Composite gasification thermogravimetric analysis method and device for biomass and coal

Abstract

The invention provides a biomass and coal combined type gasification thermogravimetric analysis method and device aiming at the programmed control problem of a multi-element gasification agent suitable for biomass and coal combined type gasification thermogravimetric analysis, relates to the technical field of biomass and coal gasification, and is suitable for biomass and coal combined type gasification process and gasification process research. Meanwhile, the gas control requirements of solid waste thermochemical conversion and catalytic conversion thermal analysis research can be met, the device is used for vaporizing with water vapor and quantitatively guiding multi-element gas into a thermal analyzer according to a program, precise gas control is achieved, and the accuracy and reproducibility of measurement in the reaction process are ensured.

Description

Technical Field

[0001] The invention relates to the technical field of biomass and coal gasification, and in particular to a composite gasification thermogravimetric analysis method and device for biomass and coal. Background Art

[0002] Biomass and coal are gasified to produce syngas with higher calorific value, such as CO, H2, CH4, etc., which can be used as fuel or chemical raw materials. The selection of gasifier and process is one of the important factors affecting the biomass and coal gasification process. Commonly used gasifiers include air, oxygen, carbon dioxide, water vapor and hydrogen. Composite gasification is the composite use of gasifiers. In the process of biomass and coal gasification, the composite gasification mechanism of biomass and coal is still unclear. Thermogravimetric analysis simulates the gasification process of biomass and coal and explores the gasification process, providing important reference data for the study of composite gasification mechanism, thermodynamics and kinetics of reactions. However, thermogravimetric analysis of the gasification process of biomass or coal usually uses a certain gasifier to study a single gasification process and process. Composite gasification requires quantitative introduction of the gas source of the required gasifying agent at different stages of thermal analysis. Invention patent CN108519301B uses a thermogravimetric analyzer to evaluate the reactivity of biomass coke. The reactivity evaluation of biomass coke is achieved by switching between different high-purity nitrogen, oxygen, and carbon dioxide. In the actual test process, the baseline gas switching time and the sample switching time are prone to experimental errors due to inconsistent operations of 1-2 seconds. The reactivity evaluation between different samples is also prone to large experimental errors due to inconsistent operation time, resulting in inaccurate results, and this method cannot achieve thermogravimetric experiments with water vapor as a gasifying agent. At the same time, the operator of the experimental process is required to be on duty during the gas switching process to adjust the gas flow and open and close the gas valve or liquid valve. Experiments with long time or complex experimental processes are also prone to failure due to fatigue or misoperation. Utility model patent ZL202223110232.1 is a multi-gas inlet device based on in-situ reaction thermal analysis. It can achieve gas control and reproducibility of thermal analysis through multi-gas programmed control. It is our summary and exploration of in-situ thermal analysis experiments. It is suitable for catalyst redox experiments. It can do 99 cycles to evaluate catalyst activity, etc., but it cannot complete thermal analysis experiments in water vapor atmosphere. Utility model patent ZL202320035441.X is a device for quantitatively introducing low-dose water vapor into thermal analyzer. It realizes water vapor adsorption experiments through low-dose water vapor vaporization and introduction into thermal analysis, but it cannot perform experiments on multiple gas switching and accurate control. Try to use utility model patent 202223110232.1 and utility model patent ZL202320035441.X together, and find that there are many places where they are not suitable, such as program control problems of water vapor.

[0003] Water vapor is an efficient and inexpensive gasifier, which plays an important role in the gasification process of biomass and coal. Conventional thermogravimetric analyzers do not have the conditions for water vapor experiments. Commercial water vapor generators and furnaces are expensive, and few institutions or companies purchase them. This experiment can perform water vapor atmosphere experiments after modifying the thermogravimetric analyzer to meet the input of water vapor in the thermal analysis process and ensure that water vapor does not condense during the input process. In the thermogravimetric analysis gasification experiment of biomass and coal, it is necessary to introduce an appropriate amount of gasifier according to different gasification processes and achieve timely switching and accurate control, study the impact of gasification processes on biomass and coal gasification, and study the gasification mechanism. Many attempts have been made in the research on the composite gasification of biomass and coal, such as self-built pipelines, when the temperature and time of thermogravimetric analysis are reached, there is inconsistency in dead volume, and the pipeline purge time is too long, which affects the research on the reaction process; manual switching of gas valves and flow adjustment are prone to sudden changes in flow during switching, which may cause excessive gasification gas, resulting in rapid gasification of biomass or coal, leading to inaccurate experimental results, or inaccurate manual switching of valve time causing large errors; it is necessary to watch the instrument to switch gas valves and set flow, which often requires staying up all night on duty, and it is also easy to cause human errors, resulting in experimental failure and re-doing. Poor reproducibility and low efficiency. Therefore, it is urgent to design a device for water vaporization and multi-element gas quantitative introduction to introduce gas into the thermal analyzer according to the program, accurately control the amount of water vaporization, and combine with mass flowmeter to accurately control multiple gasifying agents to realize the control of gas humidity and introduce thermal analysis. Combined with the device, explore the thermogravimetric analysis method suitable for composite gasification of biomass and coal. The programmed control system can greatly improve the reproducibility and stability of the experiment. Summary of the invention

[0004] The present invention aims at the problem of programmed control of multi-component gasifying agents suitable for thermogravimetric analysis of biomass and coal composite gasification, and proposes a thermogravimetric analysis method and device for composite gasification of biomass and coal. The method and device are suitable for the composite gasification process and gasification process research of biomass and coal, and can also meet the gas control requirements of thermal analysis research on thermochemical conversion and catalytic conversion of solid waste. The method is used for vaporization with water vapor and quantitative introduction of multi-component gases into a thermal analyzer according to a program, so as to realize precise gas control and ensure the accuracy and reproducibility of reaction process measurement.

[0005] In order to achieve the above object, the technical solution of the present invention is as follows:

[0006] In a first aspect, the present invention provides a gasification thermogravimetric analysis device, comprising:

[0007] Thermal analyzer;

[0008] a water vapor quantitative vaporization introduction unit connected to the thermal analyzer via a gas pipeline,

[0009] A multi-element gas control introduction unit connected to the thermal analyzer via a gas pipeline,

[0010] Wherein, the water vapor quantitative vaporization introduction unit comprises a constant flow metering pump and a vaporization chamber, pure water is injected into the vaporization chamber through the constant flow metering pump, and the vaporized water vapor enters the thermal analyzer through a transmission pipe with a heating belt, and a first manual stop valve and a third manual stop valve are provided on the transmission pipe with a heating belt;

[0011] The multi-gas control introduction unit includes gas cylinders respectively filled with hydrogen mixture, high-purity carbon dioxide, oxygen mixture and high-purity argon. The gas cylinder filled with high-purity argon is connected to the transmission pipe between the vaporization chamber and the first manual stop valve through a gas pipeline for adjusting the water vapor concentration; the gas cylinder filled with high-purity argon is connected to the thermal analyzer through another gas pipeline for providing balance protection gas and an inert gas source for the gasification process; the gas cylinders filled with hydrogen mixture, high-purity carbon dioxide, oxygen mixture and high-purity argon are respectively connected to the transmission pipe between the first manual stop valve and the third manual stop valve through gas pipelines, and a second manual stop valve is arranged at the confluence of the gas pipelines. Each gas pipeline is sequentially provided with a pressure reducing valve, a check valve, a solenoid valve and a mass flow meter along the gas flow direction, and the pressure reducing valve, the check valve, the solenoid valve and the mass flow meter are all electrically connected to the host computer.

[0012] Optionally, it also includes a liquid check valve and a liquid solenoid valve arranged between the constant flow metering pump and the vaporization chamber.

[0013] Optionally, it further includes a vaporization chamber temperature controller and a transmission tube temperature controller, wherein the vaporization chamber temperature controller is electrically connected to the vaporization chamber, and the transmission tube temperature controller is electrically connected to the transmission tube.

[0014] Optionally, a hydrogen sensor is also included.

[0015] In a second aspect, the present invention further provides a composite gasification thermogravimetric analysis method for biomass and coal, which is applicable to any of the above-mentioned gasification thermogravimetric analysis devices, and comprises the steps of:

[0016] Set the temperature of the transmission pipe with heating tape to 120°C;

[0017] Set up gasification heat analysis program, water vapor and gas control program according to gasification experiment requirements;

[0018] According to the water vapor content required by the gasification experiment, the flow rate of the constant flow metering pump and the carrier gas flow rate are set, the formula is compiled into the program, the target volume concentration of water vapor and the vaporized mass of water are input, that is, the amount of carrier gas or reaction gas to be mixed is calculated, and the liquid solenoid valve of water, the solenoid valve of carrier gas and the mass flow meter are controlled by the program to realize the programmed control of the water vapor gas path;

[0019] Other gases are controlled by program.

[0020] Optionally, set the constant flow metering pump to mg / h, and the volume of water vapor per unit time is

[0021]

[0022] In the formula, m is the mass of water per unit time input by the constant flow metering pump, in g, R is the molar gas constant, which is 8.314 J / (mol*K), T is the temperature of the vaporization chamber, in K, is the molar mass of water, which is 18 g / mol, and P is the pressure, in Pa;

[0023] Set the water vapor carrier gas flow rate to V G mL / min, the volume concentration of water vapor in the carrier gas is

[0024] During the gasification process, a balance protective gas is required with a flow rate of 20 mL / min. The volume concentration of water vapor is

[0025] .

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. The composite gasification thermogravimetric analysis method and device for biomass and coal proposed in the present invention can realize the synchronous production and introduction of multiple gases such as water vapor, carbon dioxide, hydrogen, oxygen and other gasifying agents during the biomass and coal gasification thermal analysis experiment, and can introduce different gasifying agents at different time periods during the biomass and coal gasification process to control the gasification to achieve the desired effect.

[0028] 2. The design of gas solenoid valve without back pressure is adopted. After the solenoid valve is turned off, the pressure of the pipeline is automatically released to avoid experimental errors caused by a small amount of gas flowing into the gas line.

[0029] 3. Through the control software, the water vapor content and the amount of water and carrier gas required for the corresponding water vapor content can be calculated quickly and easily, and program control can be realized.

[0030] 4. Through the programmed control of multi-element gases, the accuracy of the thermogravimetric analysis method is ensured and the reproducibility of the method is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0032] Figure 1 A schematic diagram of a composite gasification gas control device according to an embodiment of the present invention;

[0033] Figure 2 This is a graph showing the thermal weight loss curve of coal composite gasification gas according to an embodiment of the present invention.

[0034] Figure numerals: 1, hydrogen gas mixture; 2, high purity carbon dioxide; 3, oxygen gas mixture; 4, high purity argon; 5, hydrogen gas mixture pressure reducing valve; 6, carbon dioxide pressure reducing valve; 7, oxygen gas mixture pressure reducing valve; 8, argon gas pressure reducing valve; 9, first gas check valve; 10, second gas check valve; 11, third gas check valve; 12, fourth gas check valve; 13, fifth gas check valve; 14, sixth gas check valve; 15, first solenoid valve; 16, second solenoid valve; 17, third solenoid valve; 18, fourth solenoid valve; 19, fifth solenoid valve; 20, The sixth solenoid valve; 21. Host computer; 22. The first mass flow meter; 23. The second mass flow meter; 24. The third mass flow meter; 25. The fourth mass flow meter; 26. The fifth mass flow meter; 27. The sixth mass flow meter; 28. The constant flow metering pump; 29. ​​The liquid check valve; 30. The liquid solenoid valve; 31. The vaporization chamber temperature controller; 32. The transmission pipe temperature controller; 33. The vaporization chamber; 34. The first manual stop valve; 35. The transmission pipe with heating tape; 36. The second manual stop valve; 37. The hydrogen sensor; 38. The third manual stop valve. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0036] Example:

[0037] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchanged where appropriate, so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations of the embodiments of the present invention are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0038] It should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0039] In the description of the present invention, "multiple" means at least two, such as two, three, etc., unless otherwise clearly defined. In addition, unless otherwise clearly defined and defined, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0040] In the present invention, unless otherwise clearly specified and limited, a first feature being "above" or "below" a second feature may mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, a first feature being "above", "above" or "above" a second feature may mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. A first feature being "below", "below" or "below" a second feature may mean that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is lower in level than the second feature.

[0041] See also Figure 1, a gasification thermogravimetric analysis device, which specifically includes: a thermal analyzer and a water vapor quantitative vaporization introduction unit and a multi-gas control introduction unit respectively connected to the thermal analyzer through a gas pipeline, wherein the water vapor quantitative vaporization introduction unit includes a constant flow metering pump 28 and a vaporization chamber 33, pure water is injected into the vaporization chamber 33 through the constant flow metering pump 28, and the vaporized water vapor enters the thermal analyzer through a transmission pipe with a heating belt, and the transmission pipe with the heating belt is provided with a first manual stop valve 34 and a third manual stop valve 38; the multi-gas control introduction unit includes gas cylinders respectively filled with a hydrogen mixture 1, a high-purity carbon dioxide 2, an oxygen mixture 3 and a high-purity argon 4, the gas cylinder filled with high-purity argon 4 is connected to the transmission pipe between the vaporization chamber 33 and the first manual stop valve 34 through a gas pipeline, and the gas cylinder filled with high-purity argon 4 is connected to the thermal analyzer through another gas pipeline; the gas cylinders filled with a hydrogen mixture 1, a high-purity carbon dioxide 2, an oxygen mixture 3 and a high-purity argon 4 are respectively connected to the transmission pipe between the vaporization chamber 33 and the first manual stop valve 34 through a gas pipeline. A second manual stop valve 36 is provided on the transmission pipe connected to the first manual stop valve 34 and the third manual stop valve 38 and at the confluence of the gas pipelines. Each gas pipeline is provided with a pressure reducing valve (specifically a hydrogen mixed gas pressure reducing valve 5, a carbon dioxide pressure reducing valve 6, an oxygen mixed gas pressure reducing valve 7 and an argon pressure reducing valve 8), a check valve (specifically a first gas check valve 9, a second gas check valve 10, a third gas check valve 11, a fourth gas check valve 12, a fifth gas check valve 13) in sequence along the gas flow direction. The pressure reducing valve, check valve, solenoid valve and mass flow meter are all electrically connected to the host computer 21.

[0042] As an optional implementation, in some embodiments, a liquid check valve 29 and a liquid solenoid valve 30 are further included between the constant flow metering pump 28 and the vaporization chamber 33 .

[0043] As an optional implementation, in some embodiments, a vaporization chamber temperature controller 31 and a transmission tube temperature controller 32 are further included, wherein the vaporization chamber temperature controller 31 is electrically connected to the vaporization chamber 33, and the transmission tube temperature controller 32 is electrically connected to the transmission tube.

[0044] As an optional implementation, in some embodiments, a hydrogen sensor 37 is also included.

[0045] Specifically, the purpose of the embodiment of the present invention is to provide a device for water vaporization and quantitative introduction of multiple gases for biomass and coal composite gasification, which is used to introduce gas into a thermal analyzer device according to a program, and mainly includes: a water vapor quantitative vaporizer, multiple gases (carbon dioxide, hydrogen mixed gas, oxygen mixed gas) gas control, a hydrogen sensor, etc. Pure water is injected into the vaporization chamber through a constant flow metering pump, and after vaporization, the water vapor is controlled by a liquid check valve and a stop valve to enter a mixer with heating through a transmission pipe with a heating belt; argon gas is used as a carrier gas to bring water vapor into the thermal analyzer, and the control of water vapor can be achieved through a solenoid valve, a flow meter, and a program control software, and the control of water vapor concentration can be achieved through the flow rate of argon gas; the injection flow rate and injection time of multiple gases (carbon dioxide, hydrogen mixed gas, oxygen mixed gas, argon) during the reaction process can be controlled through a pressure reducing valve, a check valve, a mass flow meter, a solenoid valve control, a program control software, etc., and enter the thermal analyzer furnace through a stop valve and a transmission pipe with heating. At the same time, the computer is used to control the solenoid valve, mass flow meter, controller, hydrogen sensor, etc., and program control is performed to control the gas to be passed into the thermal analysis instrument according to the requirements of the multi-element gasification agent use in the biomass and coal composite gasification experiment. Compared with the existing technology, the present invention can control the gas switching time of the baseline and the switching time of the sample during the actual test process, and will not cause a large experimental error due to the operation time problem or the pipeline holding back the gas, resulting in a small amount of reaction gas entering the thermal analysis, thereby causing inaccurate experimental results. In addition, this experiment is suitable for both the oxidation-reduction experiment of the catalyst and the thermal analysis experiment of the water vapor atmosphere.

[0046] Exemplarily, a composite gasification thermogravimetric analysis method and gas control device for biomass and coal, some modifications are made to the thermal analyzer before the experiment. In this implementation case, the Netzsch synchronous thermal analysis 409PC is modified, the casing is opened, and a heating belt is added to the reaction gas path in front of the furnace body, and the casing is reinstalled. The other end of the transmission pipe 35 with a heating belt passing through the third manual stop valve with heating is connected to the reaction gas path of the furnace body after the thermal analysis modification, and the carbon dioxide, oxygen, and argon gas cylinders are connected to the device, and an empty flat-bottomed crucible is loaded, and a pre-weighed 10 mg sample is added. The solenoid valves and mass flow meters of the gasifying agents such as carbon dioxide, oxygen, and argon are controlled by program, and the vaporization chamber temperature controller 31 is turned on, and the vaporization temperature is set to 300°C. The temperature controller 32 with the transmission pipe is turned on and set The temperature is 120℃, edit the gas control program, such as setting 0-43 minutes, the sixth solenoid valve is opened, the sixth mass flow meter flow is 20mL / min, the fifth solenoid valve is opened, the fifth mass flow meter flow is 40mL / min, 44-74 minutes, open the liquid solenoid valve, the constant flow metering pump flow is 1g / h, the third solenoid valve is opened, the third mass flow meter flow is 20mL / min, the first solenoid valve is opened, the first mass flow meter flow is 10mL / min; 75-80 minutes, the fifth solenoid valve is opened, the fifth mass flow meter flow is 40mL / min; 81-101 minutes, the second solenoid valve is opened, the second mass flow meter flow is 2mL / min, the fifth solenoid valve is opened, and the fifth mass flow meter flow is 38mL / min. The thermal analyzer records the test data. The thermal analysis is responsible for program heating and recording weight loss changes, and the gas control device is responsible for gas control. After the thermal analysis is balanced, click the thermal analysis start, and at the same time change the manual control in the gas control software to automatic control, and introduce the program compiled by the gas installation. The experiment automatically records the thermal analysis data. When the experiment is over, the program ends automatically, the constant flow metering pump is turned off, and the solenoid valve is closed.

[0047] Unless otherwise specified, the equipment and reagents used in the present invention are conventional commercial products in the technical field, which have the advantages of easy availability of materials and low cost.

[0048] The present invention also provides a composite gasification thermogravimetric analysis method for biomass and coal, which is applicable to the above-mentioned gasification thermogravimetric analysis device, and the method comprises the following steps:

[0049] Step 1: Before the experiment, make some modifications to the thermal analyzer, add a heating belt to the reaction gas path in front of the furnace, and set the transmission pipe temperature to 120℃.

[0050] Step 2: Set up the gasification thermal analysis program, water vapor and gas control program according to the requirements of the gasification experiment. For example, for the multi-element gasification experiment of coal, set the temperature rising program to rise to 800°C at 20°C / min, keep the temperature at 800°C for 40 minutes, and then rise to 1000°C at 10°C / min. The experiment ends.

[0051] Step 3: Set the constant flow metering pump to mg / h, and the volume of water vapor per unit time is

[0052]

[0053] Where m is the mass of water per unit time input by the constant flow metering pump, in g, R is the molar gas constant, which is 8.314 J / (mol*K), T is the temperature of the vaporization chamber, in K, is the molar mass of water, which is 18 g / mol, and P is the pressure, in Pa.

[0054] Step 4: Set the water vapor carrier gas flow rate to V G mL / min, the volume concentration of water vapor in the carrier gas is

[0055] During the gasification process, a balance protective gas is required with a flow rate of 20 mL / min. The volume concentration of water vapor is

[0056] According to the water vapor content required by the gasification experiment, the flow rate of the constant flow metering pump and the carrier gas flow rate are set, the formula is programmed into the program, the target volume concentration of water vapor and the vaporized mass of water are input, and the amount of carrier gas or reaction gas to be mixed is calculated. The program controls the liquid solenoid valve of water, the solenoid valve of carrier gas and the mass flow meter to achieve programmed control of the water vapor gas path;

[0057] Step 5: Control the solenoid valves and mass flow meters of other gasification agents such as carbon dioxide, hydrogen mixture, and oxygen mixture through the program, edit the gas control program, such as setting 0-43 minutes, the sixth solenoid valve is opened, the sixth mass flow meter flow is 20mL / minute, the fifth solenoid valve is opened, the fifth mass flow meter flow is 40mL / minute, 44-74 minutes, open the liquid solenoid valve, the constant flow metering pump flow is 1g / h, the third solenoid valve is opened, the third mass flow meter flow is 20mL / minute, the first solenoid valve is opened, and the first mass flow meter flow is 10mL / minute; 75-80 minutes, the fifth solenoid valve is opened, and the fifth mass flow meter flow is 40mL / minute; 81-101 minutes, the second solenoid valve is opened, the second mass flow meter flow is 2mL / minute, the fifth solenoid valve is opened, and the fifth mass flow meter flow is 38mL / minute. At the end of the reaction, turn off the constant flow metering pump and the solenoid valve. The thermal analyzer records the test data. Other multi-element gasification thermal analysis experimental steps are similar, and the temperature rise program and gas switching can be set according to actual needs.

[0058] Step 6: Composite gasification data processing, obtain DTG data by first-order differential of TG, and calculate the gasification amount in each gasification stage.

[0059] The present invention can realize the synchronous production and introduction of multiple gases such as water vapor, carbon dioxide, hydrogen, oxygen and other gasifying agents during the biomass and coal gasification thermal analysis experiment, and can realize the introduction of different gasifying agents at different time periods during the biomass and coal gasification process to control the gasification to achieve the desired effect. Through the control software, the water vapor content and the amount of water and carrier gas required for the corresponding water vapor content can be conveniently and quickly calculated, and program control can be realized.

[0060] See also Figure 1 , adopts the design of gas solenoid valve without back pressure. After the solenoid valve is turned off, the pressure in the pipeline is automatically released to avoid experimental errors caused by a small amount of gas flowing into the gas line.

[0061] See also Figure 2 Through the programmed control of multi-element gases, the accuracy of the thermogravimetric analysis method is ensured and the reproducibility of the method is improved.

[0062] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0063] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable ordinary technicians in the field to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made based on the essence of the content of the present invention should be included in the protection scope of the present invention.

Claims

1. A gasification thermogravimetric analysis device, characterized in that: include: Thermal analyzer; a water vapor quantitative vaporization introduction unit connected to the thermal analyzer via a gas pipeline, A multi-element gas control introduction unit connected to the thermal analyzer via a gas pipeline, Wherein, the water vapor quantitative vaporization introduction unit comprises a constant flow metering pump and a vaporization chamber, pure water is injected into the vaporization chamber through the constant flow metering pump, and the vaporized water vapor enters the thermal analyzer through a transmission pipe with a heating belt, and a first manual stop valve and a third manual stop valve are provided on the transmission pipe with a heating belt; The multi-gas control introduction unit includes gas cylinders respectively filled with hydrogen mixture, high-purity carbon dioxide, oxygen mixture and high-purity argon. The gas cylinder filled with high-purity argon is connected to the transmission pipe between the vaporization chamber and the first manual stop valve through a gas pipeline for adjusting the water vapor concentration; the gas cylinder filled with high-purity argon is connected to the thermal analyzer through another gas pipeline for providing balance protection gas and an inert gas source for the gasification process; the gas cylinders filled with hydrogen mixture, high-purity carbon dioxide, oxygen mixture and high-purity argon are respectively connected to the transmission pipe between the first manual stop valve and the third manual stop valve through gas pipelines, and a second manual stop valve is arranged at the confluence of the gas pipelines. Each gas pipeline is sequentially provided with a pressure reducing valve, a check valve, a solenoid valve and a mass flow meter along the gas flow direction, and the pressure reducing valve, the check valve, the solenoid valve and the mass flow meter are all electrically connected to the host computer.

2. The gasification thermogravimetric analysis device according to claim 1, characterized in that: It also includes a liquid check valve and a liquid solenoid valve arranged between the constant flow metering pump and the vaporization chamber.

3. The gasification thermogravimetric analysis device according to claim 1, characterized in that: It also includes a vaporization chamber temperature controller and a transmission tube temperature controller, wherein the vaporization chamber temperature controller is electrically connected to the vaporization chamber, and the transmission tube temperature controller is electrically connected to the transmission tube.

4. The gasification thermogravimetric analysis device according to claim 1, characterized in that: A hydrogen sensor is also included.

5. A composite gasification thermogravimetric analysis method for biomass and coal, applicable to the gasification thermogravimetric analysis device as claimed in any one of claims 1 to 4, characterized in that: Includes steps: Set the temperature of the transmission pipe with heating tape to 120°C; Set up gasification heat analysis program, water vapor and gas control program according to gasification experiment requirements; According to the water vapor content required by the gasification experiment, the flow rate of the constant flow metering pump and the carrier gas flow rate are set, the formula is compiled into the program, the target volume concentration of water vapor and the vaporized mass of water are input, that is, the amount of carrier gas or reaction gas to be mixed is calculated, and the liquid solenoid valve of water, the solenoid valve of carrier gas and the mass flow meter are controlled by the program to realize the programmed control of the water vapor gas path; Other gases are controlled by program.

6. The composite gasification thermogravimetric analysis method of biomass and coal according to claim 5, characterized in that: Set the constant flow metering pump to mg / h, and the volume of water vapor per unit time is In the formula, m is the mass of water per unit time input by the constant flow metering pump, in g, R is the molar gas constant, which is 8.314 J / (mol*K), T is the temperature of the vaporization chamber, in K, is the molar mass of water, which is 18 g / mol, and P is the pressure, in Pa; Set the water vapor carrier gas flow rate to V G mL / min, the volume concentration of water vapor in the carrier gas is During the gasification process, a balance protective gas is required with a flow rate of 20 mL / min. The volume concentration of water vapor is 。

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