JP2005087962A - Heavy-metal fixing agent for incineration (fly) ashes - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heavy-metal fixing agent for incineration (fly) ashes that can prevent heavy metals from eluting by fixing the heavy metals present in incineration (fly) ashes and gives an extremely small amount of hazardous gas in decomposition. <P>SOLUTION: The heavy-metal fixing agent for incineration (fly) ashes is comprised of one or more kinds of cyclic phenolic sulfides selected from the group composed of a particular cyclic compound such as thiacalixarene, sulfinyl thiacalixarene and sulfonyl thiacalixarene, and metal sulfonates thereof. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a heavy metal fixing agent for incineration (flying ash) capable of fixing heavy metals present in incineration (flying) ash to prevent elution of heavy metals and a method for treating heavy metal-containing incineration (flying) ash.

  Conventionally, it means incineration (flying ash) [incineration ash, incineration fly ash or molten fly ash [fly ash obtained by melting incineration (flying) ash], and so on. As a drug for immobilizing heavy metals present therein and preventing elution of heavy metals, a polymer chelating agent in which carbon disulfide is added to polyamine or polyethyleneimine is known (for example, see Patent Document 1). ). Further, in recent years, in the treatment of incineration (flying) ash, a method of increasing the pH of the heavy metal fixing agent aqueous solution to 13 or more in order to suppress the generation of harmful gas generated from the heavy metal fixing agent (for example, see Patent Document 2). Various heavy metal immobilization methods have been proposed, such as a method of containing an amine in a heavy metal immobilizing agent (see, for example, Patent Document 3).

Japanese Patent Laid-Open No. 3-231921 Japanese Patent Laid-Open No. 10-109081 JP-A-9-234450

However, the heavy metal immobilizing agent described in Patent Document 1 has a problem that harmful gases such as hydrogen sulfide, carbon disulfide, and amine are generated due to decomposition of the dithiocarbamic acid group, and the method described in Patent Document 3 Has the effect of suppressing decomposition to some extent immediately after being added to the object to be treated, but has the problem that the effect of suppressing decomposition does not last long.
An object of the present invention is to provide a heavy metal immobilizing agent for incineration (flying ash) that generates very little harmful gas due to decomposition.

［式中、Ｒは環構造を有する炭素数４〜１４またはそれ以上の４価の炭化水素基；Ｑは−ＣＲ¹Ｒ²−、−ＮＲ³−、−Ｏ−、−ＣＯ−、−Ｓ_m−、−ＳＯ−および−ＳＯ₂−からなる群から選ばれる２価の基、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立にＨまたは炭化水素基からなる群から選ばれる１価の基；Ｘ、Ｚはそれぞれ独立にＨまたは炭化水素基、アシル基、アミノ基、アミド基、チオアミド基、シアノ基、チオール基、水酸基、カルボキシル基、スルホ基、硫酸基、ホスホン酸基、リン酸基およびそれらの金属塩基からなる群から選ばれる１価の基；ｍは１〜７の整数、ｎは３〜８の整数を表す。］；並びに、重金属を含有する焼却（飛）灰に該重金属固定化剤および必要により水を含有させて撹拌または混練することを特徴とする重金属含有焼却（飛）灰の処理方法である。 The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is a heavy metal fixing agent for incineration (flying) ash comprising a cyclic compound (a) represented by the general formula (1) (A).

[Wherein, R is a tetravalent hydrocarbon group having 4 to 14 or more carbon atoms having a ring structure; Q is —CR ¹ R ² —, —NR ³ —, —O—, —CO—, —S _m -, - SO- and -SO ₂ - 2 divalent group selected from the group consisting of a monovalent group selected from R ^1, R ² and R ³ is the group consisting of independently H or a hydrocarbon group; X and Z are each independently H or a hydrocarbon group, acyl group, amino group, amide group, thioamide group, cyano group, thiol group, hydroxyl group, carboxyl group, sulfo group, sulfuric acid group, phosphonic acid group, phosphoric acid group and A monovalent group selected from the group consisting of those metal bases; m represents an integer of 1 to 7, and n represents an integer of 3 to 8. In addition, the heavy metal-containing incineration (flying ash) treatment method is characterized in that the incineration (flying ash) containing heavy metal is stirred or kneaded by containing the heavy metal fixing agent and water as necessary.

  Since the heavy metal immobilizing agent of the present invention is excellent in the effect of immobilizing heavy metals, it is possible to immobilize heavy metals in incineration (flying) ash by adding a small amount. Moreover, since it is excellent in heat resistance, it does not generate harmful gas during the treatment of high-temperature incineration (flying ash) and is extremely excellent in safety and workability.

［式中、Ｒは環構造を有する炭素数４〜１４またはそれ以上の４価の炭化水素基；Ｑは−ＣＲ¹Ｒ²−、−ＮＲ³−、−Ｏ−、−ＣＯ−、−Ｓ_m−、−ＳＯ−および−ＳＯ₂−からなる群から選ばれる２価の基、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立にＨまたは炭化水素基からなる群から選ばれる１価の基；Ｘ、Ｚはそれぞれ独立にＨまたは炭化水素基、アシル基、アミノ基、アミド基、チオアミド基、シアノ基、チオール基、水酸基、カルボキシル基、スルホ基、硫酸基、ホスホン酸基、リン酸基およびそれらの金属塩基からなる群から選ばれる１価の基；ｍは１〜７の整数、ｎは３〜８の整数を表す。］ The cyclic compound (a) in the present invention is represented by the following general formula (1).

[Wherein, R is a tetravalent hydrocarbon group having 4 to 14 or more carbon atoms having a ring structure; Q is —CR ¹ R ² —, —NR ³ —, —O—, —CO—, —S _m -, - SO- and -SO ₂ - 2 divalent group selected from the group consisting of a monovalent group selected from R ^1, R ² and R ³ is the group consisting of independently H or a hydrocarbon group; X and Z are each independently H or a hydrocarbon group, acyl group, amino group, amide group, thioamide group, cyano group, thiol group, hydroxyl group, carboxyl group, sulfo group, sulfuric acid group, phosphonic acid group, phosphoric acid group and A monovalent group selected from the group consisting of those metal bases; m represents an integer of 1 to 7, and n represents an integer of 3 to 8. ]

In the general formula (1), R is a tetravalent hydrocarbon group having 4 to 14 or more (preferably 6 to 10) carbon atoms having a ring structure. If the carbon number of R is less than 4, the stability during storage of (A) will be poor.
Examples of R include residues of aromatic ring-containing hydrocarbons (for example, benzene, naphthalene and anthracene) and alicyclic hydrocarbons (for example, cyclohexane) excluding 4 H atoms. Of these, a residue of an aromatic ring-containing hydrocarbon is preferred, and a benzene residue is more preferred.

Q is a divalent group selected from the group consisting of —CR ¹ R ² —, —NR ³ —, —O—, —CO—, —S _m —, —SO— and —SO ₂ —, ¹ , R ² and R ³ each independently represents a monovalent group selected from the group consisting of H or a hydrocarbon group.
When R ¹ , R ² or R ³ is a hydrocarbon group, examples of the hydrocarbon group include aliphatic hydrocarbon groups (having 1 to 6 carbon atoms such as methyl, ethyl, butyl and hexyl groups), alicyclic hydrocarbons. Groups (4 to 8 carbon atoms such as cyclobutyl, cyclopentyl and cyclohexyl groups) and aromatic ring-containing hydrocarbon groups (7 to 10 carbon atoms such as benzyl and phenylethyl groups). Among these, from the viewpoint of solubility in water, an aliphatic hydrocarbon group is preferred, and methyl, ethyl, propyl and butyl groups are more preferred.
Of the above R ¹ , R ² or R ³ , H is preferred from the viewpoint of solubility in water.
M in —S _m — represents an integer of 1 to 7, preferably 1 to 4, and more preferably 1 to 2. When m exceeds 7, the stability during storage of (A) is deteriorated.
Of the above divalent groups constituting Q, —NR ³ —, —O—, —CO—, —S _m —, —SO— and —SO ₂ —, are preferable from the viewpoint of the effect of immobilizing heavy metals. further preferred are -S _m -, - SO- and -SO ₂ - it is.

In the general formula (1), X and Z are each independently H or a hydrocarbon group, an acyl group, an amino group (primary or secondary), an amide group, a thioamide group, a cyano group, a thiol group, a hydroxyl group, a carboxyl group, It represents a monovalent group selected from the group consisting of a sulfo group, a sulfuric acid group, a phosphonic acid group, a phosphoric acid group and their metal bases.
When X or Z is a hydrocarbon group, examples of the hydrocarbon group include those exemplified as the hydrocarbon group for R ¹ , R ² or R ³ , and from the viewpoint of solubility in water, A hydrocarbon group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl and butyl groups);
When X or Z is a secondary amino group, examples of the substituent include a hydrocarbon group having 1 to 6 carbon atoms. From the viewpoint of solubility in water, an alkyl group having 1 to 4 carbon atoms (for example, methyl group) is preferable. Ethyl, propyl and butyl groups).
When X or Z is a monovalent group of a metal salt, the metals include alkali metals (eg, lithium, sodium, potassium, cesium and frangium) and alkaline earth metals (eg, magnesium and calcium) and From the viewpoint of solubility, preferred are alkali metals, and more preferred are sodium and potassium.
Of the above X and Z, at least one of (a) is preferable from the viewpoint of water solubility and heavy metal immobilization effect, thiol group, hydroxyl group, carboxyl group, sulfo group, sulfate group, phosphonic acid group, phosphorus In the case of a monovalent group selected from the group consisting of acid groups and their metal bases, more preferred are selected from the group consisting of thiol groups, hydroxyl groups, sulfo groups, sulfate groups and their metal (sodium or potassium) bases. A monovalent group, particularly preferably, X and Z are both monovalent groups selected from the group consisting of a thiol group, a hydroxyl group, a sulfo group, a sulfate group, and a metal (sodium or potassium) base thereof.
n represents an integer of 3 to 8, preferably 4 to 6, and more preferably 4. When n is less than 3 and exceeds 8, the effect of immobilizing heavy metal (a) is deteriorated.

In (a), in general formula (1), X is a hydroxyl group, R is a benzene residue excluding four H atoms, Q is —S—, —SO— or —SO ₂ —, Z is a sulfo group or its Cyclic phenol sulfides selected from the group consisting of thiacalixarene, sulfinylated thiacalixarene, sulfonylated thiacalixarene and their sulfonic acid metal salts, wherein the metal base and n is an integer of 4-6 are included. Of these, from the viewpoint of the solubility in water of (a) and the effect of immobilizing heavy metals, a cyclic phenol sulfide in which Z is a metal group having a sulfo group, and more preferably a thiacalix in which n is 4, 4] Metal arene sulfonate, especially thiacalix [4] sodium arene sulfonate.

The outline of the method for producing thiacalixarene, sulfinylated thiacalixarene, sulfonylated thiacalixarene and sodium sulfonate thereof among (a) will be described below.
(1) Thiacalixarene and its sodium sulfonate After adding simple sulfur and sodium hydroxide to a phenol derivative (eg, 4-t-butylphenol) in a solvent (eg, tetraethylene glycol dimethyl ether) under a nitrogen atmosphere, gradually The temperature is raised to about 230 ° C. The reaction mixture is cooled, dissolved by adding ether, and hydrolyzed with an aqueous sulfuric acid solution. The reaction mixture obtained by distilling off volatile components from the separated ether phase was separated by silica gel column chromatography (hexane / chloroform) to obtain a crude product, and then the crude product was re-reacted from chloroform / acetone. The thiacalixarene is obtained by crystallization.
95% concentrated sulfuric acid is added to the thiacalixarene, suspended, heated and reacted at 90 ° C. After cooling, it is diluted with ion-exchanged water, and the unreacted raw material is filtered. Sodium chloride is added to the filtrate for salting out. The resulting powder is washed with ethanol and recrystallized from water to obtain sodium thiacalixarene sulfonate.

(2) Sulfonylated thiacalixarene and its sodium sulfonate The thiacalixarene obtained in (1) above is dissolved in chloroform, and acetic acid and sodium perborate are added and reacted at 50 ° C. The product is extracted from the reaction solution with chloroform, and the chloroform phase is washed with 2N hydrochloric acid, and then volatile components are distilled off. The resulting powder is recrystallized from benzene-methanol to obtain a sulfonylated thiacalixarene.
Hydrogen peroxide water is added to the sulfonylated thiacalixarene, and trifluoroacetic acid is added dropwise to the mixed solution, followed by reaction at room temperature, and acetone is added to the resulting reaction solution to precipitate a solid. By recrystallizing the precipitated solid from acetone-water, sodium sulfonylated thiacalixarene sulfonate is obtained.

(3) Sulfinylated thiacalixarene and its sodium sulfonate The solution of thiacalixarene obtained in (1) above in chloroform is added dropwise with a solution of hydrogen peroxide-glacial acetic acid and allowed to react at room temperature for about 24 hours. . Sulfinylated thiacalixarene is obtained by adding ion-exchanged water to the reaction solution, extracting with chloroform, washing the chloroform phase with ion-exchanged water, and distilling off the volatile components.
A sulfinylated thiacalixarene sulfonate sodium salt is obtained by the same method as the above sulfinylated thiacalixarene production method except that the thiacalixarene sodium sulfonate obtained in the above (1) is used in place of the thiacalixarene.
The above (a) may be used alone or in combination of two or more.

If necessary, the heavy metal fixing agent of the present invention may be used in combination with another heavy metal fixing agent (B) as long as the effects of the present invention are not inhibited.
(B) includes known organic heavy metal immobilizing agents (B1) and inorganic heavy metal immobilizing agents (B2) except for (A).
Examples of (B1) include those described in JP-A-8-269434, such as dithiocarbamic acid group, thiocarbamic acid group, thioamide group, thioureido group, xanthogenic acid group, thiol group, thiophenol group, and alkali metals thereof. (E.g. lithium, sodium and potassium), ammonium or amine (mono-, di- and trialkylamines having 1 to 8 carbon atoms such as methylamine, mono-, di- and triethylamine) bases.
Examples of (B2) include sodium monosulfide, poly (2-5) sodium sulfide, and sodium hydrogen sulfide.
Among these, from the viewpoint of the effect of immobilizing heavy metals, (B1) is preferred, and a heavy metal immobilizing agent having a dithiocarbamic acid group and an alkali metal base thereof is more preferred.

  When the other heavy metal immobilizing agent (B) is used in combination, the amount used is usually 50% or less based on the total weight of (A) and (B), and the preferred lower limit is 0.1 from the viewpoint of the effect of immobilizing heavy metals. %, More preferably 1%, and from the viewpoint of heat resistance, the upper limit is preferably 30%, more preferably 20%.

  When treating incineration (flying) ash containing heavy metal using the heavy metal fixing agent (A) of the present invention, a method of using one kind alone, a method of using it as a mixture of two or more kinds, or two or more kinds May be carried out by any of the methods of adding them to the object to be processed in random order.

  The form of (A) may be either a solid or an aqueous solution in which (A) is dissolved in water. In the case of an aqueous solution, the lower limit of the pure content of (A) is preferably 5% by weight, more preferably 10% by weight, particularly preferably 15% by weight, and most preferably 20% by weight from the viewpoint of transportation cost. From the viewpoint of stability at low temperature storage, the upper limit is preferably 70% by weight, more preferably 60% by weight, particularly preferably 55% by weight, and most preferably 50% by weight.

  The amount of (A) used can be arbitrarily adjusted according to the heavy metal content contained in the incineration (flying) ash and is not particularly limited, but the lower limit is heavy metal as the solid content based on the weight of the incineration (flying) ash. From the viewpoint of the immobilization effect, preferably 0.1%, more preferably 0.5%, particularly preferably 1%, and the upper limit is preferably 50%, more preferably 35%, particularly preferably 20% from the viewpoint of drug cost. It is.

  The temperature of the incineration (flying) ash when adding the heavy metal fixing agent of the present invention is preferably 20 ° C., more preferably 50 ° C. from the viewpoint of reducing the processing cost without adjusting the temperature at the lower limit. Particularly preferably 80 ° C., most preferably 100 ° C., and the upper limit is preferably 400 ° C., more preferably 350 ° C., particularly preferably 300 ° C., most preferably 250 ° C. from the viewpoint of preventing decomposition of the heavy metal fixing agent.

  The method of adding (A) to the object to be treated is not particularly limited, and is a method of adding to the incineration (flying ash) in the form of the solid or aqueous solution, dissolving the solid in water in advance or the aqueous solution. May be diluted (for example, about 10 to 100 times) to make an aqueous solution having a content of (A) of 0.1 to 70% by weight and then added to the incinerated (flying) ash. Further, (A) and water may be added separately in any order.

  As a method for treating incineration (flying ash), (A) and, if necessary, water and other heavy metal fixing agent (B) may be sprayed on the surface of incineration (flying ash). From the viewpoint of the effect, it is more preferable to add to the incinerated (flying) ash and stir or knead. Further, in addition to the above addition method, the aqueous solution (A) may be sprayed and added to the flue gas of the incinerator.

In the incineration (flying ash) treatment method of the present invention, a commonly used flocculant and pH adjuster may be used in combination.
The flocculant includes inorganic (for example, aluminum sulfate, polyaluminum chloride, sodium aluminate, ferrous sulfate, ferric sulfate, and ferric chloride) and organic (for example, poly (meth) acrylic acid (salt)). , (Meth) acrylamide polymers [eg poly (meth) acrylamide, poly (meth) acrylamide partial hydrolyzate, poly (meth) acrylamide methylolation cationized product, (meth) acrylamide / (meth) acrylic acid (salt) copolymerization , Quaternized product of (meth) acrylamide / dialkylaminoethyl (meth) acrylate copolymer and copolymer of (meth) acrylamide / dialkylaminoethyl (meth) acrylate quaternized product], dialkylaminoethyl (meth) acrylate Quaternized polymers, polyethyleneimine and natural products [For example guar gum, alginates and chitosan] contain].
When the coagulant is used in combination, the use amount is usually 5% or less based on the weight of incineration (flying ash), and preferably 0.0001 to 3% from the viewpoint of exhibiting a sufficient coagulation effect.

The pH adjuster is not particularly limited, and acidic substances include, for example, mineral acids (for example, sulfuric acid, hydrochloric acid and phosphoric acid), inorganic solid acidic substances (for example, acidic sodium phosphate, acidic sodium sulfate, ammonium chloride, ammonium sulfate, ammonium sulfate). And sulfamic acid) and organic acids (2 to 24 carbon atoms, such as oxalic acid and succinic acid); as alkaline substances, inorganic alkaline substances (for example, sodium hydroxide, potassium hydroxide, slaked lime, quicklime and ammonia) and organic alkaline substances ( For example, guanidine).
The amount used in combination with the pH adjuster is not particularly limited, but is preferably 0.1% or less based on the weight of the incinerated (flying) ash, and is preferably 0.1% from the viewpoint of reducing the weight after treatment. -10%.

  The kneading apparatus for adding (A) to the incineration (flying) ash and kneading is not particularly limited, and examples thereof include ordinary ones such as a kneader and a Hobart mixer.

  Examples of heavy metals contained in incineration (flying) ash include lead, cadmium, copper, zinc, mercury, chromium, nickel, arsenic, and selenium, but the heavy metal immobilizing agent (A) of the present invention includes: Especially, heavy metal immobilization effect is high for lead, cadmium, copper, zinc, mercury and nickel.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example represents a weight part and% represents weight%.

Production Example 1
{5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathia [1.9.3.1.1 ^3,7 1 ^{9 , 13} 1 ^15,19 ] octacosa-1 (25), 3, 5, 7 (28), 9, 11, 13 (27), 15, 17, 19 (26), 21,23-dodecaene [ie, thia Calix [4] arene, hereinafter referred to as (a1). 〕Manufacturing of}
To 90 parts of 4-t-butylphenol, 29 parts of elemental sulfur, 6 parts of sodium hydroxide, and 15 parts of tetraethylene glycol dimethyl ether were added and gradually heated to 230 ° C. over 4 hours while stirring in a nitrogen atmosphere. Stirring was continued for another 2 hours, during which water and hydrogen sulfide produced by the reaction were removed. After cooling, 350 parts of ether was added and dissolved, followed by hydrolysis with a 4.8% aqueous sulfuric acid solution. The separated ether layer was washed with water and dried over magnesium sulfate. Further, ether was distilled off to obtain 13 parts of (a1).

Production Example 2
{25,26,27,28- tetrahydroxy--2,8,14,20- Tetorachia [1.9.3.1.1 ^3,7 1 ^9,13 1 ^15,19] Okutakosa -1 (25), 3,5,7 (28), 9, 11, 13 (27), 15, 17, 19 (26), 21,23-dodecaene-5,11,17,23-sodium tetrasulfonate [ie, thiacalix [4] Sodium arene sulfonate, hereinafter referred to as (a2). 〕Manufacturing of}
In a eggplant-shaped flask equipped with a reflux condenser, 10 parts of (a1) and 184 parts of 95% concentrated sulfuric acid were added and suspended, heated to 90 ° C. and reacted for 24 hours. The reaction solution was cooled with water and filtered with a glass filter, and 50 parts of ion-exchanged water was added to the filtrate to filter unreacted raw materials. Next, 20 parts of sodium chloride was added to the filtrate for salting out to obtain 10 parts of (a2).
Example 1
(A2) was dissolved in ion-exchanged water to obtain a heavy metal fixing agent aqueous solution (A1) having a concentration of 20%.

Comparative Example 1
Production of aqueous solution of sodium polyethylenimine dithiocarbamate (X1) After charging 887 parts of ion-exchanged water and 500 parts of 30% aqueous solution of polyethylenimine having a number average molecular weight of 70,000 in a reaction vessel capable of cooling and stirring and capable of nitrogen substitution Then, 233 parts of a 48% aqueous sodium hydroxide solution was charged, and 212 parts of carbon disulfide was added dropwise over 2 hours while stirring vigorously at 45 ° C. in a nitrogen atmosphere. After completion of the dropwise addition, aging was performed at the same temperature for 15 hours to obtain a 26% aqueous solution (X1) of the heavy metal immobilizing agent sodium polyethyleneimine dithiocarbamate.

Example 2 and Comparative Example 2
Weighing 50 parts of incineration fly ash generated by municipal waste incineration into a 200 ml glass container (cylindrical shape with a diameter of 5 cm and a height of 10 cm), sealing it with a lid, and then in a 200 ° C circulating air dryer Heated for hours. After taking out from the dryer, 0.8 parts and 8 parts of water are added as (A1) or (X1) as the solid content of the heavy metal immobilizing agent instantly and kneaded quickly (about 30 seconds) with a spatula. . After covering again and adjusting the temperature in the dryer for 30 minutes, the concentrations of amine, carbon disulfide and hydrogen sulfide in the gas phase in the container immediately after removal were measured with gas detector tubes [amine, carbon disulfide and hydrogen sulfide are No. manufactured by Gastec Co., Ltd. 180L, No. 13 and no. 4LT]. In Example 2 and Comparative Example 2, neither amine nor hydrogen sulfide was detected. The results are shown in Table 1. From this result, it can be seen that the heavy metal fixing agent (A1) of the present invention does not generate harmful gas during the treatment.

(Dissolution test)
Concentration of lead ions eluted by conducting a dissolution test (Environment Agency Notification No. 13) on the treated fly ash and untreated fly ash after treatment in Example 2 and Comparative Example 2 (without adding a heavy metal fixing agent) Was measured by atomic absorption measurement. The results are shown in Table 1.
From this result, it can be seen that the heavy metal immobilizing agent (A1) of the present invention is superior in the effect of immobilizing heavy metals in incineration fly ash as compared with the conventional heavy metal immobilizing agent (X1).

  The heavy metal immobilizing agent of the present invention is excellent in safety and workability because it generates very little harmful gas during immobilization of heavy metal-containing materials, and also has high heat resistance, so it must be treated at high temperatures. It can be suitably used as a heavy metal fixing agent for incineration (flying) ash.

Claims (6)

A heavy metal immobilizing agent (A) for incineration (flying) ash comprising the cyclic compound (a) represented by the general formula (1).

[Wherein, R is a tetravalent hydrocarbon group having 4 to 14 or more carbon atoms having a ring structure; Q is —CR ¹ R ² —, —NR ³ —, —O—, —CO—, —S _m -, - SO- and -SO ₂ - 2 divalent group selected from the group consisting of a monovalent group selected from R ^1, R ² and R ³ is the group consisting of independently H or a hydrocarbon group; X and Z are each independently H or a hydrocarbon group, acyl group, amino group, amide group, thioamide group, cyano group, thiol group, hydroxyl group, carboxyl group, sulfo group, sulfuric acid group, phosphonic acid group, phosphoric acid group and A monovalent group selected from the group consisting of those metal bases; m represents an integer of 1 to 7, and n represents an integer of 3 to 8. ] X is a hydroxyl group, R is a benzene residue excluding four H atoms, Q is —S—, —SO— or —SO ₂ —, Z is a sulfo group or a metal base thereof, and n is an integer of 4 to 6. The heavy metal fixing agent according to claim 1. 2. (a) is one or more cyclic phenol sulfides selected from the group consisting of thiacalixarene, sulfinylated thiacalixarene, sulfonylated thiacalixarene, and metal sulfonates thereof. 2. The heavy metal fixing agent according to 2. Furthermore, the heavy metal fixing agent in any one of Claims 1-3 formed by using other heavy metal fixing agent (B) together. A heavy metal-containing incineration (flying) ash characterized in that the incineration (flying) ash containing heavy metal is stirred or kneaded with the heavy metal fixing agent according to any one of claims 1 to 4 and water as required. Method. The processing method according to claim 5, wherein the temperature of the incinerated (flying) ash is 80 to 300 ° C.