JP2016003896A - Heat separation type ch analysis measurement system in transparent heating furnace - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of controlling combustion by various conditions, while watching a changing state caused by heating of a sample, and determining simply and accurately carbon and hydrogen in the state.SOLUTION: While controlling a combustion state by each condition such as a heating temperature, heating speed and an oxygen amount, each amount of carbon and hydrogen is determined simultaneously, simply and accurately by using a calibration curve by an organic compound standard sample.

Description

     The present invention relates to the determination of carbon and hydrogen in soot (elemental carbon) combustion studies.

Regarding soot (elemental carbon) generated by incomplete combustion of organic carbon, 1) measurement of atmospheric particulate matter (PM2.5), 2) research on diesel exhaust particles (DEP), 3) biomass and industry Many researches have been conducted on the use of wastes and 4) the production of activated carbon that is effective in removing toxic substances in the environment.

In particular, as an analysis method of carbon components in atmospheric fine particulate matter (PM2.5), measurement is performed as organic carbon category OC and elemental carbon category EC, but soot generated by incomplete combustion due to heating in He However, it has been pointed out that there is an obstacle in the classification of OC and EC.

    On the other hand, there is no good research tool to determine the optimum conditions by controlling the performance of activated carbon used for environmental purification, the production of charcoal, and the combustion of biomass and industrial waste as energy resources. Biomass power generation requires elemental analysis (carbon, hydrogen) as an industrial analysis, but visual observation during heating and measurement of CH content are also important in order to capture the characteristics of each material.

Ministry of the Environment Air Microparticulate Matter (PM2.5) Component Measurement Manual April 19, 2012 Ministry of the Environment

Mitsui Engineering & Shipbuilding Technical Report no.190 (2007-3)

In order to distinguish soot generated by incomplete combustion of organic carbon and soot in collected PM2.5 during measurement by IMPROVE method of carbon component measurement of fine particulate matter (PM2.5) in the atmosphere. Use the appropriate method. First, the elemental carbon in the collected filter paper is irradiated, and the amount of organic carbon due to incomplete combustion is determined by the reaction of the optical device with respect to the soot discharged later by heating. However, it is difficult when the amount of elemental carbon in the collection filter paper is large or when the density is not uniform. Furthermore, several problems have been pointed out, such as deterioration of optical instruments and false reaction of colored objects. Some actual measurement data has a too large amount of correction for the measurement value, which is problematic. If it is possible to search for a condition where the organic material burns without producing soot, no correction is necessary. It is effective if there is a method that can directly measure the amount of carbon and hydrogen at the same time, and can observe the occurrence of soot in a small amount of sample.

In the production research of charcoal and activated carbon, the carbonization process of the material is important as a pyrolysis process. Since the calorific value varies depending on the carbonization temperature, it is possible to look directly at the state of various soot generation using a small amount of sample. Efficient research is also possible by directly observing the combustion of pellets and biomass and quantifying the situation.

Similarly, while studying soot in diesel engine exhaust (DEP), tunnel dust, etc., and studying the combustion conditions of carbon atoms such as carbon fibers and carbon nanotubes, using a small amount of sample, It is useful to use a method that can easily perform accurate quantification of intermediate carbon and hydrogen by heating.

Thus, it is effective to control the combustion under various conditions while observing the state of change due to heating of the sample, and simple and accurate determination of carbon and hydrogen in that situation is effective.

  The present invention that solves the above-described object has a first transparent heating furnace, a second combustion furnace, and a transparent combustion tube for pyrolytic combustion of a sample. A portion corresponding to the second combustion furnace portion is filled with a metal catalyst, the first transparent heating furnace has a function of controlling the combustion temperature and the heating speed, and the second combustion furnace is the first furnace. It has a function to completely burn the gas generated in the above, and it is necessary from the content (μg, ppm, w / w%) and content ratio of the specified element from the gas carried by the carrier gas It has a detection and calculation means for obtaining an accurate measurement value.

Each of the furnaces has a first transparent heating furnace, a second combustion furnace, and a transparent combustion tube for thermally decomposing and burning the sample. The first heating furnace visually observes the combustion state of the sample. It has the function of controlling the combustion temperature and heating speed, and the combustion tube in the second furnace is filled with a metal catalyst so that the gas generated in the first furnace is completely burned and further carried by the carrier gas. It is characterized by having a detection and calculation means for obtaining a necessary measurement value from the content (μg, ppm, w / w%) of the predetermined element from the gas and the content ratio.

First, the method of the present invention directly looks at the generation of soot for each temperature fraction defined in the IMPROVE method for complex changes in elemental carbon generated by organic carbon during the thermal decomposition of the carbon component of fine particulate matter in the atmosphere. Since it is possible, there is an advantage that it can be accurately determined by taking basic data for the determination of OC (organic carbon).

Secondly, the method of the present invention can adjust the pyrolysis process of carbonization while looking directly at the addition of air, speed, temperature conditions, etc. in the study of carbides. it can. The sewage sludge carbide confirms the self-heating characteristics of whether carbonization is sufficiently advanced by the atomic ratio of hydrogen to carbon (= H% / C atomic weight ÷ C% / H atomic weight). And can be measured accurately.

Third, the method of the present invention is effective in analyzing the purity of low-molecular materials and high-molecular materials, which are organic semiconductor materials. Although the total carbon content is measured as an organic substance for the performance as each material, grasping the decomposition process by thermal separation is also important for the analysis of purity. As a method for analyzing impurities in a thermally decomposable organic semiconductor material, accurate quantification by a thermal separation method in which the temperature is accurately controlled is effective.

The method of the present invention is provided with a reducing part for the fourth generated gas, and if the detection system is equipped with not only a TCD detector but also a FID, detector, infrared detector, or ion chromatography meter, N, S, F, It can be used for the determination of Cl, Br, I, P. Furthermore, it can be used for the determination of metals from the ash content of combustion residues. If an absorption tube for carbon dioxide and moisture is attached to the collection and diffusion part, it can be used for the gravimetric CH meter. Instead of the collection and diffusion part, the gas is guided to the absorption liquid and can be used for the determination of S, F, Cl, Br, I, and P with an automatic titrator. Thus, there is an effect obtained quantitatively while visually observing the behavior of each element in the gas generated by the thermal decomposition.

FIG. 1 is an explanatory diagram showing the configuration of the analysis system of the present invention. FIG. 2 shows the state of carbonization by the method of the present invention. (Example 2) FIG. 3 is a visual view of the soot of oxygen-free combustion according to the method of the present invention. Example 3

An example of the configuration of the analysis system of the present invention is shown in FIG. The first and second combustion furnaces, which are transparent heating furnaces, a part for collecting and diffusing the combustion gas, a detection system, and a calculation system. One combustion tube is installed in the first and second combustion furnaces, which are transparent heating furnaces, and a sample is placed on the sample insertion rod from the outside and placed in the middle of the transparent heating furnace. The combustion gas generated in the first furnace is completely burned in the second furnace, and the carrier gas is used as a collection diffuser and further flows to the detection system. The detection system has a detector that electrically detects the amount of gas, creates a calibration curve using an organic compound standard sample, and outputs the gas generated by thermal separation to the analysis value by the calculation system. The temperature of the transparent heating furnace is raised under arbitrarily set conditions. Determine the amount of carbon and hydrogen generated by adjusting the temperature and heating speed of the soot combustion state.

Below, the multi-walled carbon nanotube MWCNT is heated to 500 ° C, the amount of carbon and hydrogen in the generated gas is quantified while observing the state visually, and the amount of carbon and hydrogen until it is completely burned up to 950 ° C is experimentally determined. An example confirmed is shown in. Originally, the multi-walled carbon nanotube MWCNT is a lump of carbon, but there are some carbons that burn at a temperature of 500 ° C. or less as described above, and the multi-wall carbon nanotube MWCNT can be examined for flammability at low temperatures.
(Experiment)

Experiments on low temperature flammability of the multi-walled carbon nanotube MWCNT are shown below.
(Table 1)
CH analysis by thermal decomposition of multi-walled carbon nanotubes Sample amount 1.7533mg
Stage Furnace temperature C% H%
1 500 ° C 11.42 0.39
2 950 ° C 80.09 0.55

Fig. 2 shows the state until it completely burns while visually observing the carbonization of this system using rice husk as a model. It was charcoal at 400 ° C (upper in the figure) but burned considerably at 500 ° C (middle in the figure) and completely burned at 700 ° C (lower in the figure), leaving a clean white ash. Since this is ash, the amount of ash is also known by the weight before and after combustion. Since the second furnace burns completely into carbon dioxide, the quantitative relationship between carbon and hydrogen under each condition can be accurately examined by quantifying with a calibration curve using an organic compound standard sample.

FIG. 3 shows the state of carbonization of each biomass in an oxygen-free state in a 550 ° C. helium stream defined by the IMPROVE method of carbon component analysis of PM2.5. Since the carbonization has not progressed yet in the upper and middle in the figure, the burned one is classified as OC4, but the lower biomass in the figure is carbonized with oxygen-free in 550 ° C helium, and it is converted to EC1 by the IMPROVE method. It will be divided. In the IMPROVE method, the point immediately after adding 2% oxygen is corrected by the optical correction method and subtracted from EC1 and added to OC4. However, in this experiment, elemental carbon does not exist, so it occurred. It is possible to verify whether the elemental carbon matches the correction amount of the DRI meter.

The DRI meter used for the determination of carbon components in PM2.5 corrects soot generated during the temperature rise process using an optical method, but some problems have been pointed out in this method. The method of the invention is useful for studying the combustion state of organic carbon because it can visually grasp the state of soot generation using a small amount of sample. In addition, CH elemental analysis is necessary for biomass development, but quantitative measurement of CH in the process of incomplete combustion seems to be more important. Quantification between the process that can be seen directly and the combustion is useful for soot research in the biomass field, coal petroleum field, waste combustion field, etc. Carbon nanotubes and carbon fibers are important in Japan, but they are also useful for quality control under combustion conditions by measuring the carbon content by the method described above. Furthermore, harmful effects in the environment are a global problem, and international efforts are important. The method of the present invention, which can create and measure a simple calibration curve using an international standard sample, is an effective technique that can produce a measurement value common to each country using a small amount of these harmful substances.

1. First furnace (transparent heating furnace)
2. Second furnace (combustion furnace)
3. Combustion tube
4.Sample introduction rod
5.Sample
6. Collection and diffusion section
7.Detector
8.Calculation system

Claims (2)

A first transparent heating furnace, a second combustion furnace, and a transparent combustion tube for pyrolyzing and burning the sample, and corresponding to the second combustion furnace portion in the combustion tube extending over the two furnaces The part to be filled is filled with a metal catalyst, and the first transparent heating furnace has a function of controlling the combustion temperature and the heating speed,
The second combustion furnace has a function of completely burning the gas generated in the first furnace, and the content of a predetermined element (μg, ppm, w / w) from the gas carried by the carrier gas. %), And an analytical measurement system having detection and calculation means for obtaining a necessary measurement value from the content ratio A first transparent heating furnace, a second combustion furnace, and a transparent combustion tube for pyrolyzing and burning the sample, the combustion tube in the second furnace is filled with a metal catalyst, 1 has a function of controlling the combustion temperature and heating speed while visually observing the combustion state of the sample.
The gas generated in the first furnace is completely burned in the second combustion furnace, and the content (μg, ppm, w / w%) of a predetermined element from the gas carried by the carrier gas, And an analytical measurement system having detection and calculation means for obtaining a necessary measurement value from the content ratio

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