valve 380 to connect with the injection tube body 312, so that the dry gas overflows from the overflow control valve 380. Then, the controller 400 controls the injection drive source 315 to drive the plunger 314 to move toward the needle 313 to discharge all the dry gas in the injection tube body 312 into the collection container 390.

[0078] ②Repeat step ① and dry for 3 consecutive times.

[0079] 2.4 Loading of the titration vessel 310 ① The controller 400 drives the rotating moving part 372 to move the titration container 310 to the third position, and the injection port of the needle 313 in the titration container 310 is aligned with the collection container 390. The controller 400 controls the injection driving source 315 to drive the plunger 314 to move toward the needle 313, so that the plunger 314 moves down to the bottom of the injection tube body 312.

[0080] ② The controller 400 controls the sample solution control valve 357 and the second main control valve 35A to connect the sample solution container 324 and the third control valve 330. The third control valve 330 is connected to the titration container 310. The controller 400 synchronously controls the injection drive source 315 to drive the plunger 314 to move in the direction away from the needle 313, and controls the sample solution delivery pump 358 to deliver the sample solution. The sample solution enters the injection tube body 312. The controller 400 also controls the overflow control valve 380 to be connected to the injection tube body 312. When the overflow sensor detects that the sample solution overflows from the outlet of the overflow control valve 380, the controller 400 controls the injection drive source 315 and the sample solution delivery pump 358 to stop, and the overflow control valve 380 is closed.

[0081] ③ The controller 400 controls the injection driving source 315 to drive the plunger 314 to move toward the needle 313 to discharge all the distilled water in the injection tube body 312 into the collection container 390 and fill the needle 313 with the sample solution.

[0082] ④ The controller 400 controls the injection drive source 315 to drive the plunger 314 to move in a direction away from the needle 313, and at the same time controls the sample solution delivery pump 358 to deliver. When the overflow sensor detects that the sample solution overflows from the outlet of the overflow control valve 380, the controller 400 controls the injection drive source 315 and the sample solution delivery pump 358 to stop, and the overflow control valve 380 is closed.

[0083] Reference Figure 1 As shown, in some specific embodiments of the present invention, the automatic titration system 300 also includes a first stopper and a second stopper which are arranged in the outer shell 311 and located at the end of the injection tube body 312 away from the needle 313. The first stopper and the second stopper are arranged in sequence along the direction of the injection tube body 312 away from the needle 313. The first stopper and the second stopper are both used to detect the end of the plunger 314 away from the needle 313, and are both connected to the controller 400; wherein the controller 400 is configured to: when the first stopper does not detect the plunger 314, control the plunger 314 to stop moving toward the needle 313; when the second stopper detects the plunger 314, control the plunger 314 to stop moving in the direction away from the needle 313.

[0084] It is worth understanding that the first stopper and the second stopper limit the limit movement position of the plunger 314, so that the limit movement position of the plunger 314 is fixed, which facilitates the control of the movement of the plunger 314. In this embodiment, the first stopper and the second stopper are both photoelectric stoppers.

[0085] Reference Figure 1 and Figure 4 As shown, in some specific embodiments of the present invention, the constant temperature environment automatic titration calorimeter further includes a controller 400 electrically connected to the calorimetric system 200; The calorimetric system 200 also includes a heat exchanger 240 disposed in the reaction container 220, and the heat exchanger 240 is used to adjust the temperature of the reaction solution. The heat exchanger 240 also includes a driving pump 244 disposed in the constant temperature chamber 110, and the driving pump 244 connects the constant temperature chamber 110 and the first heat exchange pipe 241; the controller 400 is configured to: control the driving pump 244 to drive the constant temperature solution to flow through the first heat exchange pipe 241.

[0086] It should be noted that after the development of the constant temperature environment automatic titration calorimeter entered the testing stage, when Tris was used to titrate hydrochloric acid for the calorimeter calibration, after the first titration, the temperature of the system was difficult to cool down naturally. The system reached thermal equilibrium only after about twelve hours of natural cooling. Only then could the second titration be performed. The system took too long to reach thermal equilibrium, and the instrument had no practical value.

[0087] The heat exchanger 240 includes a first heat exchange pipe 241, a first control valve 242 and a second control valve 243. The first heat exchange pipe 241 is arranged in the reaction container 220 for the heat exchange medium to pass through. The controller 400 is configured to: before titrating the sample solution, control the heat exchange medium to flow through the first heat exchange pipe 241; when the temperature of the thermometer 120 is consistent with the temperature of the calorimeter 230, control the first control valve 242 and the second control valve 243 to close the first heat exchange pipe 241. The temperature of the mixed solution of the reaction solution and the sample solution in the reaction container 220 is actively adjusted through the first heat exchange pipe 241, so that the temperature of the mixed solution can be quickly restored to the initial temperature, so as to facilitate the next titration and improve the titration calorimetry efficiency. Among them, the first heat exchange pipe 241 can be a spiral tube or a U-shaped tube or a tube of other shapes, the temperature of the heat exchange medium can be controlled by a separate system, or the heat exchange medium is a constant temperature solution in the constant temperature chamber 110, and the temperature of the constant temperature solution is adjusted to be consistent with the temperature of the reaction solution by the constant temperature control system 100, the production cost of the equipment is lower, which is conducive to the promotion of the equipment.

[0088] It should be noted that when the temperature of the thermometer 120 is consistent with the temperature of the calorimeter 230, the controller 400 directly controls the first control valve 242 and the second control valve 243 to close, so as to isolate the first heat exchange pipe 241 and the constant temperature chamber 110, so that the first heat exchange pipe 241 is not affected by the constant temperature solution in the constant temperature chamber 110, and further, the reaction container 220 is not affected by the constant temperature solution, and the heat measurement in the reaction container 220 is more accurate.

[0089] It is worth understanding that by coating the calorimetric cavity 210 with a constant temperature solution, the calorimetric cavity 210 is better isolated from the external temperature and the measurement is more accurate; after the automatic titration system 300 titrates once, the sample solution and the reaction solution react in the reaction vessel 220 and change the temperature in the reaction vessel 220. The temperature of the reaction solution is difficult to automatically return to the original temperature, and the next titration takes longer. The heat exchanger 240 quickly adjusts the temperature in the reaction vessel 220 to be consistent with the temperature of the constant temperature solution, so that the automatic titration system 300 can quickly start the next titration, and the titration calorimetry efficiency of the automatic titration system 300 is higher.

[0090] In addition, the calorimetric system 200 further includes an electric heating element 250, which is used for electrical calibration. The electric heating element 250 is a heating resistor.

[0091] In this embodiment, the driving pump 244 is a circulating water pump, and is a submersible circulating water pump. The driving pump 244 can actively transport the constant temperature solution to flow, so that the constant temperature solution can pass through the first heat exchange pipe 241, and the constant temperature solution in the constant temperature chamber 110 is heat exchanged with the reaction solution, so that the temperature of the constant temperature solution and the reaction solution can be quickly adjusted to be consistent, and the constant temperature control system 100 can adjust the temperature of the constant temperature solution, so that the temperature of the constant temperature solution is always maintained at a preset initial temperature, thereby realizing the temperature control of the entire device. Among them, both ends of the first heat exchange pipe 241 are connected to the constant temperature chamber 110 to form a circulation loop, so that the circulating water pump can continuously extract the constant temperature solution from one end of the first heat exchange pipe 241 into the first heat exchange pipe 241, and the constant temperature solution flows out from the other end of the first heat exchange pipe 241 after passing through the first heat exchange pipe 241.

[0092] It is worth understanding that the heat exchanger 240 actively inputs the constant temperature solution into the reaction container 220 by driving the pump 244, so that the temperature of the mixed solution can be quickly restored to the initial temperature to facilitate the next titration and improve the titration calorimetric efficiency.

[0093] Reference Figure 1 and Figure 5 As shown, in some specific embodiments of the present invention, the constant temperature control system 100 includes a heating element 130 disposed in a constant temperature cavity 110 and a cooling pipeline 140 partially disposed in the constant temperature cavity 110, the heating element 130 is used to heat the constant temperature solution, and the cooling pipeline 140 is used to cool the constant temperature solution.

[0094] It should be noted that the sample solution reacts with the reaction solution, and the reaction can be an endothermic reaction or a heat release reaction. The constant temperature control system 100 can adjust the temperature of the constant temperature solution in the constant temperature cavity 110 through the heating element 130 and the cooling line 140, so that the temperature of the constant temperature solution remains constant, thereby making the calorimetric system 200 in the constant temperature solution less affected by the external temperature, and the calorimetric system 200 is more accurate in measuring the heat of reaction. At the same time, after the constant temperature solution in the first heat exchange pipe 241 is mixed with the constant temperature solution in the constant temperature cavity 110, the constant temperature control system 100 can also quickly take away the temperature change brought by the constant temperature solution in the first heat exchange pipe 241, so that the temperature of the constant temperature solution in the constant temperature control system 100 remains constant, and the temperature in the reaction vessel 220 can be quickly restored to the same as the constant temperature solution, thereby improving the titration calorimetric efficiency.

[0095] In this embodiment, the constant temperature control system 100 also includes a thermistor, which is used as a temperature sensor to sense the temperature. The thermistor constitutes one of the four bridge arms of the Weston bridge, generates a voltage signal and sends it to the precision temperature controller 160. The signal is compared with the millivolt setter in the precision temperature controller 160 to obtain a deviation signal. The deviation signal is amplified and indicated by the deviation table, and sent to the PID regulator for PID operation, and outputs a 0-10mA signal with PID regulation law to the thyristor trigger. The thyristor trigger uses a single-junction tube Chixun oscillator to output a phase-shifted trigger pulse. The heating power of the heating element 130 is driven and controlled by the thyristor actuator. In order to improve the temperature control stability, the heater voltage feedback is introduced to overcome the influence of the grid voltage fluctuation on the heater heating power. In order to prevent the influence of the ambient temperature on the tank temperature when it is too high, a cooling pipeline 140 is added in the constant temperature tank to facilitate the adjustment of the tank temperature. In this embodiment, the heating element 130 is a heating resistor, and the cooling pipeline 140 is actively cooled by a semiconductor refrigeration device.

[0096] Reference Figure 6 As shown, in some specific embodiments of the present invention, the cooling circuit includes a cooling source 141, a cold end heat conductor 142, a cooling pipe 143, a cooling pipe 144 and a cooling medium, the cooling pipe 143 is arranged in the constant temperature cavity 110, the cooling pipe 144 is arranged outside the constant temperature cavity 110, and is connected with the cooling pipe 143 to form a closed loop, the cooling medium is arranged in the closed loop, and can circulate along a preset flow direction, the cold end heat conductor 142 is arranged in the cooling pipe 144, and is used to transfer the cooling capacity of the cooling source 141 to the cooling medium in the cooling pipe 144.

[0097] It is worth understanding that, at the location of the refrigeration pipe 144, the cold end heat conductor 142 transfers the cooling capacity generated by the refrigeration source 141 to the refrigerant medium in the refrigeration pipe 144, the temperature of the refrigerant medium decreases, and flows through the cooling pipe 143 through a closed loop. At the location of the cooling pipe 143, the cooling pipe 143 exchanges heat with the constant temperature solution in the constant temperature cavity 110 to cool the constant temperature solution, and then the refrigerant medium repeatedly passes through the refrigeration pipe 144-cooling pipe 143 to continuously cool the constant temperature solution.

[0098] In this embodiment, the cooling source 141 is a semiconductor refrigerator. The semiconductor refrigerator is a device that uses the thermoelectric effect of semiconductors to generate cooling capacity. If an N-type semiconductor and a P-type semiconductor are connected to each other and a direct current is connected, the temperature at one end will decrease and the temperature at the other end will increase. If the power supply is reversed, the temperature change will occur in the opposite direction. This phenomenon is called the thermoelectric effect. The temperature difference and cooling capacity generated by a pair of semiconductor thermoelectric elements are very small. In actual application, many pairs of thermoelectric elements are connected in parallel and in series, also known as thermoelectric piles. A single-stage thermoelectric pile can obtain a temperature difference of about 60°C, that is, the cold end temperature can reach -10°C to -20°C. Increasing the number of thermoelectric piles can increase the temperature difference.

[0099] In addition, the heating element 130 can also be a separate heating pipeline, and the structure of the heating pipeline is the same as that of the cooling pipeline, except that the cooling pipeline 140 is connected to the cold end of the semiconductor refrigerator through the cold end heat conductor 142, and the heating pipeline is connected to the hot end of the semiconductor refrigerator through the hot end heat conductor, wherein the heating pipeline and the cooling pipeline 140 can share the pipeline located in the constant temperature cavity 110, and this part of the pipeline is both a cooling pipe 143 and a heating pipe, and the heating pipeline and the cooling pipeline are switched by two two-position three-way valves. The cooling medium in the cooling pipeline circulates under the drive of the pump body.

[0100] Reference Figure 1 and Figure 5 As shown, in some specific embodiments of the present invention, the constant temperature control system 100 further includes a stirring member 150 disposed in the constant temperature chamber 110, and the stirring member 150 is used to stir the constant temperature solution.

[0101] It is worth understanding that by actively stirring the constant temperature solution through the stirring element 150, the constant temperature solutions of different temperatures can be quickly mixed when the constant temperature solution is locally heated or locally cooled, thereby improving the temperature uniformity of the constant temperature solution and the accuracy of the temperature detection of the constant temperature solution.

[0102] In this embodiment, the stirring element 150 includes stirring blades and a motor connected to the stirring blades. The stirring blades are arranged in the constant temperature cavity 110. The motor drives the stirring blades to stir, and the start and stop of the motor can be controlled by the controller 400.

[0103] Reference Figure 1 and Figure 5As shown, in some specific embodiments of the present invention, the constant temperature control system 100 also includes a temperature controller 160 electrically connected to the heating element 130 and the calorimeter 230; the temperature controller 160 is configured to: when the calorimeter 230 detects that the temperature of the constant temperature solution is lower than the preset temperature, obtain the first heating power of the heating element 130 required to heat the constant temperature solution to the preset temperature, and the controller 400 controls the heating element 130 to heat the first heating power.

[0104] In this embodiment, the constant temperature environment automatic titration calorimeter further includes a data processing system, which may specifically be a computer.

[0105] It is worth understanding that when the calorimeter 230 detects that the temperature of the isothermal solution has dropped, the data processing system calculates the first heating power required for the isothermal solution to rise to the original temperature, and then controls the heating element 130 to heat the first heating power so that the isothermal solution can be restored to the original temperature. Among them, when the ambient temperature is lower than the temperature of the isothermal solution, causing the temperature of the isothermal solution to change, the heating element 130 can be continuously heated, and the heating power is the heat exchange power between the isothermal solution and the ambient temperature, so that the isothermal solution can maintain a dynamic thermal balance and maintain its own temperature unchanged.

[0106] Reference Figure 1 , Figure 2 and Figure 3 As shown, in some specific embodiments of the present invention, the constant temperature environment automatic titration calorimeter further includes a controller 400 electrically connected to the automatic titration system 300; the automatic titration system 300 further includes a fifth control valve disposed between the titration container 310 and the liquid storage container 320, and the controller 400 is configured to: when the third control valve 330 is opened, control the fifth control valve to be opened; when the third control valve 330 is closed, control the fifth control valve to be closed.

[0107] In this embodiment, the fifth control valve is a solenoid valve, which is electrically connected to the controller 400 and is controlled by the controller 400 .

[0108] It should be noted that the liquid storage container 320 is inverted, and the third control valve 330 is connected to the bottom of the liquid storage container 320. When there is only the third control valve 330, the third control valve 330 is affected by the gravity of the sample solution in the liquid storage container 320, making it difficult for the third control valve 330 to be completely sealed, resulting in the sample solution in the liquid storage container 320 being easily leaked into the titration container 310, causing the titration amount to increase, affecting the accuracy of the final result. Therefore, in this embodiment, on the basis of the third control valve 330, a fifth control valve is separately provided, and the sealing effect between the liquid storage container 320 and the titration container 310 is further strengthened by the fifth control valve, so that the titrated sample solution amount is more accurate and the detection accuracy is improved. Among them, the fifth control valve can be opened together with the third control valve 330, or the fifth control valve is opened before the third control valve 330, and the fifth control valve can be closed together with the third control valve 330, or the fifth control valve is closed after the third control valve 330.

[0109] Reference Figure 1 and Figure 2 As shown, in some specific embodiments of the present invention, the automatic titration system 300 also includes a second heat exchange pipe connected to the constant temperature chamber 110, and a portion of the second heat exchange pipe is wound outside the liquid storage container 320 or is arranged inside the liquid storage container 320, and the second heat exchange pipe is used for heat exchange with the sample solution.

[0110] It is worth understanding that the second heat exchange pipe performs heat exchange with the sample solution through the constant temperature solution, so that the sample solution and the constant temperature solution reach thermal equilibrium, and finally the sample solution, the reaction solution and the constant temperature solution all reach thermal equilibrium, reducing the impact of the temperature difference on the test accuracy and improving the accuracy of the test.

[0111] In this embodiment, the second heat exchange pipe is a pipe bolted around the outer circumference of the liquid storage container 320, and the second heat exchange pipe is also connected to the constant temperature cavity 110 through a circulating water pump, and the circulating water pump can actively transport the constant temperature liquid through the second heat exchange pipe and return it to the constant temperature cavity 110. Among them, the circulating water pump is a submersible circulating water pump.

[0112] To facilitate understanding, some specific embodiments are used for illustrative purposes below.

[0113] In this embodiment, the specific calibration process of the automatic titration system 300 is used as an example to illustrate the calibration steps as follows: ① Degas the distilled water using vacuum ultrasonic degassing method.

[0114] ② Clean and load the reaction pool and syringe respectively according to the cleaning and loading operation steps of the reaction pool and syringe described above.

[0115] ③ Turn on the power of the instrument, preheat the instrument and keep the constant temperature of the constant temperature water bath at (298.15±0.001)K.

[0116] ④Operate the control panel and set the stepper motor's subdivision, up and down movement steps, up and down movement frequency and other parameters according to the experimental needs to determine the volume of degassed distilled water to be titrated. For example, when the subdivision is adjusted to 64, the up and down movement frequency is 3200, and the up and down movement steps are set to 198000, the titrated volume is 4.99973±0.00068mL.

[0117] ⑤ Click the "up" button on the control panel to allow the dehydrated distilled water in the liquid storage container 320 to enter the titration container 310. Then, the temperature is kept constant.

[0118] ⑥ Accurately weigh the clean and dry ground-mouth weighing bottle on a Sartorius CPA225D electronic balance (d=0.01 mg) and peel it.

[0119] ⑦ Place the weighing bottle under the injection port of the titration container 310, click the "Auto" button on the control panel, and add distilled water. After the titration is completed, quickly cover the ground cover and weigh accurately.

[0120] The embodiments of the present invention are described in detail above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

1. A constant temperature environment automatic titration calorimeter, characterized in that: include: A constant temperature control system, comprising a constant temperature cavity for containing a constant temperature solution and a temperature measuring device for detecting the temperature of the constant temperature solution; A calorimetric system, comprising a calorimetric cavity disposed in the constant temperature cavity, a reaction container and a calorimeter both disposed in the calorimetric cavity, wherein the calorimetric cavity is used to be coated with the constant temperature solution, the reaction container is thermally insulatedly connected to the calorimetric cavity and is used to contain the reaction solution, and the calorimeter is used to measure the temperature of the reaction solution; An automatic titration system, comprising a titration container connected to the reaction container, a liquid storage container connected to the titration container, a control pump group arranged between the titration container and the liquid storage container, and a discharge pump group connected to the reaction container and the outside, wherein the liquid storage container is used to store a solution, the titration container is used to suck out the solution in the liquid storage container or discharge the solution into the reaction container, the control pump group has an open state and a closed state, and the discharge pump group is used to discharge the solution in the reaction container; A controller, electrically connected to the control pump group; Wherein, the controller is configured to: when the control pump group is in the open state, control the control pump group to connect the liquid storage container and the titration container, and control the control pump group to transport the solution in the liquid storage container to the titration container; in the closed state, control the control pump group to disconnect the liquid storage container and the titration container.

2. The constant temperature environment automatic titration calorimeter according to claim 1, characterized in that: The liquid storage containers are arranged in plurality, the control pump groups are arranged in plurality, the plurality of liquid storage containers can store different solutions, one control pump group corresponds to one liquid storage container, and is used to control the communication between the corresponding liquid storage container and the titration container.

3. The constant temperature environment automatic titration calorimeter according to claim 1, characterized in that: The control pump group includes a delivery pipeline connecting the liquid storage container and the titration container, a control valve and a delivery pump both arranged on the delivery pipeline, the delivery pump is used to pump the solution in the liquid storage container, the control valve is used to control the on-off of the delivery pipeline, and the control valve and the delivery pump are both electrically connected to the controller.

4. The constant temperature environment automatic titration calorimeter according to claim 1, characterized in that: The automatic titration system further comprises a transfer assembly, the transfer assembly comprises a bracket and a moving part which is transmission-connected to the bracket, the moving part can move along a first direction, the moving part is connected to the titration container, and can drive the titration container to move to a first position or a second position along the first direction, and the transfer assembly is electrically connected to the controller; Wherein, the controller is configured to: control the transfer component to drive the titration container to move along the first direction to the first position, the titration container is located above the reaction container and is separated from the calorimetric cavity; control the transfer component to drive the titration container to move along the first direction from the first position to the second position, a portion of the titration container is inserted into the reaction container, and the reaction container is sealed and insulated together with the calorimetric cavity.

5. The constant temperature environment automatic titration calorimeter according to claim 4, characterized in that: The automatic titration system further comprises a collection container, the moving part can rotate around the circumference of the bracket, and the transfer assembly can also drive the titration container to rotate from the first position to a third position along the circumference of the bracket; Wherein, the controller is configured to: control the transfer component to drive the titration container to rotate from the first position to the third position along the circumference of the bracket, and the titration container moves to the top of the collection container and communicates with the collection container.

6. The constant temperature environment automatic titration calorimeter according to claim 1, characterized in that: The titration container includes an outer shell, a syringe body partially disposed within the outer shell, a needle connected to the syringe body and extending out of the outer shell, a plunger disposed within the outer shell and partially located within the syringe body, an injection drive source disposed within the outer shell and transmission-connected to the plunger, and a valve group disposed between the syringe body and the needle, the valve group being connected to the liquid storage container, and the injection drive source being electrically connected to the controller.

7. The constant temperature environment automatic titration calorimeter according to claim 6, characterized in that: The valve group includes a third control valve disposed between the titration container and the control pump group and a fourth control valve disposed between the titration container and the reaction container; The automatic titration system is configured as follows: when the control pump group is in an on state and negative pressure is formed in the titration container, the third control valve is opened, the fourth control valve is closed, and the solution in the liquid storage container enters the titration container; when the control pump group is in a off state and the pressure in the titration container increases, the third control valve is closed, the fourth control valve is opened, and the solution in the titration container is injected into the reaction container.

8. The constant temperature environment automatic titration calorimeter according to claim 6, characterized in that: The automatic titration system further comprises an overflow control valve connected to the end of the injection tube body away from the needle, a collection container connected to the overflow control valve, and an overflow sensor; Wherein, the controller is configured to: when the overflow sensor detects that the water in the overflow control valve overflows into the collection container, control the overflow control valve to close; when the control pump group is in an on state, control the overflow control valve to open.

9. The constant temperature environment automatic titration calorimeter according to claim 6, characterized in that: The automatic titration system further comprises a first stopper and a second stopper which are arranged inside the outer shell and located at the end of the injection tube body away from the needle, the first stopper and the second stopper are arranged in sequence along the direction of the injection tube body away from the needle, the first stopper and the second stopper are both used to detect the end of the plunger away from the needle, and are both connected to the controller; Wherein, the controller is configured to: when the first stopper does not detect the plunger, control the plunger to stop moving toward the needle; when the second stopper detects the plunger, control the plunger to stop moving in a direction away from the needle.

10. The constant temperature environment automatic titration calorimeter according to claim 1, characterized in that: The titration container further includes a dry gas source, a dry pipe connected between the titration container and the dry gas source, and a dry valve provided on the dry pipe. The dry gas source is used to transport dry gas. The dry valve is electrically connected to the controller and is used to control the on / off of the dry pipe.

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