JPS5810699B2 - Deodorizing performance measurement method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for measuring the deodorizing performance of a device that uses a combustion method to deodorize dry exhaust gas (hereinafter referred to as off-wheel exhaust gas) from an offset rotary printing press that uses shade set ink. The purpose is to provide a method for measuring the deodorizing performance of the deodorizing device described above, which is particularly quick, simple, and rich in objective evaluation.

Since off-road vehicle exhaust gas using heat-set ink is accompanied by a very strong odor, it is widely used to deodorize off-road vehicle exhaust gas using a combustion method.

However, the current situation is that it is not possible to objectively evaluate the performance of this deodorizing device.

This is because, as will be explained in detail below, it is unclear what causes the odor of off-wheel exhaust gas after combustion.

Therefore, this causes inconveniences such as different evaluations of the performance of the deodorizing devices on the side that manufactures them.

Under the Offensive Odor Prevention Act, offensive substances are defined as substances specified by government ordinance that cause unpleasant odors such as ammonia, methyl mercapulin, etc. and may damage the living environment. The purpose of this law is to preserve the living environment and contribute to the protection of public health by regulating the emission of foul-smelling substances generated by business activities at workplaces.

Based on this idea, ammonia, methylmercapkun, hydrogen sulfide,
Methyl sulfide and trimethylamine have been designated by government ordinance and the Offensive Odor Prevention Law has been enforced, but these five substances can be regulated by law in the kraft pulp manufacturing industry, chemical plants, fish iliac processing plants, human waste processing plants, etc. However, the current situation is that it is difficult to enforce legal regulations for other petrochemical-related factories and painting/paint factories, which have many complaints of bad odors.

The same holds true for off-cycle exhaust gas in the printing industry.

Moreover, the above laws and regulations regulate the concentration of each malodorous substance, and analysis is based on instrumental analysis.

Instrumental analysis requires advanced analysis techniques and equipment, is complicated to operate, and lacks quick response.

Further, it is necessary that the main substance causing the malodor is clear, and it is preferable that the gas has a relatively simple composition.

On the other hand, in the case of off-wheel exhaust gas, the high boiling point petroleum solvent for the ink solvent evaporates during drying, is partially thermally decomposed, and is then burned at 700 to 800°C using a gas burner or the like, or It uses a catalytic catalytic combustion method to deodorize, and as it goes through a complex thermal decomposition and combustion process, dozens of substances are produced, and the main Currently, malodorous substances are not fixed either.

In addition, in many cases, there are several odor emission sources, and the concentration of emitted gas varies greatly depending on the operating conditions of the printing press, so prompt sampling and analysis are required. In many cases, analytical methods cannot cope with the problem.

Next, there is a sensory test method that uses the human sense of smell as a direct method for measuring deodorizing performance.

This is the most practical method, and includes the ASTM method, saline solution balance method, and three-point comparison odor bag method.For example, as a guidance goal of the Tokyo Metropolitan Pollution Bureau, the three-point comparison odor bag method There are examples where the odor intensity (the number of times it is diluted with odorless air to reach the odor limit concentration) is 300 times or less.

In these cases, individual differences among olfactory test subjects (panels) are unavoidable, and it is difficult to measure a large number of samples at once due to problems such as securing panels and sensory fatigue.

Furthermore, it is extremely difficult to completely remove the odor of the syringe or the packaging itself, which causes measurement errors.

Additionally, there are drawbacks such as high costs for consumable materials such as mounting.

The present inventors have conducted research with the aim of solving the above-mentioned drawbacks and providing a method that is quick and easy to measure the deodorizing performance of a deodorizing device using the off-wheel exhaust gas combustion method and is rich in objective evaluation. However, gas chromatography (hereinafter referred to as G
At the same time, the odor intensity was measured using a sensory test, and this measurement was repeated several dozen times to collect data. Investigating the relationship between component concentration and odor intensity, rather than analyzing malodorous substances, there is a correlation between odor intensity and specific component concentration, and it is recommended to select components that are relatively high in concentration and easy to analyze. The present invention was completed by discovering the following.

That is, the present invention is a method for measuring the deodorizing performance of an apparatus that uses a combustion method to deodorize the dry exhaust gas of an offset rotary printing press that uses heat-set type ink, and the method comprises: Measurement of the deodorizing performance of the deodorizing device described above, characterized in that the concentration of lower unsaturated hydrocarbons is measured, and then the odor intensity is determined based on the positive correlation between the lower unsaturated hydrocarbon concentration and the odor intensity. The gist is the law.

Hereinafter, the above-mentioned present invention will be explained in detail.

Dry exhaust from an offset rotary printing machine that uses heat-set ink, which uses a high-melting-point resin such as maleic acid resin or phenolic resin with a small amount of oil and fat dissolved in a high-boiling petroleum solvent as a medium. Gas deodorized by combustion using various combustion deodorizing devices such as direct combustion or catalytic combustion deodorizing devices is not completely decomposed into odorless substances.
This contains various ingredients.

As mentioned above, the present inventors conducted GC analysis of this gas, and found that the C2 to C4 low boiling point components of unsaturated hydrocarbons and CI3
It was determined that about 10 of the high boiling point components of ~C15 are odor-related components that have a correlation between concentration and odor intensity.

High boiling point components of CI3 to C15 are not preferable because they are difficult to analyze and the reliability of correlation is somewhat lacking. It is appropriate to choose C4 lower unsaturated hydrocarbons.

As mentioned above, in the present invention, it is sufficient to determine the concentration of lower unsaturated hydrocarbons, and in this case, it is sufficient to determine the concentration of lower unsaturated hydrocarbons, and at this time, it is sufficient to determine the concentration of lower unsaturated hydrocarbons, and at this time, it is also possible to determine the concentration of one of the C2 to C4 components such as acetylene, ethylene, propylene, etc., or the concentration of the above two or more components. can also give good results.

In particular, it is preferable to analyze and determine the concentration of ethylene, which has a high concentration.

Hereinafter, using ethylene as an example, the relationship between its concentration and odor intensity will be explained in detail.

Figure 1 is a diagram showing the relationship between ethylene concentration and odor intensity. Considering the variations in sensory tests, there is a good positive correlation, and approximately [odor intensity] - soox (ethylene concentration) There is a relationship between strength: dilution factor and ethylene concentration: ppmC1 (methane equivalent).

Next, a simple method for analyzing ethylene will be described.

The measuring equipment will be GC, and the detector will be FID (Flame Ionization Detector), which has high detection sensitivity and is widely used, and the separation column will be one that shows good separation of lower hydrocarbons. Although any material may be used, for example, the present inventors adopted Carbosieve-B (40 to 60 mesh), which is a type of carbon grain that is easy to handle.

There are no particular limitations on other GC conditions, such as carrier gas type, flow rate, separation, column temperature, sample amount, sample introduction vaporization chamber temperature, etc., and can be freely selected taking into account analysis accuracy, time, etc. GC analysis techniques may be applied.

To sample a sample gas, it is sufficient to collect 10 ml or more of the gas using a syringe, vacuum bottle, plastic bag, etc., and accurately introduce 1 to 5 ml of the gas directly into the GC using the syringe or the like.

FIG. 2 shows a GC chart obtained by exhaust gas analysis of the catalytic combustion type deodorizing apparatus according to the above method.

In each peak, 1 is methane, 2 is acetylene, 3 is ethylene, and 4 is ethane, and components beyond these are adsorbed under these analysis conditions and are not detected.

In this case, the concentration of ethylene is 7 ppm C1 in terms of methane.
According to the graph in FIG. 1, the odor intensity can be read as 5,600 times stronger.

The time required for analysis is approximately 3 minutes, and even if gas sampling time is included, measurement can be completed within 10 minutes per point.

According to the present invention, the deodorizing performance of a combustion-type deodorizing device for off-wheel exhaust gas can be determined by measuring the concentration of lower unsaturated hydrocarbons in the combustion-deodorized gas using GC, and determining the odor intensity from the concentration. It is simple and quick, does not require sample preparation, and analysis and measurement are simple and quick.As it is an instrumental analysis, it is more reliable than sensory testing and allows for numerical control.

Furthermore, since the substance most closely related to the odor of off-wheel exhaust gas is measured, it is possible to accurately measure the deodorizing performance.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 An offset rotary printing machine (manufactured by Mitsubishi Heavy T Co., Ltd., 8-color B-
Type B) dry exhaust gas was deodorized by combustion using a catalyst catalytic combustion deodorizer that was thought to have reduced catalytic activity and poor deodorizing performance, and was then subjected to measurements under the following conditions.

○Sample gas Sampling; Syringe 100m1O Analytical equipment; Hitachi Gas Chromatography Model 063 Sample introduction amount; Syringe 5m1 OGC conditions; Column: Carbosieve-B 40/60 mesh 1m x 3mm Dacolumn temperature = 200C Detector: FID Injection temperature: 250C Carrier gas: N240ml/mln GC range = 1x4 Chart speed: 10mm/min The GC chart obtained under these conditions is shown in Figure 2.

The numbers in the figure are as described above. The concentration of ethylene 3 in this case was 7 ppmC1 in terms of methane, and the positive correlation between the ethylene concentration and odor intensity shown in FIG. 1 showed that the odor intensity was 5600 times greater, and it was found that the deodorizing effect was extremely poor.

The measurement time was 3 minutes for sampling and 3 minutes for analysis, and the measurement was completed in about 10 minutes including the rest.

Example 2 The same dry exhaust gas as in Example 1 was measured using a catalytic catalytic combustion type deodorizing device in the same manner as in Example 1 for those that had relatively high catalytic activity and seemed to have good deodorizing performance.

The results are shown in FIG. The concentration of ethylene 3 is 0.35
ppmCI, and exhibits good deodorizing performance with 280 times the odor intensity.

Example 3 FIG. 4 shows the analysis results of exhaust gas after deodorization by a direct combustion type deodorizing device for dry exhaust gas similar to Example 1.

The results showed that ethylene was 1.8 ppmC1 and the odor intensity was 1400 times higher, indicating that it was necessary to further increase the combustion temperature to improve the deodorizing effect.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the correlation between ethylene concentration and odor intensity, and FIGS. 2 to 4 are GC charts of the measurement results. 1...Methane, 2...Acetylene, 3
...Ethylene, 4...Ethane.

Claims (1)

[Scope of Claims] 1. A method for measuring the deodorizing performance of an apparatus for deodorizing dry exhaust gas of an offset rotary printing press using a heat-set type ink using a combustion method, the method comprising: A measuring method for the deodorizing device described above, characterized in that the concentration of lower unsaturated hydrocarbons of at least one species is measured, and then the odor intensity is determined based on the positive correlation between the lower unsaturated hydrocarbon concentration and the odor intensity. . 2. The measuring method according to claim 1, wherein the lower unsaturated hydrocarbon has 2 to 4 carbon atoms. 3. The measuring method according to claim 1, wherein the lower unsaturated hydrocarbon is at least one member of the group consisting of acetylene, ethylene, and propylene. 4. The measuring method according to claim 1, wherein the lower unsaturated hydrocarbon is ethylene.