JP4827657B2 - Method for analyzing halogen compounds and sulfur oxides in exhaust gas, pretreatment device for analyzing halogen compounds and sulfur oxides in exhaust gas, and pretreatment kit for analyzing halogen compounds and sulfur oxides in exhaust gas - Google Patents

Description

  The present invention relates to a method, a pretreatment device for analysis, and a pretreatment kit for analysis, which can easily and simultaneously analyze halogen compounds such as fluorine, hydrogen chloride and bromine and sulfur oxides in exhaust gas generated from a chemical reaction device. It is.

  For example, exhaust gas generated when burning municipal waste or industrial waste contains trace amounts of halogen compounds in addition to sulfur oxides as harmful substances. Generation of air pollutants is a problem.

  On the other hand, as a method for measuring toxic substances generated from fixed sources such as incinerators such as municipal waste and industrial waste, Japanese Industrial Standards (JIS) defines an exhaust gas analysis method. In this exhaust gas analysis method, the measurement target components are classified into approximately 25 types, and a measurement method is defined for each measurement target component. And among the halogen compounds in the exhaust gas, analysis methods of hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr) and sulfur oxide (SOx) are also defined, but in this method, These components need to be measured separately by sampling (sampling) the exhaust gas separately for each component.

  As an analysis method of halogen compounds in exhaust gas, which is standardized by JIS, analysis methods such as lanthanum-alizarin complexone spectrophotometry (LAC method) and ion electrode method are adopted for HF, and thiocyanic acid for HBr. Mercury (II) absorptiometry and thiosulfate titration are used.

  In recent years, regulations on exhaust gas have been strengthened, and desulfurization treatment and exhaust gas treatment technology have been improved, and these harmful substances tend to be reduced in concentration. Therefore, it is difficult to accurately analyze low concentrations of HF and HBr by the analysis methods such as the ion electrode method and the titration method. On the other hand, as a method for measuring and analyzing such a low-concentration halogen compound, for example, there is an ion chromatography method (hereinafter sometimes referred to as an IC method).

  As a technique for measuring and analyzing fluorine, according to the following Patent Document 1, after a fluororesin or a compound containing a fluororesin is absorbed in an alkali salt such as sodium carbonate and dissolved in water, a cation exchange resin is used. A configuration is adopted in which the fluoride ion in the remaining aqueous solution is measured by the IC method except for the alkali. In addition, as a technique for measuring and analyzing HBr, the arc tube is crushed in an alkaline solution, the crushed material generated by the crushed is removed from the alkaline solution, and then the halogen contained in the alkaline solution is quantified by the IC method. Is adopted. However, the configurations of these patent documents and the like are techniques for individually measuring the target halogen compounds, and the target measurement samples are limited and a very small amount. Therefore, these methods are used for municipal waste in which various substances are mixed. It is difficult to apply it to the analysis of halogen compounds and sulfur oxides in exhaust gas generated when burning industrial waste and the like.

  In the exhaust gas analysis method according to the current JIS, as described above, it is necessary to sample each component separately and analyze it separately. However, the halogen compound and SOx in these exhaust gases are sampled once and once. If measurement can be performed by analysis, measurement time can be shortened and analysis cost can be reduced.

On the other hand, in the following Non-Patent Document 1, the IC method employed as a method for analyzing SOx and HCl has a feature that a low concentration anion component can be simultaneously analyzed in a short time. In this method, after collecting exhaust gas with 0.3% or 0.03% hydrogen peroxide (H ₂ O ₂ ) water, chloride ion and sulfate ion are measured by IC method, and SOx in exhaust gas is measured. This is a method for analyzing HCl.

As a method for simultaneously analyzing four types of halogens (fluorine, chlorine, iodine, bromine) and sulfur in an organic compound, a dilute sodium hydroxide aqueous solution containing hydrogen peroxide or saturated hydrazine by burning the organic compound ( In the following, there is a method in which a sample solution is absorbed into an ion chromatograph and is simultaneously analyzed by an IC method (Patent Document 3 below).
JP 2002-214217 A JP 2002-289100 A JP-A-8-262000 Japanese Industrial Standard (JIS) K 0103 Method for analyzing sulfur oxides in exhaust gas (2005)

  The method according to Patent Document 3 uses a dilute aqueous sodium hydroxide solution containing hydrogen peroxide or saturated hydrazine as an absorbent. And this measuring method is measuring the halogen and sulfur in the organic compound in fields such as medicine and agricultural chemicals, and the amount of the sample is as small as 1 to several mg. Accordingly, since the amount of carbon dioxide and halogen compounds generated when the sample is burned is small, a dilute sodium hydroxide aqueous solution can be used as the absorbing solution.

  However, since the exhaust gas generated when combusting municipal waste or industrial waste contains 10% or more high concentration carbon dioxide in addition to halogen compounds, the exhaust gas absorption solution is a dilute alkaline solution. Then, the acidic component in the exhaust gas is not sufficiently absorbed, and the acidity of the absorbing liquid is increased, and the halogen compound once absorbed volatilizes from the absorbing liquid. Therefore, there is a possibility that the halogen compound in the exhaust gas cannot be measured accurately.

On the other hand, also in the analysis method of hydrogen chloride and sulfur oxide by IC method defined by the above JIS (Non-patent Document 1), a 0.3% H ₂ O ₂ aqueous solution is used as an exhaust gas absorbing solution. When an aqueous solution of H ₂ O ₂ is used, hydrogen chloride and sulfur oxide can be measured with high accuracy as chlorine ions (Cl ⁻ ) and sulfate ions (SO ₄ ²⁻ ), respectively. However, even when simultaneous measurement of other halogen components (fluorine, bromine) and hydrogen chloride is attempted by this method, the collection rate of HF and HBr when a 0.3% H ₂ O ₂ aqueous solution is used is not clear. In addition, when exhaust gas containing carbon dioxide is absorbed, hydrogen fluoride and hydrogen bromide may be volatilized out of the absorbing solution, so it is difficult to accurately measure these low-concentration halogen components simultaneously. Therefore, there is a problem of what should be used as the exhaust gas absorbing liquid.

  However, as exhaust gas regulations are advancing, it is possible to measure low-concentration halogens in exhaust gases that cannot be measured by the ion electrode method or titration method described above, and at the same time, highly accurate measurement of halogen compounds and acidic components such as sulfur oxides in exhaust gases. Therefore, there is a demand for a simple measuring method, measuring apparatus, and the like that can be measured and analyzed by the above.

  An object of the present invention is to solve the above-described problems. Specifically, acidic components such as low-concentration halogen compounds and sulfur oxides in exhaust gas generated from a chemical reaction device such as a garbage incinerator are reduced to 1 It is to provide an analysis method that can be accurately measured simultaneously with one sampling. It is another object of the present invention to provide a pretreatment apparatus for analysis and a pretreatment kit for analysis that enable simple and easy pretreatment for such an analysis method in a short time.

The present invention can be achieved by employing the following configuration.
According to the first aspect of the present invention, after absorbing exhaust gas containing a halogen compound and sulfur oxide generated from a chemical reaction apparatus in an aqueous sodium hydroxide solution, a cation exchange resin is added to a certain amount of the absorbing solution to add sodium ions. Is adsorbed and removed by a cation exchange resin, and a carbon dioxide purge gas in the absorption liquid is passed through the absorption liquid to which the cation exchange resin is added to remove carbonate ions in the absorption liquid as carbon dioxide. Then, a method for analyzing halogen compounds and sulfur oxides in exhaust gas, in which halide ions and sulfate ions in the absorbing solution are measured by ion chromatography.

  According to a second aspect of the present invention, the gas for purging carbon dioxide is a gas in which the halogen compound in the exhaust gas and the analysis inhibiting component of the sulfur oxide are removed in advance to remove the halogen compound in the exhaust gas. And a method for analyzing sulfur oxides.

  According to a third aspect of the present invention, in the exhaust gas according to the first or second aspect, ozone for oxidizing the sulfite ions in the absorption liquid into sulfate ions is vented into the absorption liquid together with or separately from the carbon dioxide purge gas. This is a method for analyzing halogen compounds and sulfur oxides.

  The invention according to claim 4 is characterized in that an absorption liquid obtained by absorbing an exhaust gas containing a halogen compound and sulfur oxide generated from a chemical reaction apparatus through a sodium hydroxide aqueous solution and a cation exchange resin are brought into contact with each other in the absorption liquid. A neutralization degasser that adsorbs and removes sodium ions and removes carbon dioxide in the absorbent by passing a purge gas of carbon dioxide in the absorbent into the absorbent, and the carbon dioxide purge gas In the exhaust gas provided with venting means for venting the absorbent into the absorbing liquid in the neutralization degasser and exhaust means for exhausting carbon dioxide generated from the absorbing liquid by the purge gas vented by the venting means This is a pretreatment device for analysis of halogen compounds and sulfur oxides.

  According to a fifth aspect of the present invention, there is further provided a gas cleaning device for cleaning the carbon dioxide purging gas to remove a halogen compound and a sulfur oxide analysis inhibiting component in the exhaust gas. This is a pretreatment apparatus for analysis of halogen compounds and sulfur oxides.

  According to a sixth aspect of the present invention, ozone for oxidizing the sulfite ions in the absorption liquid into sulfate ions is vented to the absorption liquid in the neutralization degasser together with or separately from the carbon dioxide purge gas. The pretreatment device for analysis of halogen compounds and sulfur oxides in exhaust gas according to claim 4 or 5, wherein the ozone ventilation means is provided.

  A seventh aspect of the present invention is a pretreatment apparatus for analysis of halogen compounds and sulfur oxides in exhaust gas according to any one of the fourth to sixth aspects, which is a pretreatment apparatus for analysis by ion chromatography.

The invention according to claim 8 is a sealed container that can be broken by a pressing force in which a cation exchange resin that adsorbs and removes sodium ions is sealed, and hydroxylation that absorbs exhaust gas containing the sealed container and a halogen compound and sulfur oxide. An absorption container having an opening that can store an aqueous sodium solution and can be sealed by a cap, and a vent for venting a purge gas for removing carbon dioxide in the absorbing solution of the aqueous sodium hydroxide solution that has absorbed the exhaust gas Is a pretreatment kit for analysis of halogen compounds and sulfur oxides in exhaust gas having a structure in which

Invention of claim 9, wherein the breakable sealed container is made of glass, wherein the absorption vessel is pretreated kit for the analysis of halogenated compounds and sulfur oxides in the exhaust gas according to claim 8, wherein Ru der made soft plastic It is.

A tenth aspect of the invention is a pretreatment kit for analysis of halogen compounds and sulfur oxides in exhaust gas according to the eighth or ninth aspect, which is a pretreatment kit for analysis by ion chromatography .

(Function)
In the non-patent document 1, the IC method employed as a method for analyzing SOx and HCl is characterized in that a low concentration anion component can be simultaneously analyzed in a short time. The inventors of the present invention have made it possible to analyze not only SOx and HCl but also HF and HBr at the same time with an IC method having such characteristics, an analytical pretreatment apparatus for such a method, After extensive research on treatment kits, etc., they found the following.

As described above, in the analysis method based on the SOx and HCl IC method in Non-Patent Document 1, an H ₂ O ₂ aqueous solution is used as the absorbing solution. When this absorbing solution is used, the fluorine compound and bromine compound The collection rate is not clear. In addition, it is difficult to accurately measure chloride ions, fluoride ions, and bromide ions in the absorption liquid due to the change in liquidity of the absorption liquid caused by absorbing carbon dioxide in the exhaust gas. On the other hand, the measurement of halogen compounds (HF, HBr, HCl) in exhaust gas stipulated by JIS is that the exhaust gas is absorbed in a 0.1 M (mol / L) sodium hydroxide aqueous solution having a relatively higher concentration than the above patent documents. And then analyzing by lanthanum-alizarin complexone absorptiometry (LAC method), mercury (II) thiocyanate absorptiometry, thiosulfate titration method, silver nitrate titration method, ion electrode method and the like (JIS K 0105). (HF), JIS K 0085 (HBr), JIS K 0107 (HCl)).

  Therefore, the present inventors have paid attention to the fact that the above method uses a 0.1 M sodium hydroxide aqueous solution as the exhaust gas absorbing solution. That is, since the exhaust gas contains a large amount of carbon dioxide, an absorbing solution having a relatively high concentration of alkali is suitable, and 0.1 M water is employed because it can absorb acidic gas as an absorbing solution for halogen gas. Focusing on the aqueous solution of sodium oxide, it was considered that if other halogen components were collected using the absorbing solution, it could be measured by the IC method, and the present invention was completed.

However, in the IC method, since a few mmoles of sodium carbonate and sodium hydrogen carbonate solution are usually used as an eluent, for example, when an aqueous sodium hydroxide solution is used as an absorbent, absorption is performed when the alkali concentration is relatively high. When the liquid is analyzed, the water dip due to sodium hydroxide increases. Further, the carbon dioxide in the exhaust gas is trapped in the absorption liquid, and affected, F on the chromatogram ^- overlap with the peak F ^{- -} and Cl and Cl ^- is the separability is poor.

That is, as a problem when a relatively high concentration sodium hydroxide aqueous solution such as 0.1 M is used for the exhaust gas absorption liquid, for example, (1) the eluent is less than a few mM carbonate solution. Since the alkali concentration (100 mM) is high, the water dip becomes large and interferes with the measurement of F ⁻ and Cl ⁻ . (2) When carbon dioxide (CO ₂ ) in exhaust gas is simultaneously collected, F ^- and Cl ^- peak and overlap separability there are problems such as bad.

However, according to the present invention, after the halogen compound and SOx in the exhaust gas are absorbed in the NaOH solution, the alkali component (Na ⁺ ) and carbonate ion (CO ₃ ²⁻ ) that cause interference when analyzed by the IC method are used. Since the anion (F ⁻ , Cl ⁻ , Br ⁻ , SO ₄ ²⁻ ) can be analyzed accurately, the halogen compounds (HF, HCl, HBr) and sulfur oxides (SOx) in the exhaust gas have been improved. ) Can be analyzed simultaneously.

That is, according to the first aspect of the present invention, sodium ions that cause water dip can be adsorbed and removed by the cation exchange resin by adding the cation exchange resin to the absorbing solution that has absorbed the exhaust gas. Furthermore, by separating the purge gas through the absorption liquid to remove carbon dioxide in the absorption liquid, the separation of the F ⁻ and Cl ⁻ peaks on the chromatogram in the IC method is improved. The “gas” means a purge gas for driving off carbon dioxide in the absorption liquid.

Further, according to the invention described in claim 2, in addition to the operation of the invention described in claim 1, even if the purge gas is not a clean gas, the halogen compound and the sulfur oxide in the exhaust gas are washed in advance. By using the gas from which the analysis-inhibiting components are removed as the purge gas, for example, acidic components and contaminants in the gases that are analysis-inhibiting components in the IC method are removed, and contamination of the absorption liquid due to these acidic components and contaminants is removed. Nation can be prevented and carbon dioxide in the absorbent can be removed. Therefore, further, F on the chromatogram ^- and Cl ^- separation of the peaks of the better.

On the other hand, SOx in the exhaust gas may exist as unstable sulfite ions if the oxidation when absorbed by the aqueous sodium hydroxide solution is insufficient. However, according to the invention described in claim 3, in addition to the above action of the invention described in claim 1 or 2, the sulfite ion (SO ₃ ^2- ) in the absorbing solution is oxidized to sulfate ion (SO ₄ ^2- ). By allowing the ozone to be passed through the absorption liquid, all SOx in the exhaust gas can be changed to sulfate ions.

  In addition, if the pretreatment of various analytical methods when sodium ion or carbon dioxide is contained in the exhaust gas absorption liquid and these components cause interference in the analysis, measurement and analysis can be performed easily, easily, and in a short time. Can also save time.

According to the fourth aspect of the present invention, a series of pretreatment operations for removing sodium ions and carbon dioxide in the exhaust gas absorbing solution can be performed only by setting the apparatus.
According to the invention described in claim 5, in addition to the above-described operation of the invention described in claim 4, analysis of halogen compounds and sulfur oxides in the exhaust gas from a purge gas that is not a clean gas is possible only by setting the apparatus. Inhibitory components can be removed, and the purge gas can be easily and easily cleaned.

According to the invention described in claim 6, in addition to the above-described action of the invention described in claim 4 or 5, in the case where sulfite ions (SO ₃ ^2- ) are present in the exhaust gas absorption liquid, all SOx in the exhaust gas is reduced. The operation for oxidizing to sulfate ions can be performed simply, easily and in a short time by simply setting the apparatus.

According to the invention described in claim 7, in addition to the above-described action of the invention described in any one of claims 4 to 6, sodium ions which cause water dip in the IC method are removed, and further F ⁻ and Cl ⁻ A pretreatment operation for removing carbon dioxide, which is an obstacle to peak separation, can be performed simply, easily and in a short time just by setting the apparatus.

  According to the eighth aspect of the invention, the sodium hydroxide absorption liquid is absorbed and removed by the cation exchange resin by destroying the sealed container sealed with the cation exchange resin. The sodium ion in it can be removed easily and easily.

Moreover , since carbon dioxide can be expelled from the absorbing liquid by ventilating the carbon dioxide purging gas from the vent, the carbon dioxide in the absorbing liquid can be removed. Therefore, the removal operation of sodium ions and carbon dioxide in the exhaust gas absorbing solution can be performed easily and easily.

According to the invention of claim 9, wherein, in addition to the above effect of the invention of claim 8 Symbol mounting, since the absorption container made soft plastic, easy by dividing the glass press sealed container in the absorption vessel from the outside The container can be unsealed. Further, since the glass sealed container is housed in the soft plastic absorbing container, the sealed container is not easily broken even if the absorbing container is dropped. Furthermore, since the absorption container is made of a soft plastic, it can be easily deformed by external pressure and the sample after pretreatment can be taken out.
According to the invention of claim 1 0, wherein, in addition to the above effect of the invention according to claim 8 or 9, simplify the operations required pretreatment for IC analysis of the exhaust gas absorbing liquid, easily, cheaply It can be carried out.

  According to the present invention, acidic components such as low-concentration halogen compounds and sulfur oxides in exhaust gas generated from a chemical reactor such as a waste incinerator can be accurately measured simultaneously by one sampling and one analysis. Specifically, it has the following effects. In addition, the analysis of halogen compounds and sulfur oxides in exhaust gas is performed quickly, simply and inexpensively.

According to the invention of claim 1, wherein, F with carbon dioxide of the influence of water dip and in the exhaust gas with sodium ions as sodium hydroxide absorption solution in the IC method ^- and Cl ^- of the can eliminate the separation issues, F ^- and Cl ^- good chromatogram separation of peaks is obtained. Therefore, halogen compounds such as HF, HBr, and HCl and sulfur oxides in the exhaust gas generated from the chemical reaction apparatus can be accurately measured and analyzed simultaneously by one sampling and one analysis.

According to the invention described in claim 2, in addition to the above-described effect of the invention described in claim 1, even if the purge gas is not a clean gas, it is washed in advance and analyzed for halogen compounds and sulfur oxides in the exhaust gas. Since the inhibitory component can be removed, F ⁻ , Cl ⁻ , Br ⁻ and SO ₄ ²⁻ can be analyzed with high accuracy.

According to the invention described in claim 3, in addition to the above-described effect of the invention described in claim 1 or 2, all SOx in the exhaust gas can be changed to sulfate ions, so that accurate SOx concentration measurement / analysis is possible. Become.
According to invention of Claim 4, a series of pretreatment operation | movement of the removal operation of the sodium ion in a waste gas absorption liquid and a carbon dioxide can be performed simply and easily.

According to the invention described in claim 5, in addition to the above-described effect of the invention described in claim 4, the analysis of halogen compounds and sulfur oxides in the exhaust gas from the purge gas that is not a clean gas is possible only by setting the apparatus. Pretreatment for removing inhibitory components can be performed easily and easily.
According to the invention described in claim 6, in addition to the effect of the invention described in claim 4 or 5, the operation for oxidizing all SOx in the exhaust gas into sulfate ions can be performed simply and easily in a short time.

  According to the invention described in claim 7, in addition to the effects of the invention described in any one of claims 4 to 6, the pretreatment when analyzing the exhaust gas absorbing solution by the IC method can be performed easily and easily. Rapid analysis is possible.

  According to the invention described in claim 8, since sodium ions in the sodium hydroxide absorbing solution can be easily and easily removed, when it is necessary to remove sodium ions as a pretreatment for analysis, it is simple, easy and quick. The operation can be performed. Moreover, since it has an integrated and compact structure in which a sealed container is housed in an absorption container, it is excellent in workability and convenient for storage and carrying. Furthermore, it is possible to process an exhaust gas sample inexpensively, quickly and simply. Moreover, it can be easily confirmed that the decomposition solution has changed from alkaline to neutral even with pH test paper or the like. Furthermore, it can be generally used for pretreatment of various analysis methods.

Further, the simple even when it is necessary to remove the carbon dioxide gas absorbing liquid, easily can be carried out quickly the operation, the measurement can be saved the time required for analysis also.

According to the invention of claim 9, wherein, in addition to the effect of the invention of the claim 8 Symbol mounting, also closed container drop the absorption vessel, in order to not break easily, excellent further storage stability and storage stability, convenient to carry It is. Furthermore, the sample after the pretreatment can be easily taken out by pushing and deforming the absorption container from the outside, and further simple and quick pretreatment becomes possible.
According to the invention of claim 1 0, wherein, in addition to the effects of the invention described in claim 8 or 9, simple pretreatment when the exhaust gas absorbed solution analyzed by IC method, easily, cheaply performed, further Rapid analysis is possible.

  The present invention is described in detail below. The exhaust gas to be measured and analyzed in the present invention is from a chemical reaction device used in combustion of fuel, waste, etc., ore roasting, metal refining, sulfur production process, other chemical reaction, desulfurization process, etc. For example, municipal waste and industrial waste incineration exhaust gas are targeted.

The exhaust gas to be measured is sampled and absorbed in an absorption solution of an aqueous sodium hydroxide solution, and a certain amount of the absorption solution is taken in a neutralization degasser. As a sampling method, a known method such as suction with a pump or the like may be used. For example, incineration exhaust gas from municipal waste and industrial waste contains a large amount of CO _2, so an aqueous sodium hydroxide solution of about 0.1M is preferable. When the concentration of the sodium hydroxide aqueous solution is lower than this concentration, the acidic component in the exhaust gas cannot be sufficiently absorbed, and the absorbed acidic component may be volatilized. Further, when the concentration is higher than this, there is a problem of the water dip described above, and it is necessary to increase the amount of the cation exchange resin used for removing Na ^{+ in} the absorbing solution, which takes time and labor for the removal. .

  The amount of the absorbing liquid taken in the neutralization degasser may be about 5 to 20 ml, for example, about 10 ml. The sampling tube used for sampling is not particularly limited, but it is preferable to use a glass tube, a quartz tube, or a tetrafluoroethylene resin that is not attacked by or adsorbed by the corrosive gas in the exhaust gas.

  In addition, the neutralization degasser is not particularly limited, but if a glass-made impinger is used, a cation exchange resin described later is well mixed in the absorbing solution and sodium ions can be collected. Further, it is preferable because the purge gas can be sucked and exhausted easily.

Next, a certain amount of the cation exchange resin is added to the neutralization degasser, and the sodium ion (Na ⁺ ) in the absorption liquid is adsorbed on the resin to make the absorption liquid a neutral solution. The amount of the cation exchange resin to be added may be about 1 to 2 g per 5 to 10 ml of the absorbing solution, and may be appropriately adjusted depending on the amount of the absorbing solution. The kind of cation exchange resin to be added is not particularly limited, and either strong acidity or weak acidity may be used. Various forms such as a gel form and an MR (macroreticular) form can be used, and a styrenic or acrylic cation exchange resin can be used as the matrix structure of the resin. These cation exchange resins may be H ⁺ type cation exchange resins or Na ⁺ type cation exchange resins, but in the case of Na ⁺ type, after regenerating to H ⁺ type with nitric acid. Use it.

Next, air is used as the purge gas for CO ₂ , and this is passed through a neutralization degasser to expel and remove CO ₂ in the neutralized absorbent. If a gas that has been washed in advance to remove the halogen-containing compounds and sulfur oxides in the exhaust gas is used as a CO ₂ purge gas, absorption by these analysis-inhibiting components can be achieved without using clean gas. Prevents liquid contamination and removes carbon dioxide in the absorbent.

  Analysis inhibiting components include acidic components such as halogen compounds and sulfur oxides and carbon dioxide. If these acidic components are included in the purge gas, the acidic components in the exhaust gas and the exhaust gas absorption liquid It becomes impossible to accurately measure halogen compounds in exhaust gas. Cleaning of the purge gas can be facilitated by passing an alkaline solution. As the alkaline solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or the like can be used. Among these, an aqueous sodium hydroxide solution is preferred because it efficiently absorbs acidic components and carbon dioxide. The concentration and amount of the sodium hydroxide aqueous solution used for gas cleaning vary depending on the amount of exhaust gas to be measured, but may be about 10 to 20 ml as long as it is about 1 to 5M.

  Further, the purge gas flowing through the neutralization degasser may be air or nitrogen. Use of normal air is preferable because it is simple and inexpensive. When air in the atmosphere is used, the analysis inhibiting component may be removed by washing the air. The operation of venting the purge gas into the absorbing solution may be performed by taking a certain amount of the exhaust gas absorbing solution into the neutralization degasser, adding a certain amount of the cation exchange resin, and blowing air. The flowing time may be about 5 to 15 minutes as long as the amount of absorbing liquid is about 10 ml.

On the other hand, when SOx in the exhaust gas is collected in the sodium hydroxide aqueous solution, most of it becomes SO ₄ ²⁻ , but some of it may exist as SO ₃ ²⁻ . When air is ventilated for a long period of time, for example, about 30 to 60 minutes, SO ₃ ^2- changes to SO ₄ ^2-. Ozone can be flowed. As a method for generating ozone, a generally well-known method such as an ultraviolet ray method, a silent discharge method, or an electrolysis method can be used. If an ozone generator (ozonizer) is attached to the purge gas vent tube, ozone can be flowed into the absorbent easily and easily. In addition, when SO ₃ ^2- is not present as a result of actual analysis using an analysis method such as the IC method, it is not necessary to flow ozone.

In this way, by removing the alkali components (Na ⁺ ) and carbonate ions (CO ₃ ²⁻ ) that interfere with the analysis by the IC method from the exhaust gas absorbent, anions (F ⁻ , Cl ⁻ , Br ⁻ , SO ₄ ²⁻ ) can be analyzed with high accuracy, and halogen compounds (HF, HCl, HBr) and sulfur oxides (SOx) in exhaust gas can be measured simultaneously by one sampling and one analysis. Moreover, if ozone is allowed to flow in the absorbing solution, all SOx in the exhaust gas can be changed to sulfate ions, and accurate SOx concentration measurement / analysis becomes possible. This method is not limited to the IC method, and can be used as a pretreatment for various analytical methods that require removal of alkali components (Na ⁺ ) and carbonate ions (CO ₃ ²⁻ ) from the exhaust gas absorbing solution.

  By the way, like the above-mentioned patent document 3, there is a method in which a halogen compound and sulfur in an organic compound are decomposed by a combustion tube method, and the gas is collected in an absorbing solution and then analyzed by an ion chromatography method. Similar pretreatment apparatuses are commercially available (for example, Dia Instruments Co., Ltd., automatic sample combustion apparatus, AQF-100 type). Since these combustion apparatuses have a high content of halogen compounds and sulfur in organic substances, and because the analysis is automated, the amount of sample collected is as small as 1 to several mg. JIS has established a method for analyzing total chlorine and sulfur in solid waste fuel by combining the combustion tube method and ion chromatograph method (the analysis method for total chlorine is Japan Industrial Standards (JIS)). Z 7302-6 Waste solidified fuel: Total chlorine content test method (1999) In addition, sulfur analysis method is Japanese Industrial Standard (JIS) Z 7302-7 Waste solidified fuel: Sulfur content test method (2002) )by).

  According to this rule, a sample (up to about 1 g) is burned, absorbed in hydrogen peroxide, and analyzed for total chlorine and sulfur by ion chromatography. Furthermore, recently, bromine in polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE), which are brominated flame retardants contained in plastics, are combined with this combustion tube method and ion chromatography method. Analysis is done by the method.

  However, when analyzing halogenated compounds and sulfur in solid waste fuels and brominated flame retardants, the sample is collected because the content of halogen and sulfur in the sample is less than when analyzing conventional organic substances. The amount must be as large as 1g. Therefore, the amount of carbon dioxide generated by combustion also increases, and the absorption rate of the hydrogen peroxide solution is not sufficient for collecting halogen compounds.

  Therefore, by using a 0.1 M aqueous sodium hydroxide solution as the absorbing solution instead of the hydrogen peroxide solution defined by JIS, the collection can be completed. By using the analytical pretreatment device shown in FIG. 7 of the present invention and the analytical pretreatment kit shown in FIG. 8 for a certain amount of this absorbing solution, the halogenated compounds in the waste solidified fuel and brominated flame retardant It can be applied to sulfur analysis.

FIG. 1 shows a flow of a method for analyzing a halogen compound and sulfur oxide in exhaust gas, which is an embodiment of the present invention.
The exhaust gas discharged from the chimney of the incineration plant is collected by a sampling tube by the JIS method (for example, JIS K 0095) and used as a measurement target, absorbed in an absorption solution of 0.1M sodium hydroxide aqueous solution, and the absorption solution is kept constant. An amount (10 ml) was placed in the neutralization degasser. The sampling tube was made of stainless steel, and the neutralization degasser was made of glass.

Next, a certain amount (2 g) of H ⁺ type cation exchange resin (Amberlite (trade name) IR124HAG manufactured by Organo Corp.) was added to the absorbing solution in the neutralization degasser, and sodium ions in the absorbing solution were added. (Na ⁺ ) was adsorbed on the resin to make the absorbing solution a neutral solution. It may be confirmed using a pH test paper that the absorbing solution has become a neutral solution.

Next, purge air (air in the atmosphere) from which acid components and the like have been removed by washing through a 1.0 M aqueous sodium hydroxide solution (20 ml) in advance for about 5 to 15 minutes in the neutralization degasser. A constant flow rate (0.2 to 0.5 L / min) is passed through the absorption liquid to drive out the CO ₂ in the neutralized absorption liquid and use it as a measurement sample, and the supernatant is injected into the ion chromatograph. Then, halide ion and sulfate ion were measured.

FIG. 2 shows the result (chromatogram) obtained by measuring the solution obtained by removing sodium ions and carbonate ions from the absorbing solution by the above-described method by the IC method. As a comparative example, FIG. 3 shows the results when the absorption liquid was directly measured by the IC method, and FIG. 4 shows the measurement results when Na ⁺ was removed by adding a cation exchange resin to the absorption liquid. FIG. 5 shows a chromatogram of an anion standard solution (7 types). The measurement conditions for the IC method are shown below (same as in FIGS. 2 to 5).

Apparatus: DX500 model manufactured by Dionex Co., Ltd. Column: IonPac AG12A / AS12A manufactured by Dionex Co., Ltd .: Suppressor: ASRS-II in electrodialysis type Detector: Electrical conductivity Eluent: Mixed solution of 2.7 mM sodium carbonate and 0.3 mM sodium bicarbonate Liquid flow at 1.3 ml / min Sample injection volume: 25 μl Column temperature: 35 ° C.
When the absorbing solution was directly measured by the IC method, as is apparent from the chromatogram of FIG. 3, a peak of sodium ion (Na ⁺ ) due to the influence of alkali was observed, and further F ⁻ and Cl due to the influence of carbonate ion. ^- it can not be poor analytical separation of the peak of. When Na ⁺ is removed by adding a cation exchange resin to the absorbing solution, the Na ⁺ peak disappears and the chromatogram is improved, as is apparent from the chromatogram of FIG. In this case, F ⁻ and Cl ⁻ are disturbed, and F ⁻ and Cl ⁻ cannot be measured accurately.

However, as shown in FIG. 2, after adding cation exchange resin to the absorption liquid, if purge air is vented through the absorption liquid to drive out CO ₂ in the absorption liquid, the influence of carbonate ions disappears and the base line stably even, F ^- and Cl ^- peak of is improved. This chromatogram is an anion standard solution shown in FIG. 5 (each component is dissolved in ion-exchanged water, and each concentration is shown below. F: 1.00 ppm Cl: 2.00 ppm NO ₂ : 3.00 ppm Br : 2.00 ppm NO ₃ : 6.00 ppm PO ₄ : 6.00 ppm SO ₄ : 8.00 ppm).

表１の結果から、排ガス中にはＨＣｌやＳＯｘに加えて、微量のＨＦとＨＢｒが含まれていることが確認された。そして、Ｃｌ^-やＳＯ₄ ^2-と共に、Ｆ^-、Ｂｒ^-も精度良く検出できた。 Table 1 shows the analysis results of HCl, HF, HBr, and SOx in the exhaust gas when the exhaust gas is sampled four times in an actual waste incineration plant.

From the results in Table 1, it was confirmed that the exhaust gas contained trace amounts of HF and HBr in addition to HCl and SOx. Then, Cl ^- and SO ₄ with ^2-, F ^-, Br - was also able to accurately detect.

  In Table 2, exhaust gas sampling is performed four times as a reference example, and the concentration of hydrogen chloride in the exhaust gas is analyzed by mercury thiocyanate (II) spectrophotometry (JIS K 0107). The result analyzed by IC method by an Example is shown.

  From Table 2, since the analysis results having almost the same concentration were obtained four times, it can be said that the method according to this example is highly reliable as a method for analyzing the concentration of halogen compounds such as HCl and SOx in exhaust gas. . From the above results, it was confirmed that acidic components such as low-concentration halogen compounds and sulfur oxides in exhaust gas can be accurately measured simultaneously by one sampling and one analysis. In addition, analysis of halogen compounds and sulfur oxides in exhaust gas can be performed quickly, simply and inexpensively.

On the other hand, when SOx in the exhaust gas is collected in a 0.1 M NaOH solution, most of the SOx is converted to SO ₄ ²⁻ , but some of the SOx ²⁻ may exist as SO ₃ ²⁻ . In the chromatograms shown in FIGS. 2 to 4 according to Example 1, a slight peak of SO ₃ ²⁻ is confirmed. When purge air is vented into the absorbent for a long time, SO ₃ ²⁻ changes to SO ₄ ²⁻ , but in order to shorten the time, in this embodiment, ozone is generated from the ozonizer, and SO ₃ ²⁻ An attempt was made to promote oxidation to SO ₄ ^2- . The conditions of this example were as follows: an ozonizer (model YGR-103N, manufactured by Lacy Co., Ltd.) was used, and purge air was aerated at a constant flow rate (0.2 to 0.5 L / min) for about 5 to 15 minutes.

The same procedure as in Example 1 was performed except that ozone generated from the ozonizer was bubbled into the absorbent together with purge air. The result is shown in FIG.
From FIG. 6, the disappearance of the SO ₃ ²⁻ peak was confirmed as compared with the chromatograms shown in FIGS. According to this embodiment, all SOx in the exhaust gas can be changed to sulfate ions, and accurate SOx concentration measurement / analysis can be performed.

  In FIG. 7, the block diagram of the pre-processing apparatus for the analysis of the halogen compound and sulfur oxide in exhaust gas which is one Example of this invention is shown.

A gas cleaning container 4 for cleaning a purge gas for removing carbon dioxide in the absorbing liquid 1 in the neutralization degasser 2 contains 20 ml of 1M NaOH solution as the cleaning liquid 6, and the gas is stored in the cleaning container. When the gas passes through 4, CO ₂ and acidic components in the gas are absorbed and removed in the NaOH solution and are passed through the gas vent pipe 7 to the neutralization degasser 2. The upper part of the gas cleaning container 4 and the neutralization degasser 2 is capped with a stopper 10 or the like and passed through the gas vent pipe 7 or the like.

A fixed amount (10 ml) of 0.1 M sodium hydroxide aqueous solution 1 in which the impinger-type neutralization degasser 2 has absorbed the exhaust gas similar to that of Example 1, and a cation exchange resin 3 similar to that of Example 1 placing a certain amount of (2g), Na ⁺ and the cation exchange resin by contacting in solution, Na ⁺ in the absorption liquid 1 is adsorbed and removed to a cation exchange resin 3.

The pump 5 is turned on and air in the atmosphere is sucked at a constant flow rate (0.2 to 0.5 L / min) for a certain time (about 5 to 15 minutes). A gas flow meter 9 is connected to the downstream side of the pump 5. After the air is cleaned in the gas cleaning container 4, the air flows into the neutralization degasser 2 from the gas vent pipe 7. At this time, the cation exchange resin 3 in the neutralization degasser 2 is mixed in the liquid by the inflow of air, efficiently adsorbs Na ⁺ in the liquid, and the pH of the absorption liquid 1 changes from alkaline to neutral. . At the same time, CO ₃ ²⁻ in the liquid is discharged from the exhaust pipe 8 to the outside of the neutralization degasser ₂ as CO ₂ . Then, 1 ml of the supernatant of the absorbent 1 is taken with a syringe and injected into an ion chromatograph to measure the halide ions and sulfate ions in the absorbent 1 in the same manner as in Example 1. Analyze sulfur oxides.

On the other hand, in the pretreatment apparatus for analysis according to this example, the ozonizer 12 used in Example 2 is connected to the gas vent pipe 7 (portion surrounded by a dotted line in FIG. 7). When SOx in the exhaust gas is collected in a 0.1 M NaOH solution, most of the SOx becomes SO ₄ ^2- , but some of it may exist as SO ₃ ^2- . When purge air is passed through the absorbent 1 for a long time, SO ₃ ²⁻ changes to SO ₄ ²⁻ , but in this embodiment, ozone is generated from the ozonizer 12 in order to shorten the time, and SO ₃ ^{2 -} and to promote the oxidation of SO ₄ to ² from. Note that it is needless to say that the ozonizer may be omitted from the analysis result by the IC method or the like when SO ₃ ^2- is not present. Further, the ozonizer 12 may be connected to a pipe different from the gas vent pipe 7, but if it is connected to the gas vent pipe 7, ozone can be vented into the absorbing liquid 1 without providing another pipe. It is simple, easy and inexpensive, and does not require much effort.

As described above, when the pretreatment apparatus for analysis according to the present embodiment is used, for example, separation of F ⁻ and Cl ⁻ by water dip by sodium hydroxide absorbing liquid and carbon dioxide in exhaust gas in an analysis method such as IC method. You can solve the problem, F ^- and Cl ^- good chromatogram separation of peaks is obtained. Therefore, pretreatment for measuring and analyzing halogen compounds and sulfur oxides such as HF, HBr, HCl, etc. in exhaust gas generated from chemical reactors simultaneously and accurately with a single sampling is simple, easy and in a short time. it can. Moreover, if the ozonizer 12 is used, all SOx in the exhaust gas can be changed to sulfate ions, and pretreatment that enables accurate measurement and analysis of the SOx concentration can be performed.

In FIG. 8, the front longitudinal cross-sectional view of the analysis pretreatment kit 20 which is one Example of this invention is shown.
A cation exchange resin (about 1.0 to 2.0 g) 3 is enclosed in a glass tube 24 and contained in an absorption container 21, and the upper part of the absorption container 21 is used in a state of being sealed by a cap 22. .

  The glass tube 24 is not limited to the glass tube as long as it can be easily unsealed, and may be of any material or shape. Further, the glass tube is not limited as long as the cation exchange resin 3 can be kept stable and sealed. Although there is no limitation also about the raw material of the absorption container 21, since it is light, strong, and cheap, the product made from a plastic is preferable. Further, if the absorption container 21 is made of a soft plastic, it can be easily broken by pushing the glass tube 24 from the outside, and the absorbent 1 can be easily pushed out by pushing the side of the absorption container 21. It is. The color of the glass tube 24 and the absorption container 21 is not particularly limited, but if it is transparent, the contents of the absorption container 21 can be seen well, so that the operation is easy.

  The analytical pretreatment kit 20 according to an embodiment of the present invention has a structure in which a screw-in type cap 22 is attached to the upper part of an absorption container 21 and can be sealed. The structure of the cap 22 is not particularly limited, and the absorption container 21 is not limited to the cap 22 as long as it can be easily unsealed, and may have any structure. For example, the cap 22 and the absorption container 21 may be integrated. Further, not limited to the sealing means by the cap 22, there is no particular limitation as long as the absorbing container 21 can be sealed and the means can be easily unsealed (for example, plugged).

  Although the magnitude | size of the absorption container 21 is not limited, the diameter which is about 15-20 mm in diameter and about 130-150 mm in length and easy to hold | maintain may be simple. Furthermore, the cation exchange resin-encapsulated glass tube 24 preferably has a diameter of about 7 to 9 mm and a length of about 30 to 45 mm.

9 and 10 are diagrams illustrating an example of use of the analytical pretreatment kit 20 shown in FIG. As shown in FIG. 9 (a), a certain amount (1 g) of H ⁺ type cation exchange resin 3 enclosed in a glass tube 24 is placed in an absorption container 21 of a soft plastic tube, and then in FIG. 9 (b). As shown, a certain amount (about 5 ml) of the exhaust gas absorbent 1 collected in the same manner as in Example 1 is added. The order of this operation is not limited. For example, after the exhaust gas absorbing liquid 1 is put, the glass tube 24 enclosing the H ⁺ type cation exchange resin 3 may be put. Next, as shown in FIG. 9 (c), a cap 22 is attached to the absorption container 21, and as shown in FIG. 9 (d), the absorption container 21 of a soft plastic tube is bent by hand to form an H ⁺ type cation exchange resin. The glass tube 24 containing 3 is divided, and the absorbing liquid 1 and the H ⁺ type cation exchange resin 3 are brought into contact with each other and shaken.

  Then, as shown in FIG. 10, the cap 22 of the analytical pretreatment kit 20 is removed, a pipe 7 for passing a purge gas for removing carbon dioxide in the absorbent 1 is inserted, and the pump 5 is set. . Then, the pump 5 is turned on and air is blown at a constant flow rate (0.2 to 0.5 L / min) for a fixed time (5 to 15 minutes). The cap 22 may be replaced with a cap having two ventilation holes and two exhaust holes, and a tube 7 for venting purge gas may be inserted into the ventilation hole. Moreover, even if it is not a cap, a hole may be made in the absorption container 21 itself, and if not used, a stopper or a cap may be provided.

When air is passed through the absorbent 1, the cation exchange resin 3 in the absorbent container 21 is mixed in the liquid, and when the Na ⁺ in the liquid is adsorbed, the pH of the absorbent 1 changes from alkaline to neutral. At the same time, CO ₃ ²⁻ in the liquid is discharged out of the system from the absorption container 21 as CO ₂ . The liquid property of the absorbing liquid 1 can be confirmed with a pH test paper.

  Then, the supernatant liquid of the absorption liquid 1 is taken with a syringe and injected into an analyzer such as an ion chromatograph to measure halide ions and sulfate ions in the absorption liquid 1, and halogen compounds and sulfur oxidation in the exhaust gas are measured. Analyze things.

This pretreatment kit for analysis 20 can be used when no acid component is contained in the air (clean air), and when SO ₃ ^2- is not present when analyzed by the IC method or the like. Further, if the absorption container 21 is fixed and the gas cleaning container 4 and the ozonizer 12 of the third embodiment are connected to the vent pipe 7, the same usage method as that of the neutralization degasser 2 of the third embodiment is possible. .

The H ⁺ type cation exchange resin 3 enclosed in the glass tube 24 does not dry because it retains moisture, and does not elute anion components from the resin and is stable for at least about one year. There is the feature that it is. Therefore, it has excellent storability and can be used whenever necessary. And the pre-processing which removes the sodium ion and carbon dioxide of exhaust gas absorption liquid can be performed simply, easily, and inexpensively.

Reference example 1

FIG. 11 shows a reference example in the case where an apparatus for collecting the gas in the absorbent is further provided in the analytical pretreatment apparatus shown in FIG.
The analytical pretreatment apparatus shown in FIG. 11 is obtained by connecting an absorption container 15 for absorbing chlorine, hydrogen sulfide, hydrogen cyanide, etc. in exhaust gas from the chemical industry etc. to the analytical pretreatment apparatus shown in FIG. is there. In this case, the concentration of carbon dioxide in the exhaust gas is 1% or less.

  As shown in FIG. 11, when the exhaust gas contains a compound such as chlorine, hydrogen sulfide, or hydrogen cyanide, it is preferable to further provide an absorption container 15 for collecting the gas in the absorbent 1. As the absorption liquid 16 to be put into the absorption container 15, a fixed amount (10 ml) of an absorption liquid such as a 0.1 M sodium hydroxide aqueous solution is used as in the above-described examples. The target exhaust gas is absorbed in the absorption liquid 1 in the neutralization degasser 2 and the absorption container 21 of the pretreatment kit 20 in the same manner as in the above embodiment, and the pH of the absorption liquid 1 is made acidic and the purge gas is allowed to flow. Then, gases such as chlorine, hydrogen sulfide, and hydrogen cyanide in the absorption liquid 1 are expelled and absorbed and collected by the absorption liquid 16 in the absorption container 15.

  Then, the absorbing liquid 16 that collects these chlorine, hydrogen sulfide, hydrogen cyanide and the like may be analyzed. The analysis method is not limited to the IC method. For example, if chlorine, 4-pyridinecarboxylic acid-pyrazolone absorptiometry, if hydrogen sulfide, ion electrode method, if hydrogen cyanide, 4-pyridinecarboxylic acid-pyrazolone method and Analyze by ion electrode method.

  As described above, the analytical pretreatment apparatus shown in FIG. 7 and the analytical pretreatment kit 20 shown in FIG. 8 are also used for a degassing process for separating chlorine, hydrogen sulfide, and hydrogen cyanide in exhaust gas from a chemical factory or the like. Can do.

Reference example 2

Further, the analytical pretreatment apparatus shown in FIG. 7 and the analytical pretreatment kit 20 shown in FIG. 8 can be used for separation of free cyanide in wastewater such as industrial wastewater.
The sample wastewater is taken into the neutralization degasser 2 and the absorption container 21 of the pretreatment kit 20, and free cyan in the wastewater is adjusted to pH 5 by a method according to JIS K 0102, and then the washed air is supplied at a constant flow rate (1 .2 L / min) for a certain period (60 minutes), and aerated into the drainage, discharged as free cyanide (hydrogen cyanide) in the sample, and collected in an aqueous sodium hydroxide solution. This is analyzed by the IC method or other methods. The analytical pretreatment apparatus shown in FIG. 7 and the analytical pretreatment kit 20 shown in FIG. 8 can be used as a simplification of the JIS method.

  The present invention is an analytical method, an analytical pretreatment device and an analytical pretreatment kit that are extremely effective for analyzing exhaust gas samples containing low concentrations of halogen compounds and sulfur oxides. Industrial applicability is high as an analysis method, a pretreatment device for analysis, and a pretreatment kit for analysis, and can be applied to various technical fields such as environmental analysis.

It is the flow of the analysis method of the halogen compound and sulfur oxide in the exhaust gas which is one Example of this invention. It is the result measured by the analysis method of the halogen compound and sulfur oxide in exhaust gas which is one Example of this invention. It is the result of measuring the absorbing solution directly by the IC method. It is the result of having measured the sample of the step which added the cation exchange resin to the absorption liquid by IC method. It is a chromatogram of an anion standard solution (7 types). It is the result of having measured by the analysis method of the halogen compound and sulfur oxide in the exhaust gas which is one Example of this invention, and is a chromatogram at the time of ventilating ozone in the absorption liquid with purge air. It is a block diagram of the pre-processing apparatus for the analysis of the halogen compound and sulfur oxide in exhaust gas which is one Example of this invention. It is a front longitudinal cross-sectional view of the analysis pretreatment kit which is one Example of this invention. It is a figure explaining the usage example of the pre-processing kit for analysis shown in FIG. It is a figure explaining the usage example of the pre-processing kit for analysis shown in FIG. It is a block diagram of the pre-processing apparatus for the analysis of compounds, such as chlorine, hydrogen sulfide, hydrogen cyanide, etc. in the exhaust gas which is a reference example of the present invention (Reference Example 1).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Absorption liquid 2 Neutralization degasser 3 Cation exchange resin 4 Gas washing container 5 Pump 6 Cleaning liquid 7 Gas ventilation pipe 8 Exhaust pipe 9 Gas flow meter 10 Plug 12 Ozonizer 15 Absorption container 16 Absorption liquid 20 Analytical pretreatment kit 21 Absorption container 22 Cap 24 Glass tube

Claims (10)

  After the exhaust gas containing halogen compounds and sulfur oxides generated from the chemical reaction apparatus is absorbed in the aqueous sodium hydroxide solution, a cation exchange resin is added to a fixed amount of the absorption liquid to adsorb sodium ions with the cation exchange resin. The carbon dioxide purge gas in the absorption liquid is passed through the absorption liquid to which the cation exchange resin is added to remove carbonate ions in the absorption liquid as carbon dioxide, and then the halogen in the absorption liquid is removed. A method for analyzing halogen compounds and sulfur oxides in exhaust gas, characterized in that fluoride ions and sulfate ions are measured by ion chromatography.   2. The halogen compound and sulfur oxidation in exhaust gas according to claim 1, wherein the carbon dioxide purging gas is a gas that has been previously cleaned to remove the halogen compound and sulfur oxide analysis-inhibiting components in the exhaust gas. Analytical method.   The halogen compound in exhaust gas according to claim 1 or 2, wherein ozone for oxidizing sulfite ions in the absorbing solution into sulfate ions together with or separately from the gas for purging carbon dioxide is passed through the absorbing solution. And sulfur oxide analysis method. Adsorbing and removing sodium ions in the absorbing liquid by contacting the cation exchange resin with the absorbing liquid that has absorbed the exhaust gas containing halogen compounds and sulfur oxides generated from the chemical reactor through an aqueous sodium hydroxide solution. A neutralization degasser for removing carbon dioxide in the absorption liquid by passing a gas for purging carbon dioxide in the absorption liquid into the absorption liquid;
A vent means for venting the carbon dioxide purge gas into the absorbent in the neutralization degasser;
A pretreatment device for analyzing halogen compounds and sulfur oxides in exhaust gas, characterized by comprising exhaust means for exhausting carbon dioxide generated from the absorbing liquid by a purge gas vented by the vent means.   5. The halogen compound in the exhaust gas according to claim 4, further comprising a gas cleaning device for cleaning the carbon dioxide purge gas to remove an analysis inhibiting component of the halogen compound and sulfur oxide in the exhaust gas. And pretreatment equipment for the analysis of sulfur oxides.   Furthermore, ozone ventilation means for ventilating ozone for oxidizing the sulfite ions in the absorption liquid into sulfate ions together with the carbon dioxide purge gas or separately in the absorption liquid in the neutralization degasser is provided. The pretreatment device for analysis of halogen compounds and sulfur oxides in exhaust gas according to claim 4 or 5.   The pretreatment device for analysis of halogen compounds and sulfur oxides in exhaust gas according to any one of claims 4 to 6, which is a pretreatment device for analysis by ion chromatography. A hermetically sealed container that can be broken with a pressing force sealed with a cation exchange resin that adsorbs and removes sodium ions;
The closed container and the sodium hydroxide aqueous solution that has absorbed the exhaust gas containing the halogen compound and sulfur oxide can be stored, and the carbon dioxide in the absorbent of the sodium hydroxide aqueous solution that has absorbed the exhaust and the opening that can be sealed by the cap A pretreatment kit for analysis of halogen compounds and sulfur oxides in exhaust gas, characterized in that it has a structure in which an absorption container having a vent for venting purge gas for removing water is integrated. The breakable sealed container is made of glass, wherein the absorption vessel is pretreated kit for the analysis of halogenated compounds and sulfur oxides according to claim 8, wherein in the exhaust gas, characterized in der made soft plastic Rukoto. The pretreatment kit for analysis of halogen compounds and sulfur oxides in exhaust gas according to claim 8 or 9, wherein the pretreatment kit is for analysis by ion chromatography .

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