JP5975130B1 - Compound treatment agent for acid gas and heavy metal, and method for treating acid gas and heavy metal - Google Patents

Abstract

[Problem] To solve the problem of the subsequent fly ash treatment process caused by excess and deficiency of acid gas treatment agent caused by changes in the properties of waste, sufficient alkalinity in the fly ash is achieved in a wide range of addition amount Can be reduced. An acidic gas and heavy metal combined treatment agent according to the present invention includes a powder containing calcium hydroxide, having a specific surface area of 20 m 2 / g or more and a median diameter (d50) of less than 30 μm, and chloride. , Mixtures with one or more compounds selected from sulfates and hydroxides. Since both the material stability and the blending stability are excellent, the chloride is preferably copper chloride, and the sulfate is preferably magnesium sulfate, sulfate-containing aluminum hydroxide, zinc sulfate or copper sulfate, The hydroxide is preferably magnesium hydroxide, aluminum hydroxide, iron hydroxide, zinc hydroxide or copper hydroxide. [Selection] Figure 3

Description

  The present invention relates to an acid gas and heavy metal composite treatment agent, and an acid gas and heavy metal treatment method. More specifically, the present invention relates to acid gases (hydrogen chloride, sulfur oxides, etc.) contained in exhaust gas generated in combustion facilities such as municipal waste waste incinerators, industrial waste incinerators, power generation boilers, carbonization furnaces, and private factories. And a composite treatment agent and a composite treatment method used for treatment of heavy metals contained in fly ash generated in this combustion facility.

  In general, exhaust gas containing hydrogen chloride or sulfur oxide is treated with an alkali agent such as calcium hydroxide and then discharged from a chimney via a dust collector such as a bag filter. On the other hand, the fly ash collected by the dust collector contains heavy metals such as harmful lead and cadmium, and the heavy metal is stabilized by the heavy metal fixing agent, and then landfilled (for example, Patent Document 1). reference).

JP-A-9-99215

  When the addition amount of the acid gas treatment agent varies greatly due to the change in the acid gas load caused by the change in the properties of municipal waste or industrial waste, an excess acid gas treatment agent can be supplied to the flue. In such a case, since the acid gas treating agent is alkaline, an alkaline compound remains in the fly ash collected by the dust collector, and a heavy metal fixing agent is applied to the fly ash collected by the dust collector. Even if supplied, this heavy metal fixing agent is consumed not only by immobilization of heavy metals contained in the fly ash, but also by neutralization reaction with the remaining acid gas treatment agent, and as a result, the heavy metals contained in the fly ash are suitably used. It may not be possible to suppress it.

  The present invention has been made in view of the above circumstances, and in order to solve the problem of the subsequent fly ash treatment process due to the excess or deficiency of the acid gas treatment agent caused by the change in the properties of the waste, The purpose is to sufficiently reduce the alkalinity in the fly ash in the added amount range.

  As a result of intensive studies to achieve the above object, the present inventors have used a powder containing calcium hydroxide in combination with an alkalinity reducing agent in place of the conventional acid gas treatment agent including slaked lime. By treating acid gas contained in the exhaust gas, the alkalinity of the fly ash collected by the dust collector can be reduced, and the amount of heavy metal elution from the fly ash after treatment with the heavy metal fixing agent can be suppressed. As a result, the present invention has been completed. Specifically, the present invention provides the following.

  (1) The present invention is a combined treatment agent of acidic gas and heavy metal containing a mixture of a powder containing calcium hydroxide and an alkalinity reducing agent.

(2) Moreover, this invention is a composite processing agent as described in (1) whose specific surface area of the powder containing the said calcium hydroxide is 20 m < ² > / g or more, and a median diameter (d50) is less than 30 micrometers. is there.

  (3) Moreover, this invention is a composite processing agent as described in (1) or (2) whose said alkalinity reducing agent is 1 or more types of compounds selected from a chloride, a sulfate, and a hydroxide. It is.

  (4) Further, according to the present invention, the compound contains copper chloride, magnesium sulfate, sulfate-containing aluminum hydroxide, zinc sulfate, copper sulfate, magnesium hydroxide, aluminum hydroxide, iron hydroxide, zinc hydroxide, and hydroxide. It is a composite processing agent as described in (3) containing 1 or more types selected from copper.

  (5) Further, the present invention provides the composite treating agent according to any one of (1) to (4), wherein the acidic gas is an acidic gas contained in exhaust gas, and the heavy metal is a heavy metal contained in fly ash. It is.

  (6) Further, the present invention treats acid gas and heavy metals by adding powder containing calcium hydroxide to exhaust gas, collecting fly ash, and adding an alkalinity reducing agent to the fly ash after dust collection. Is the method.

  According to the present invention, the acidity contained in the exhaust gas can be suitably treated, and the alkalinity of the fly ash collected by the dust collector can be reduced. As a result, the amount of heavy metal elution from the fly ash after treatment with the heavy metal fixing agent Can also be suppressed.

The schematic structure of the simulation dust collector indoor evaluation apparatus used in the Example is shown. The relationship between the addition amount of the various processing agent which concerns on an Example and a comparative example, and the hydrogen chloride gas removal rate in the apparatus shown in FIG. 1 is shown. The relationship between the addition amount of the various processing agent which concerns on an Example and a comparative example, and the alkalinity of the residue obtained with the apparatus shown in FIG. 1 is shown.

  Hereinafter, although embodiment of this invention is described, this does not limit this invention.

<Compounding agent of acid gas and heavy metal>
The composite treatment agent according to the present invention includes a mixture of a powder containing calcium hydroxide and an alkalinity reducing agent.

〔powder〕
The powder contains calcium hydroxide as an essential component. If the powder does not contain calcium hydroxide, the acidic gas contained in the exhaust gas cannot be suitably treated, which is not preferable.

  Although the kind of calcium hydroxide is not particularly limited, it is preferably a highly reactive slaked lime having a higher reactivity with acid gas than JIS special slaked lime which is generally widely known. This highly reactive slaked lime is obtained by adding the same amount of digested water as quick lime together with digestion retarders such as sugar and polyhydric alcohol. By adding the same amount of digested water as quicklime with a digestion retardant, the specific surface area of slaked lime can be increased and the reactivity with acidic gas can be improved.

  Known digestion retarders include sugars such as sugar, alcohols such as ethanol, propanol, ethylene glycol, diethylene glycol, and propylene glycol, and amino alcohols such as ethanolamine, diethanolamine, and triethanolamine. The digestion retardant is added in an amount of 0.1 to 1.0 part by mass with respect to 100 parts by mass of quicklime.

The specific surface area of the powder is not particularly limited, but is preferably 20 m ² / g or more, more preferably 30 m ² / g or more, and further preferably 40 m ² / g or more. By setting the specific surface area to 20 m ² / g or more, a sufficient contact area with the acid gas (hydrogen chloride gas, sulfur oxide gas, etc.) can be secured, so that the acid gas can be appropriately treated. Further, along with this, unreacted powder is reduced and the alkalinity of the fly ash is lowered, and as a result, the amount of heavy metal elution from the fly ash after treatment with the heavy metal fixing agent can be suitably suppressed.

In this specification, the alkalinity refers to a sample in which a sample (0.1 to 0.5 g) and 1,000 times the amount of pure water (100 to 500 ml) are put into a beaker and stirred for 1 hour with a magnetic stirrer. Take a predetermined amount (ml) with a micropipette, add a few drops of phenolphthalein indicator, mix, and then quickly titrate until 1 / 50N sulfuric acid changes color (to reach pH 8.3). The titration amount (ml) of sulfuric acid is recorded, and the value calculated by the following conversion formula is used.
(Conversion formula)
Alkalinity (mgCaCO ₃ / g)
= 0.02 {Titration sulfuric acid concentration (mol / L)} x A (ml) ÷ B (g) x C (ml) ÷ D (ml) x 100 ÷ 2
= A (ml) / B (g) x C (ml) / D (ml)

  In the conversion formula, A is a sulfuric acid titration amount (ml), B is a sample amount (g), C is a pure water addition amount (ml), and D is a preparative amount after stirring (ml). ml).

  The median diameter (d50) of the powder is not particularly limited, but is preferably 30 μm or less, and more preferably 20 μm or less.

  The lower limit of the median diameter is not particularly limited, but is preferably 5 μm or more.

  In the present specification, the “median diameter” refers to a particle diameter (d50) at which the integrated value of the number of particles in a particle size distribution on a volume basis obtained by a laser diffraction method is 50%.

(Alkalinity reducing agent)
The composite treating agent according to the present invention contains a compound having an alkalinity reducing action such as chloride, sulfate, hydroxide and the like. Hereinafter, this compound is referred to as “alkalinity reducing agent” for convenience.

  When the composite treatment agent is supplied to the flue, the acid gas reacts with the above-described powder (mainly calcium hydroxide component). The reaction products and unreacted substances in this reaction are collected as fly ash by a dust collector. And when water is added to the collected fly ash, the alkali content derived from calcium hydroxide contained in the unreacted substance reacts with the alkalinity reducing agent to reduce the alkalinity of the fly ash.

  The alkalinity reducing agent is not particularly limited as long as it can reduce the alkali content derived from calcium hydroxide contained in the unreacted material, but one or more selected from chlorides, sulfates and hydroxides. Those containing the compound are preferred. Examples of chlorides include magnesium chloride, aluminum chloride, iron (II) chloride, iron (III) chloride, zinc chloride, copper chloride and the like. Examples of sulfates include magnesium sulfate, aluminum sulfate, sulfate-containing aluminum hydroxide, iron (II) sulfate, iron (III) sulfate, zinc sulfate, copper sulfate and the like. Examples of the hydroxide include magnesium hydroxide, aluminum hydroxide, iron (II) hydroxide, iron (III) hydroxide, zinc hydroxide, copper hydroxide and the like. Among them, since the stability of the substance itself is high and heat generation when supplying the alkalinity reducing agent can be kept low, the alkalinity reducing agent includes copper chloride, magnesium sulfate, sulfate-containing aluminum hydroxide, zinc sulfate, sulfuric acid. It is preferable to include at least one selected from copper, magnesium hydroxide, aluminum hydroxide, iron hydroxide, zinc hydroxide and copper hydroxide.

The ratio between the powder and the alkalinity reducing agent is not particularly limited, but either the effect of treating acidic gas with calcium hydroxide contained in the powder or the effect of reducing the alkalinity of fly ash with the alkalinity reducing agent. Is preferably in the range of powder: alkaliness reducing agent = 10: 0.5 to 10: 8, preferably in the range of 10: 1 to 10: 6. More preferably, it is within. Further, when setting the ratio of the powder and the alkalinity reducing agent, the alkalinity of the fly ash is preferably 100 mgCaCO ₃ / g or less, more preferably 70 mgCaCO ₃ / g or less, more preferably 50 mgCaCO ₃ / g. Make sure that:

[Must be a mixture]
The composite treating agent according to the present invention is a mixture of a powder containing calcium hydroxide and an alkalinity reducing agent. In the present invention, the alkalinity reducing effect by the alkalinity reducing agent and, in some cases, the alkalinity reducing effect by the reaction product of acid gas and powder can be obtained. As a result, the elution amount of heavy metal from the fly ash after the treatment with the heavy metal fixing agent can be suppressed.

  Then, the powder and the alkalinity reducing agent may be added separately to the flue through which the exhaust gas flows, or may be added as a mixture. As a mixture of powder and alkalinity reducing agent, the installation cost and space are efficient, and (b) because it is sufficiently dispersed in the flue, it is uniformly mixed with the fly ash. It is preferable to add. In addition, when adding powder and an alkalinity reducing agent separately, you may add an alkalinity reducing agent as aqueous solution or a slurry.

[Other ingredients]
If it is a range which does not inhibit this invention, a composite processing agent may contain the other component different from a powder and an alkalinity reducing agent. Examples of other components include activated carbon for treating dioxin contained in acid gas, diatomaceous earth used as a filter aid for bag filters, and the like. Further, the composite treatment agent may contain a heavy metal fixing agent. In this case, the mixing step of the heavy metal fixing agent can be omitted, which is an effective means.

[Method for producing composite treatment agent]
The composite treatment agent can be obtained by uniformly mixing the various components described above by a conventionally known method.

<Method of treating acid gas and heavy metal>
In the treatment method according to the present invention, the above-mentioned composite treatment agent is supplied to the flue to treat the acidic gas contained in the exhaust gas, and then the fly ash is collected, and the heavy metal contained in the fly ash after the dust collection is heavy metal. Treating with a fixative.

  The type of exhaust gas is not particularly limited. For example, hydrogen chloride and sulfur oxides generated in combustion facilities such as municipal waste waste incinerators, industrial waste incinerators, power generation boilers, carbonization furnaces, private factories, etc. Exhaust gas containing any acid gas.

  The timing for supplying the composite treatment agent is not particularly limited as long as the fly ash is not collected in the dust collector. For example, the timing for incinerating waste in an incinerator, flue gas generated by incineration Until the temperature reduction tower that reduces the temperature of the exhaust gas, and after the exhaust gas is cooled by the temperature reduction tower, the exhaust gas after cooling reaches the bag filter provided in front of the dust collector Timing etc. are mentioned.

  Although the supply amount of the composite treatment agent is not particularly limited, in order to avoid both becoming too small and becoming too large, the concentration of acid gas passing through the flue is monitored and adjusted as appropriate. It is preferable to supply so as to satisfy the management target value for each combustion facility.

  After supplying the composite treatment agent to the flue, fly ash containing the reaction product of the acid gas and the composite treatment agent and the unreacted material as components is collected. The fly ash may be collected by a known dust collector.

  Here, an example in which the exhaust gas is treated with the composite treatment agent has been described as an example, but as a separate form, powder containing calcium hydroxide is supplied to the flue, fly ash is collected, The form which adds an alkalinity reducing agent to fly ash may be taken.

  In the present invention, the alkalinity of the fly ash after dust collection is kept low by the alkalinity reducing effect of the alkalinity reducing agent and, in some cases, the alkalinity reducing effect of the reaction product of acid gas and powder. Yes. Therefore, elution of heavy metals such as lead can be suppressed without treating heavy metals contained in fly ash after dust collection with heavy metal fixing agents. However, when a small amount of heavy metal is eluted or heavy metals other than lead are eluted, it is preferable to treat the heavy metal contained in the fly ash after dust collection with a heavy metal fixing agent.

  Examples of heavy metal fixing agents include generally used organic chelate-based and inorganic-based ones. Examples of inorganic heavy metal fixing agents include phosphoric acid compounds, silicon dioxide compounds, iron-containing compounds, and acidic neutralizers, and at least one selected from these can be used. Phosphoric acid compounds exhibit a long-term fixing effect of heavy metals at a disposal site, and are effective materials from the viewpoint of environmental protection. A phosphoric acid compound reacts with lead which is a heavy metal, for example, forms lead chloropyromorphite or lead pyromorphite, and can fix lead in the form of a mineral.

  Phosphoric acid compounds exhibit a long-term fixing effect of heavy metals at a disposal site, and are effective materials from the viewpoint of environmental protection. A phosphoric acid compound reacts with lead which is a heavy metal, for example, forms lead chloropyromorphite or lead pyromorphite, and can fix lead in the form of a mineral.

  The phosphoric acid compound can be used without particular limitation as long as it contains phosphoric acid, and may be a phosphate or a mineral. Specific examples include orthophosphoric acid (orthophosphoric acid), polyphosphoric acid, metaphosphoric acid, hypophosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, superphosphoric acid, primary phosphoric acid soda, and secondary phosphoric acid. Soda, trisodium phosphate, primary potassium phosphate, dibasic potassium phosphate, tertiary potassium phosphate, primary calcium phosphate, secondary calcium phosphate, primary magnesium phosphate, secondary magnesium phosphate, primary phosphate Ammonium, dibasic ammonium phosphate, lime superphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium phosphite, potassium phosphite, hypophosphorous acid Examples thereof include sodium and potassium hypophosphite. Among these, minerals having the form of orthophosphoric acid, primary phosphate, secondary phosphate, tertiary phosphate, tripolyphosphate, hexametaphosphate, pyrophosphate, hydroxyapatite, especially apatite (apatite Compound) exhibits a good heavy metal fixing effect.

  Phosphoric acid compounds are particularly useful for immobilization of lead among heavy metals.

The silicon dioxide-containing compound has the effect of containing calcium metal in fly ash and silicon dioxide to produce calcium silicate mineral (3CaO · 2SiO ₂ · 3H ₂ O), and encapsulating heavy metals in the mineral, In addition, it is considered that the effect of fixing heavy metal can be obtained by silicon dioxide directly acting on heavy metal to form hardly soluble heavy metal silicate (PbSiO3 or the like). The heavy metal fixation of the silicon dioxide-containing compound is affected by the alkali content in the fly ash, and if the alkali content in the fly ash is large, the required addition amount increases. Therefore, according to the present invention, the required addition amount can be greatly reduced even in the silicon dioxide-containing compound.

The silicon dioxide-containing compound can be used without particular limitation as long as it is a compound having an SiO ₂ component, and may be silicon dioxide itself, a salt, or a mineral.

  Silicon dioxide-containing compounds include silicates containing alkali metals and alkaline earth metals such as sodium silicate and potassium silicate, silica fume, silica gel, activated clay, zeolite, bentonite, kaolinite, halloysite, antigolite, piolite. Wright, talc, montmorillonite, savonite, permiculite, muscovite, barragonite, illite, phlogopite, biotite, margarite, zansophylite, donpasite, sudite, clinochlore, chamosite, sepiolite, palygorskite, imogolite, allophane, and hychinguerite And silicate minerals.

  Silicon dioxide-containing compounds are particularly useful for immobilizing lead among heavy metals.

  The iron-containing compound only needs to contain iron, and examples thereof include ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, polyferric sulfate, and iron powder.

  Iron-containing compounds are particularly useful for immobilization of hexavalent chromium, arsenic, selenium and mercury among heavy metals.

  The acidic neutralizing agent has a role of reducing the elution amount of heavy metals. The acidic neutralizer is also affected by the alkali remaining in the fly ash, and if the alkali content in the remaining fly ash is large, the required addition amount increases. Therefore, according to the present invention, the necessary addition amount of the acidic neutralizer can be greatly reduced.

  Examples of the acidic neutralizer include hydrochloric acid, sulfuric acid, nitric acid, aluminum chloride, polyaluminum chloride, aluminum sulfate and the like.

  The acidic neutralizer may be used alone, but is preferably used in combination with the above-described inorganic heavy metal fixing agent from the viewpoint of further suppressing elution of heavy metals. Moreover, when an inorganic heavy metal fixing agent and an acidic neutralizing agent are used in combination, it is preferable in that the amount of the expensive inorganic heavy metal fixing agent can be reduced. Furthermore, the effect of the present invention can be obtained even when a neutralizing agent and a chelate heavy metal fixing agent are used in combination.

  Here, the pH of the eluate when the liquid-solid ratio of the fly ash after adding the inorganic heavy metal fixing agent and / or the acidic neutralizer is 10 is preferably 8.0 to 11.5, particularly More preferably, it is 9.0-10.5.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.

<Screening for alkalinity reducing agents>
The alkalinity reducing agent is sufficient if it can reduce the alkali content derived from calcium hydroxide contained in the unreacted material, and includes one or more compounds selected from chloride, sulfate and hydroxide. There is no particular limitation.

  First, in order to confirm the effect of the alkalinity reducing agent, the presence or absence of the alkalinity reducing action was confirmed for various compounds shown in Table 1.

For the ash generated from the municipal waste waste incinerator A factory (alkalinity: 106 mg CaCO ₃ / g, lead content: 4290 mg / kg, lead elution amount: 127 mg / L), various alkalinities listed in Table 1 The reducing agent was added in the proportions listed in Table 1. And the alkalinity after alkalinity reducing agent supply was measured. The results are shown in Table 1. From Table 1, the alkalinity reducing action was confirmed for various compounds.

Next, in order to find a more suitable alkalinity reducing agent in terms of stability of the substance itself and suppression of heat generation when supplying the alkalinity reducing agent, screening of the alkalinity reducing agent for various compounds shown in Table 2 is performed. went.
Material stability was evaluated by allowing the alkalinity reducing agent to stand for 1 week at room temperature / humidity and confirming the appearance.
For compounding stability, 70 parts by weight of highly reactive slaked lime specified in the examples, 30 parts by weight of alkalinity reducing agent and 20 parts by weight of water were added, stirred with a spatula, and temperature rise (Δ ° C.) before and after stirring was measured. It was evaluated by doing.
The results of screening are shown in Table 2.

  From the evaluation results shown in Table 2, copper chloride, magnesium sulfate, zinc sulfate, copper sulfate, magnesium hydroxide, aluminum hydroxide, iron hydroxide, zinc hydroxide and copper hydroxide are either of material stability or compounding stability. It was also confirmed that it is more suitable as an alkalinity reducing agent.

  Moreover, the relationship of the elution density | concentration of harmful lead when alkalinity was reduced was confirmed using the fly ash of B factory. At this time, magnesium sulfate was used as an alkalinity reducing agent. The elution concentration of lead was determined by an elution test based on a method for testing metals contained in industrial waste (environmental agency notification No. 13 in 1973). The results are shown in Table 3.

  From Table 3, it was confirmed that when the alkalinity is reduced, the lead elution amount is also reduced.

Furthermore, for conditions where the landfill reference value (0.3 mg / L) could not be satisfied, using a phosphate compound (75% normal phosphoric acid aqueous solution) as a heavy metal fixing agent, lead fixation was performed under the conditions shown in Table 4. Processed. As a result, it was found that the necessary addition rate of the heavy metal fixing agent is reduced by reducing the alkalinity.

<Preparation of composite treatment agent>
[Example 1]
70 parts by weight of highly reactive slaked lime that is generally available (specific surface area: 46 m ² / g, median diameter (d50): 7.9 μm, pore volume: 0.26 ml / g), and sulfate-containing hydroxide 30 parts by weight of aluminum (product name: Ashnite I-201, a compound represented by the chemical formula Alx (SO ₄ ) y (OH) z, manufactured by Kurita Kogyo Co., Ltd.) is mixed, and the composite treating agent according to Example 1 is mixed. Obtained.

[Example 2]
The composite according to Example 2 was prepared in the same manner as in Example 1 except that the sulfate-containing aluminum hydroxide was changed to magnesium sulfate (specific surface area: 5.8 m ² / g, median diameter (d50): 228 μm). A treating agent was obtained.

[Comparative Example 1]
The same highly reactive slaked lime as the highly reactive slaked lime used in Example 1 was used as the treatment agent according to Comparative Example 1.

  In Examples and Comparative Examples, “specific surface area” is a specific surface area calculated by the BET method, and “pore volume” is a pore volume calculated by the BJH method. All of these can be measured by a measuring apparatus such as NOVA2000 manufactured by Quanta Chrome. The “median diameter (d50)” is a particle diameter (d50) at which the integrated value of the number of particles in the particle size distribution determined by the laser diffraction scattering method is 50%, and is measured by SALD-2100 manufactured by Shimadzu Corporation. It can be measured by the device.

<Comparison of processing performance # 1>
Using the simulated dust collector indoor evaluation device shown in FIG. 1, the processing performance of various processing agents according to Examples and Comparative Examples was evaluated. In this apparatus, the test conditions were as follows.
Gas flow rate: 0.43 m ³ / min
Filtration area: 0.43 m ²
Filtration speed: 1 m / min
HCl concentration load; 350ppm
Dust collection chamber temperature: 180 ° C

  First, after adjusting the HCl concentration at the inlet of the dust collection chamber to 350 ppm, supply of various treatment agents according to Examples and Comparative Examples was started. Twenty minutes after the start of supply, an HCl meter (product name: HL-22, manufactured by Kyoto Electronics Co., Ltd.) was used to measure the outlet HCl concentration, and the average value of 30 minutes of data collected every other minute was measured under HCl under the test conditions. The outlet concentration was used. Then, the HCl removal rate was calculated from the inlet HCl concentration and the outlet HCl concentration. The results are shown in Table 5 and FIG.

  It was confirmed that the composite treatment agents according to Examples 1 and 2 were able to treat acid gas suitably as with the various treatment agents so far. The addition amount of the composite treatment agent necessary to achieve the HCl removal rate of 90% is 1.0 g / min in Example 1 and 1.1 g / min in Example 2, which is related to the comparative agent. Although a slight increase in the addition rate was seen compared to the treatment agent, the amount of heavy metal fixative added was optimized by reducing the alkalinity of fly ash as described later, including exhaust gas treatment and heavy metal treatment. From a perspective, it is in a range where there is no problem.

  Next, the alkalinity of the residue from which the filter cloth deposits were removed under each condition was measured. The results are shown in Table 6 and FIG.

When the composite treatment agent according to Example 1 is used, the alkalinity is about 340 mg CaCO ₃ / g, and when the composite treatment agent according to Example 2 is used, the alkalinity changes about 350 mg CaCO ₃ / g. 1 shows a remarkable alkalinity reduction effect as compared with the treating agent. Moreover, this tendency was confirmed in the wide range with the addition amount of a composite processing agent 0.7g / min-1.2g / min.

<Comparison of processing performance # 2>
In the above <Comparison of processing performance, part 1>, the residue after evaluating the processing performance of the various processing agents according to the examples and comparative examples was obtained from the C factory with the ash that was not blown with the acid gas processing agent. Then, 4 parts by weight of the first ash of the two-stage bag filter was mixed with 1 part by weight of the residue to prepare simulated fly ash. Table 3 shows the properties of ash obtained from Factory C and the properties of various simulated fly ash.

In this example, the lead content, eluate pH, and lead elution concentration are measured by the following methods.

Method for measuring lead content Fly ash is heated and concentrated with concentrated nitric acid and concentrated hydrochloric acid and allowed to cool. After standing to cool, pure water is added, and the heated and dissolved solution is filtered through a quantitative filter paper (Advantech, No. 6), and the lead concentration in the filtrate is measured by an atomic absorption photometer (Hitachi, Z-2000). Measured with

Method for Measuring Eluate pH After performing an elution test based on the Environmental Agency Notification No. 13 test method, the pH of the eluate was measured.

Method for measuring lead elution amount After conducting an elution test based on the Environmental Agency Notification No. 13 test method, the lead concentration in the eluate was measured with an atomic absorption photometer (manufactured by Hitachi, Z-2000).

Subsequently, each of the simulated fly ash was subjected to lead fixing treatment under the conditions shown in Table 8 using various heavy metal fixing agents (phosphoric acid compounds, silicon dioxide-containing compounds, iron-containing compounds). In the lead fixation treatment, 20% by weight of pure water and a predetermined amount of various heavy metal fixatives (phosphate-based compounds, silicon dioxide-containing compounds, iron-containing compounds) are added to each fly ash sample. With thorough stirring. And while measuring the alkalinity and lead content of various samples after a lead fixation process, the elution test was done to Environment Agency Notification No. 13 test method, and eluate pH and lead elution concentration were measured. The results are shown in Tables 8-10.

  As can be seen from Tables 8 to 10, in Examples 1 and 2, the alkalinity was reduced, and accordingly, the amount of lead elution was reduced. In addition, with the reduction in alkalinity, the addition rate of heavy metal fixing agent for reducing the amount of lead elution to a landfill reference value or less was reduced.

Claims (6)

Including a mixture of a powder containing calcium hydroxide and an alkalinity reducing agent,
The alkalinity reducing agent is at least one selected from magnesium sulfate, aluminum hydroxide, iron hydroxide, zinc hydroxide, and copper hydroxide, and is a combined treatment agent of acidic gas and heavy metal. The composite treatment agent according to claim 1, wherein the powder containing calcium hydroxide has a specific surface area of 20 m ² / g or more and a median diameter (d50) of less than 30 µm. The acidic gas is an acidic gas contained in exhaust gas,
The composite treatment agent according to claim 1, wherein the heavy metal is a heavy metal contained in fly ash. After adding powder containing calcium hydroxide to the exhaust gas, collecting fly ash, adding an alkalinity reducing agent to the fly ash after dust collection;
Adding a heavy metal fixing agent to the fly ash after adding the alkalinity reducing agent,
The alkalinity reduction agent, magnesium sulfate, water aluminum oxide, iron hydroxide and at least one selected from zinc hydroxide and copper hydroxide,
The heavy metal fixing agent includes one or more selected from a phosphoric acid compound, a silicon dioxide-containing compound and an iron-containing compound,
When the heavy metal fixing agent contains the phosphoric acid compound, the phosphoric acid content contained in the phosphoric acid compound added to the fly ash is 3% by mass to 4.5% by mass with respect to the fly ash. Is less than
When the heavy metal fixing agent includes the silicon dioxide-containing compound, the amount of the silicon dioxide-containing compound added to the fly ash is 7% by mass or more and less than 12% by mass with respect to the fly ash.
When the heavy metal fixing agent contains the iron-containing compound, the iron content contained in the iron-containing compound added to the fly ash is 1.7% by mass or more and less than 2.8% by mass with respect to the fly ash. A method for treating acid gas and heavy metal. After adding the combined treatment agent of acid gas and heavy metal to the exhaust gas, collecting fly ash, adding heavy metal fixing agent to the fly ash after dust collection,
The composite treatment agent includes a mixture of a powder containing calcium hydroxide and an alkalinity reducing agent,
The alkalinity reduction agent, magnesium sulfate, water aluminum oxide, iron hydroxide and at least one selected from zinc hydroxide and copper hydroxide,
The heavy metal fixing agent includes one or more selected from a phosphoric acid compound, a silicon dioxide-containing compound and an iron-containing compound,
When the heavy metal fixing agent contains the phosphoric acid compound, the phosphoric acid content contained in the phosphoric acid compound added to the fly ash is 3% by mass to 4.5% by mass with respect to the fly ash. Is less than
When the heavy metal fixing agent includes the silicon dioxide-containing compound, the amount of the silicon dioxide-containing compound added to the fly ash is 7% by mass or more and less than 12% by mass with respect to the fly ash.
When the heavy metal fixing agent contains the iron-containing compound, the iron content contained in the iron-containing compound added to the fly ash is 1.7% by mass or more and less than 2.8% by mass with respect to the fly ash. A method for treating acid gas and heavy metal.   The method for treating acidic gas and heavy metal according to claim 4 or 5, wherein the heavy metal fixing agent and the acidic neutralizer are used in combination.

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