JPS60154140A - Method and apparatus for thermal weight analyzing measurement under high temperature and high pressure atmosphere - Google Patents

Abstract

PURPOSE:To use repeatedly the titled apparatus without corrosion problem by measuring directly the weight variation of a sample accompanied by the reaction and the state variations in a high temp. and high pressure system by using a quartz spring under precise temp. control. CONSTITUTION:The quartz spring 10 is hung down in a main body from the top part, a quartz rod 11, next a sample holder 13 are hung down thereunder. The temp. of the sample part is controlled by a furnace 14 and a program controller 27 up to a prescribed temp., and measurements in a fixed temp. rising rate, fixed temp. lowering rate and fixed temp. are possible. The temp. in the system is measured by a thermocouple 16 inserted into the apparatus main body 9. The reaction occurs under some condition in a gaseous atmosphere, as the result, the weight of the sample in the holder 13 is varied. But the weight variation thereat is measured by reading the position of a quartz marker 11 moved by a displacement of the spring 10 through a high pressure peep hole 12 by using a reading telescope 18, an image sensor 19.

Description

[Detailed description of the invention] Undeveloped 1jJ is a solid-gas reaction at high temperature and high pressure, and a change in state between solid and liquid in a supercritical gas atmosphere (solid → gas, solid → liquid → gas, liquid → gas). This invention relates to a device that determines a+1 the weight change of a sample due to ).

Conventionally, weight changes due to reactions under high temperature and high pressure were measured using 1111
The determination is carried out using an electric balance installed in a high-temperature, high-pressure system. Before the practical use of electric balances, thermogravimetric analysis under high temperature and pressure was hardly performed.

In devices using electric balances, the displacement caused by a single weight change is returned to the original position (before the weight change occurs) by generating torque by the electromagnetic force generated by passing a current through the magnet. A method is used to extract the current required at this time as an electrical signal and convert the displacement. In this case, the main body of the electric balance is installed in a high-voltage system, and only electrical signals are taken out of the system and recorded.

When filling a high-pressure system with a corrosive gas as a reactive gas (
For example, high-pressure sulfidation reaction of iron oxide Fe2O3+1-i2
+2H2S+2FeS+3H20) or when a corrosive gas is generated as a result of the reaction (e.g. reaction of iron sulfide in high pressure hydrogen Fe32 +H,, -+FeS+H
7S) corrodes the metal parts in the high-pressure system of the electric balance body, making it impossible to use it for a long time or repeatedly.

In addition to using a double electric balance, an electric balance using an optical sensor may also be used, but the problems when corrosive debris is involved are the same.

The present invention is suitable for thermogravimetric analysis under high temperature and high pressure using corrosive scum or when corrosive gas is produced as a by-product of the reaction. It is an object of the present invention to provide a method and apparatus that can be used repeatedly without the above-mentioned corrosion problem.

Furthermore, knowledge regarding the physical properties of supercritical gases is particularly important in extraction and separation technology using supercritical gases. The supercritical gas used is mainly ethylene (critical pressure 5.03
MPa, critical temperature -8 °C), carbon oxide (critical pressure 7.38 MPa, critical temperature 31 °C), toluene (critical pressure 4-14-1 l, critical temperature 319 °C), etc.
Conditions of temperature of 20 to 300°C (near J) and pressure of 50 kg/am2 or more are often used. When investigating phase equilibrium and physical properties in supercritical gas, it is necessary to change the temperature and pressure. There is.

The object of the present invention is to provide a method and apparatus that can control the temperature and pressure separately or simultaneously.

Furthermore, in order to maintain the supercritical gas-like fm, it is necessary to maintain the entire high-pressure system at a temperature below the critical temperature of the gas.

(For example, if there is a region below the critical temperature in a part of the system, a supercritical state cannot be maintained.) Therefore, since the sample weight measuring section also reaches a temperature above the critical temperature, a method such as an electric balance is used. It is impossible to measure with a balance that is

The present invention enables measurement even in this high temperature atmosphere.

In order to achieve the second object, the present invention has the structure described in the claims, that is, under precise temperature control, a quartz spring is used to detect reactions and state changes of a sample. By directly measuring the weight change of the sample due to the change from the high-temperature and high-pressure system, the above-mentioned corrosion problem does not occur.

In addition, temperature and pressure can be measured separately or simultaneously by converting the weight change of a sample under a high-temperature, high-pressure cloud atmosphere into the displacement of a quartz spring, and by optically reading and measuring the displacement directly from the high-temperature, high-pressure system through a high-pressure observation window. Since it can be controlled, it is extremely effective and suitable as a means of thermogravimetric analysis in a high-temperature, high-pressure cloud atmosphere.

Next, embodiments of the device according to the present invention will be described with reference to the drawings.

Reference numeral 9 denotes a main body of a high-temperature, high-pressure thermogravimetric analyzer which is the main subject of the present invention. Inside this main body, a quartz spring lO is suspended from the top, and a quartz rod (used as a marker) 11 is placed below it.
, and then the sample holder 13 is suspended. Atmosphere debris such as corrosive gas is removed from cylinder 1 to pressure regulator 2.
The air is then sent to the compressor 3, where it is boosted to a predetermined pressure. The pressurized gas is stored in a pressure accumulator 4, and the pressure is maintained at a constant pressure up to a predetermined pressure by an automatic pressure regulator 5. Next, it passes through a mass flow meter 6 and is introduced into the main body of the apparatus. The flow rate is adjusted by flow control valves 7 and 21. The pressure within the system is measured by a pressure transmitter 8.

By the quartz spring 10, 1. ) 1llll change
In the case of 'd', the buoyant force exerted on the sample and the sample holder 13 may be taken into consideration, and the gas may be allowed to flow from - to do, or from below to above, as necessary. Device body 9
The scum that has passed through the inside passes through a drain separator 20, an automatic pressure regulator (pressure relief valve) 22 for pressure reduction, and is discharged to the outside of the system.

The temperature of the sample section is controlled to a predetermined temperature by the furnace 14 and the program controller 27, making it possible to perform measurements at constant temperature increases, constant temperature decreases, and constant temperatures. The temperature within the system is measured by a thermocouple 16 inserted into the main body 9 of the device.

The pressure in the system is controlled to a constant pressure increase, constant pressure drop, and constant pressure by automatic pressure regulators 5 and 22. The temperature, pressure, and flow rate in the system are measured by a temperature measurement unit 28 and a pressure measurement unit 23.
Data is stored in the microcomputer 26 from the flow rate measurement unit 24 via each A/D converter 25. 1
5 is a thermocouple for controlling the furnace.

A reaction occurs under the condition of atmospheric gas, and as a result, a change in weight of the sample in the sample holder 13 is caused, but the measurement of the weight change at that time is based on the position of the quartz marker 11 moved by the displacement of the quartz spring IO. is read through the high-pressure peephole 12 through the telescope 18 and image sensor 1.
Measure at 9.

In this case, two high-voltage viewing windows 12 installed in the main body 9 of the apparatus are placed diagonally, and the displacement of the marker 11 can be easily seen from one side using a light source 17. The obtained data is stored in the microcomputer 26.

Next, an example for measuring the phase equilibrium or physical properties of a substance in a supercritical gas will be described. A sample whose weight is known and whose physical properties under supercritical conditions are to be measured is placed in the sample holder 13 . In order to maintain the gas in a supercritical state, it is necessary to maintain the entire system at 11M degrees above the critical temperature.

Therefore, the temperature of the entire device is controlled in a constant temperature room, and the container and piping in which supercritical gas flows are controlled using ribbon heaters, etc.
It is also possible to control the temperature. If the gas is a gas at room temperature, the compressor 3 increases the pressure to a critical pressure or higher.

In addition, when the liquid is in a liquefied state at room temperature, the liquid supplied from the liquid tank 30 is pumped into the high-pressure system by the liquid feed pump 29 (then converted to supercritical gas in the vaporizer 31. 1) Physical phase equilibrium under supercritical gas Measurements are performed under temperature and pressure control.The temperature of the entire system is controlled in a constant temperature room, etc., and is also controlled under constant A and temperature decreasing rates.The pressure is controlled by an automatic pressure regulator 5. - At 22, it is controlled to be constant A, - to a pressure lowering rate, or to a constant pressure.The flow rate of the supercritical gas is also controlled, and the flow rate is monitored by the □ mass flow meter 6.

In particular, in measuring the extraction separation power and extraction separation rate when a sample is extracted and separated using supercritical gas, the results can be obtained more efficiently by +13 than the knowledge obtained by conventional methods.

[Brief explanation of the drawing]

The drawing is a block diagram of the invention. 9 is the device main body, 10 is a quartz spring, 11 is a quartz rod marker, 12 is a high-pressure sight glass, 13 is a sample holder,
14 is a furnace, 15-16 are thermocouples, 17 is a light source, 18 is a telescope, 19 is an image sensor, 25 is an A/D converter, 2
6 is a microcomputer. 4゜＋i Establishment - Continuation of page 1 of the Artificial Millet Surgery Clinic @ Inventor Shin Yokoyama - @ Inventor Sei 1) Hideo @ Inventor Wakunori Maekawa @ Inventor Totabe Goto @ Inventor Jun Watanabe - Toyohira, Sapporo City Nishioka 5-jo 14-48 Hatachi, Sapporo City Toyohira-ku Tsukisamu Higashi 2-jo 17T 2-2 Tsukisamu Higashi 2-jo 1 Tamome 6-1, Toyohira-ku, Sapporo City Tsukisamu Higashi 2-jo 1'7T, Toyohira-ku, Sapporo City 2-4 143 Kitakase, Saiwai-ku, Kawasaki City

Claims (1)

[Claims] (1) Under precise temperature control, a quartz spring is used to measure the weight of the sample as it reacts and changes in state! - A thermogravimetric analysis measurement method in a high-temperature, high-pressure atmosphere, which is characterized by directly measuring changes from a high-temperature, high-pressure system. (2) Thermogravimetric analysis measurement characterized by converting the weight change of the sample in a 1η temperature and high pressure atmosphere into the displacement of a quartz spring, and reading and measuring the displacement optically directly from the high temperature and high pressure system through a high pressure viewing window. Method. (3) The device according to claim (2), in which changes in the quartz spring are directly read with a telescope through a high-pressure peephole, and automatically recorded by an image sensor and a microcomputer installed in the telescope. (2) Claims (2) for measuring changes in the reaction and state of a sample in a high-temperature, high-pressure system under static or flowing normal gas, corrosive gas, or supercritical gas
The device described. (5) Claims that measure the state, weight change, and behavior of substances due to reactions in a high-temperature, high-pressure system under a constant temperature or pressure increase/decrease rate, -electronic increase/decrease rate, or constant temperature and constant pressure (2)
) device described.