JP2005074281A - Toxic heavy metal trapping material and method for trapping toxic heavy metal - Google Patents
Toxic heavy metal trapping material and method for trapping toxic heavy metal Download PDFInfo
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本発明は、主に、水処理や廃液処理等において使用される有害重金属捕集材及び有害重金属の捕集方法に関する。本発明における部や％は特に規定しない限り質量基準で示す。 The present invention mainly relates to a hazardous heavy metal collecting material and a method for collecting harmful heavy metals used in water treatment, waste liquid treatment, and the like. Unless otherwise specified, parts and% in the present invention are shown on a mass basis.
環境問題が顕在化している。化学産業、電子産業、医療施設、及び各種研究施設等では多様な有害重金属が使用されており、これらの産業や施設から排出される汚水中の有害重金属、例えば、クロム、セレン、ヒ素、及びモリブデン等の有害重金属は、環境基本法に基づく環境基準が定められており、この基準値以下の水準を保つことが必要とされている。 Environmental problems are becoming apparent. Various hazardous heavy metals are used in the chemical industry, electronics industry, medical facilities, and various research facilities. Harmful heavy metals in sewage discharged from these industries and facilities, such as chromium, selenium, arsenic, and molybdenum Environmental standards based on the Basic Environmental Law have been established for toxic heavy metals such as these, and it is necessary to maintain a level below this standard value.
これらの有害重金属の中でも、クロム、セレン、ヒ素、及びモリブデンを含む化合物は毒性がきわめて高く、たとえ微量であっても公害病等、社会に甚大な被害をもたらす物質として広く認知されている。 Among these toxic heavy metals, compounds containing chromium, selenium, arsenic, and molybdenum are extremely toxic and are widely recognized as substances that cause great damage to society, such as pollution diseases, even in trace amounts.
このような有害重金属を捕集して低減する有害重金属捕集材として、CaO成分とAl2O3成分等を主体とする水和物の１種であるハイドロカルマイトを汚水中で生成させる方法や（特許文献１〜３等参照）、R2O成分、CaO成分及びAl2O3成分を含む重金属溶出低減材が知られている（特許文献４等参照）。 A method for generating hydrocalumite, one of hydrates mainly composed of CaO component and Al 2 O 3 component, in sewage as a hazardous heavy metal collector that collects and reduces such hazardous heavy metals. (Refer to Patent Documents 1 to 3 etc.), a heavy metal elution reducing material containing an R 2 O component, a CaO component and an Al 2 O 3 component is known (see Patent Document 4 etc.).
一方、R2O-CaO-Al2O3-SO4系の水和物（RはNaやK等のアルカリ金属）が知られている。RがNaであるNa2O-CaO-Al2O3-SO4系水和物がDoschらによって初めて報告された（非特許文献１等参照）。Doschらによれば、その組成は、0.5Na2O・4CaO・0.9Al2O3・1.1SO4・16H2Oと示された。Doschらはこの水和物をU相と名づけた。U相に関する最近の研究で、更に詳細な検討が加えられ、その組成は、0.5Na2O・3.9CaO・Al2O3・1.4SO4・13H2Oであるとされている（非特許文献２等参照）。Rがカリウム(K)であるK型のU相、すなわち、K2O-CaO-Al2O3-SO4系の水和物の存在も認められている（非特許文献３等参照）。 On the other hand, R 2 O—CaO—Al 2 O 3 —SO 4 hydrate (R is an alkali metal such as Na or K) is known. The Na 2 O—CaO—Al 2 O 3 —SO 4 hydrate, in which R is Na, was first reported by Dosch et al. (See Non-Patent Document 1, etc.). According to Dosch et al., The composition was shown as 0.5Na 2 O · 4CaO · 0.9Al 2 O 3 · 1.1SO 4 · 16H 2 O. Dosch et al. Named this hydrate U phase. A more detailed study was added in recent research on the U phase, and the composition is 0.5Na 2 O · 3.9CaO · Al 2 O 3 · 1.4SO 4 · 13H 2 O (non-patent literature) (See 2nd grade). The presence of a K-type U phase in which R is potassium (K), that is, a hydrate of the K 2 O—CaO—Al 2 O 3 —SO 4 system is also recognized (see Non-Patent Document 3, etc.).
本発明は有害重金属捕集材及びそれを用いた有害重金属の捕集方法を提供する。 The present invention provides a harmful heavy metal collecting material and a method for collecting harmful heavy metals using the same.
本発明は、R2O成分（Rはアルカリ金属）、CaO成分、Al2O3成分を含有する有害重金属捕集材及びそれを用いた有害重金属の捕集方法である。 The present invention is a harmful heavy metal collecting material containing an R 2 O component (R is an alkali metal), a CaO component, and an Al 2 O 3 component, and a method for collecting harmful heavy metals using the same.
本発明の有害重金属捕集材は、高濃度の有害重金属を含む溶液から、効率良く有害重金属を捕集することができ、また、捕集した有害重金属を再溶脱しにくく、固定化能力に優れる等の効果を奏する。 The hazardous heavy metal collecting material of the present invention can efficiently collect harmful heavy metals from a solution containing a high concentration of harmful heavy metals, and it is difficult to re-dissolve the collected hazardous heavy metals, and has excellent immobilization ability. There are effects such as.
本発明の有害重金属捕集材は、有害重金属であるCr,As,Se,Mo等の有害重金属を高濃度で含む溶液から、効率良く重金属を捕集すること等を特徴とするものである。有害重金属の種類及びその形態は特に限定されず、重クロム酸等の6価クロム、3価クロム、ヒ酸、亜ヒ酸、セレン酸、モリブデン酸等の有害重金属及びその形態が挙げられる。 The hazardous heavy metal collecting material of the present invention is characterized in that heavy metals are efficiently collected from a solution containing harmful heavy metals such as Cr, As, Se, and Mo, which are harmful heavy metals, at a high concentration. The type and form of the toxic heavy metal are not particularly limited, and examples thereof include toxic heavy metals such as hexavalent chromium such as dichromic acid, trivalent chromium, arsenic acid, arsenous acid, selenic acid, and molybdic acid, and forms thereof.
R2O成分、CaO成分、Al2O3成分を含有する有害重金属捕集材とは、R2O成分、CaO成分、Al2O3成分の3成分を含み、かつ、アルカリ金属の含有量が酸化物換算で30%以上であれば特に限定されるものではない。すなわち、CaOをC,Al2O3をA,R2OをR（Rはアルカリ金属、R=Li,Na,K等）と表記すると、例えば、
(a)R2O−CaO−Al2O3系物質を用いる。
(b)R2O成分を含む物質と、CaO成分を含む物質と、Al2O3成分を含む物質をそれぞれ別々の化合物として併用する。
(c)R2O成分とCaO成分を含む物質と、Al2O3成分を含む物質を併用する。
(d)カルシウムアルミネートやその水和物等、CaO成分とAl2O3成分の両方を含む物質と、R2O成分を含む物質
を併用する。
(e)アルミン酸のアルカリ金属塩等、R2O成分とAl2O3成分の両方を含む物質と、CaO成分を含む物質を併用する。
等の実施形態が挙げられる。
R 2 O component, CaO component, and harmful heavy metals trapping material containing Al 2 O 3 component comprises R 2 O component, CaO component, the three components of Al 2 O 3 component and the content of alkali metal If it is 30% or more in terms of oxide, there is no particular limitation. That is, when CaO is expressed as C, Al 2 O 3 as A, and R 2 O as R (R is an alkali metal, R = Li, Na, K, etc.), for example,
(a) R 2 O—CaO—Al 2 O 3 based material is used.
(b) A substance containing an R 2 O component, a substance containing a CaO component, and a substance containing an Al 2 O 3 component are used together as separate compounds.
(c) A substance containing an R 2 O component and a CaO component is used in combination with a substance containing an Al 2 O 3 component.
(d) A substance containing both a CaO component and an Al 2 O 3 component, such as calcium aluminate or a hydrate thereof, and a substance containing an R 2 O component are used in combination.
(e) A substance containing both an R 2 O component and an Al 2 O 3 component, such as an alkali metal salt of aluminate, and a substance containing a CaO component are used in combination.
And the like.
R2O成分、CaO成分、Al2O3成分を含有する化合物の具体例としては、CaO成分を含む物質として、例えば、生石灰CaO、消石灰Ca(OH)2、炭酸カルシウムCaCO3、塩化カルシウムCaCl2が挙げられ、Al2O3成分を含む物質としては、例えば、α型やγ型等の酸化アルミニウム、水酸化アルミニウム、アルミニウムゲル、オキシ水酸化アルミニウム等が挙げられ、R2O成分を含む物質としては、例えば、水酸化リチウムや水酸化ナトリウムや水酸化カリウム等の水酸化物、酸化リチウムや酸化ナトリウムや酸化カリウム等の酸化物、塩化物、炭酸塩、リン酸塩、ケイ酸塩、及び有機酸塩等が挙げられる。 Specific examples of the compound containing the R 2 O component, the CaO component, and the Al 2 O 3 component include, for example, quick lime CaO, slaked lime Ca (OH) 2 , calcium carbonate CaCO 3 , calcium chloride CaCl 2, and examples of materials containing Al 2 O 3 component comprising, for example, alpha-type and aluminum oxide γ-type, etc., aluminum hydroxide, aluminum gel, aluminum oxyhydroxide and the like, the R 2 O component Examples of substances include hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, oxides such as lithium oxide, sodium oxide, and potassium oxide, chlorides, carbonates, phosphates, silicates, And organic acid salts.
CaO成分とAl2O3成分の両方を含有する物質としてカルシウムアルミネート類やその水和物等が挙げられる。カルシウムアルミネート類とは、CaOとAl2O3を主体とする化合物を総称するものであり、特に限定されるものではない。その具体例としては、CaOをC,Al2O3をAと表記すると、CA2（CaO・2Al2O3）、CA(CaO・Al2O3）、C12A7（12CaO・7Al2O3）、C11A7・CaF2（11CaO・7Al2O3・CaF2）、C3A（3CaO・Al2O3）、3CaO・3Al2O3・CaSO4等の結晶性のものや、CaOとAl2O3を主体とする非晶質の化合物等が挙げられる。 Examples of the substance containing both the CaO component and the Al 2 O 3 component include calcium aluminates and hydrates thereof. Calcium aluminate is a general term for compounds mainly composed of CaO and Al 2 O 3 and is not particularly limited. For example, if CaO is C and Al 2 O 3 is A, CA 2 (CaO · 2Al 2 O 3 ), CA (CaO · Al 2 O 3 ), C 12 A 7 (12CaO · 7Al 2 O 3 ), C 11 A 7 · CaF 2 (11CaO · 7Al 2 O 3 · CaF 2 ), C 3 A (3CaO · Al 2 O 3 ), 3CaO · 3Al 2 O 3 · CaSO 4 And amorphous compounds mainly composed of CaO and Al 2 O 3 .
Al2O3成分とR2O成分の両方を含有する物質としてアルミン酸ナトリウムやアルミン酸カリウム等のアルミン酸アルカリ金属塩の含水塩や無水塩、リューサイト(K2O、Na2O)・Al2O3・SiO2等が挙げられる。CaO成分とAl2O3成分とR2O成分をすべて含有する物質として、カルシウムアルミネートのAl2O3又はCaOの一部をR2Oで置換した化合物やその水和物等が挙げられる。 Hydrous and anhydrous salts of alkali metal aluminates such as sodium aluminate and potassium aluminate, leucite (K 2 O, Na 2 O), as a substance containing both Al 2 O 3 component and R 2 O component Al 2 O 3 · SiO 2 and the like can be mentioned. As a substance containing all of CaO component and Al 2 O 3 component and R 2 O component include R 2 O compounds substituted with or hydrate thereof or the like part of the Al 2 O 3 or CaO of calcium aluminate .
CaO成分とAl2O3成分とR2O成分の3種類の成分を含有する化合物としては、C8A3R（8CaO・3Al2O3・R2O）、C14A5R（14CaO・5Al2O3・R2O）、C3A5R2(3CaO・5Al2O3・2R2O）等のR2O成分を含む結晶性のCaO-Al2O3-R2O系化合物や、CaO-Al2O3-R2O系の非晶質化合物等が挙げるられる。 Compounds containing three types of components, CaO, Al 2 O 3 and R 2 O, include C 8 A 3 R (8CaO · 3Al 2 O 3 · R 2 O), C 14 A 5 R (14CaO・ Crystalline CaO-Al 2 O 3 -R 2 O containing R 2 O component such as 5Al 2 O 3・ R 2 O), C 3 A 5 R 2 (3CaO ・ 5Al 2 O 3・ 2R 2 O) And a CaO—Al 2 O 3 —R 2 O amorphous compound.
R2Oの含有量は、有害重金属捕集材中、R2O換算で30〜70％であることが好ましく、35〜60％がより好ましい。本発明者らは、U相(R2O-CaO-Al2O3-SO4)の硫酸イオンをCr、As、Se、Mo等の有害重金属の酸化物イオンで置換したU相であるR2O-CaO-Al2O3-MOx系水和物（MはCr、As、Se、Mo等の有害重金属、xは正数、以下U*相という）の存在を見出したが、このようなU相が生成する条件下で、CaO成分とAl2O3成分とR2O成分の3種類の成分とCr、As、Se、Mo等の有害重金属を反応することにより、高濃度の有害重金属を効率良く捕集することが可能である。R2Oの含有量が30％未満や70％を超えるとU相及びU*相が生成しにくく、有害重金属捕集能力が低下する傾向にある。 The content of R 2 O during hazardous heavy metals trapping material is preferably 30 to 70% in the R 2 O conversion, more preferably 35% to 60%. The inventors of the present invention have prepared a R phase which is a U phase in which sulfate ions of the U phase (R 2 O—CaO—Al 2 O 3 —SO 4 ) are replaced with oxide ions of harmful heavy metals such as Cr, As, Se, and Mo. 2 O-CaO-Al 2 O 3 -MO x- based hydrates (M is a harmful heavy metal such as Cr, As, Se, Mo, etc., x is a positive number, hereinafter referred to as U * phase) By reacting three kinds of components, CaO, Al 2 O 3 and R 2 O, with harmful heavy metals such as Cr, As, Se and Mo It is possible to efficiently collect harmful heavy metals. When the content of R 2 O is less than 30% or exceeds 70%, the U phase and the U * phase are difficult to be generated, and the ability to collect toxic heavy metals tends to decrease.
本発明では、カルシウムアルミネート類とアルカリ金属化合物を含有する有害重金属捕集材や、水酸化カルシウム等のカルシウム塩とアルミン酸アルカリ金属塩を含有する有害重金属捕集材を用いることが、有害重金属捕集能力やその効果の迅速性の面から好ましい。 In the present invention, it is possible to use harmful heavy metal collectors containing calcium aluminates and alkali metal compounds, or harmful heavy metal collectors containing calcium salts such as calcium hydroxide and alkali metal aluminates. It is preferable from the viewpoint of collection ability and quickness of its effect.
本発明の有害重金属捕集材を工業的に得る場合、不純物が含まれることがあるが、その種類及び含有量は、本発明を阻害しない範囲内であれば特に制限されるものではない。その具体例としては、例えば、Fe2O3、SiO2、MgO、TiO2、S、P2O5、及びB2O3等が挙げられる。 When the harmful heavy metal collection material of the present invention is industrially obtained, impurities may be contained, but the type and content thereof are not particularly limited as long as they do not hinder the present invention. Specific examples thereof include Fe 2 O 3 , SiO 2 , MgO, TiO 2 , S, P 2 O 5 , and B 2 O 3 .
カルシウムアルミネート類に上記不純物が含まれる場合、化合物としては、4CaO・Al2O3・Fe2O3、6CaO・2Al2O3・Fe2O3、6CaO・Al2O3・2Fe2O3等のカルシウムアルミノフェライト、2CaO・Fe2O3やCaO・Fe2O3等のカルシウムフェライト、ゲーレナイト2CaO・Al2O3・SiO2やアノーサイトCaO・Al2O3・2SiO2等のカルシウムアルミノシリケート、メルビナイト3CaO・MgO・2SiO2やアケルマナイト2CaO・MgO・2SiO2やモンチセライトCaO・MgO・SiO2等のカルシウムマグネシウムシリケート、トライカルシウムシリケート3CaO・SiO2やダイカルシウムシリケート2CaO・SiO2やランキナイト3CaO・2SiO2やワラストナイトCaO・SiO2等のカルシウムシリケート等が混在する場合がある。これらの化合物は本発明の目的を実質的に阻害しない範囲であれば混在していてもよい。 When calcium aluminates contain the above impurities, the compounds include 4CaO · Al 2 O 3 · Fe 2 O 3 , 6CaO · 2Al 2 O 3 · Fe 2 O 3 , 6CaO · Al 2 O 3 · 2Fe 2 O calcium of 3 such as alumino-ferrite, calcium ferrite such as 2CaO · Fe 2 O 3 and CaO · Fe 2 O 3, gehlenite 2CaO · Al 2 O 3 · SiO 2 and anorthite CaO · Al 2 O 3 · 2SiO 2 calcium, etc. aluminosilicate, Merubinaito 3CaO · MgO · 2SiO 2 and Akerumanaito 2CaO · MgO · 2SiO 2 and Monte celite CaO · MgO · SiO 2 such as calcium magnesium silicate, tri-calcium silicate 3CaO · SiO 2 or dicalcium silicate 2CaO · SiO 2 and rankinite Calcium silicates such as knight 3CaO · 2SiO 2 and wollastonite CaO · SiO 2 may be mixed. These compounds may be mixed as long as the object of the present invention is not substantially inhibited.
本発明の有害重金属捕集材は、CaO／Al2O3のモル比が1〜6の範囲とすることが好ましく、2〜4がより好ましい。CaO／Al2O3のモル比が上記範囲外の場合は、有害重金属の捕集量が低下することがある。 The harmful heavy metal collecting material of the present invention preferably has a CaO / Al 2 O 3 molar ratio in the range of 1 to 6, more preferably 2 to 4. When the molar ratio of CaO / Al 2 O 3 is outside the above range, the amount of harmful heavy metals collected may decrease.
本発明では、モンモリロナイトやカオリナイト等に代表される層状化合物であるベントナイト類、クリノプチロライトやモルデナイトに代表されるゼオライト類、セピオライト、アパタイトやリン酸ジルコニウム等のリン酸塩、ハイドロタルサイト類、活性炭、多硫化物や硫化物やチオ硫酸塩類や亜硫酸塩類等のイオウ化合物、アマルガム、硫酸第一鉄や塩化第一鉄等の鉄化合物、セルロース類、ポリビニルアルコール、キトサン等の水溶性高分子類、ジアルキルジチオカルバミン酸類、キノリン化合物類、ポリアミン類、及び糖類等の公知の有害物質低減材料を１種又は２種以上を併用してもよい。 In the present invention, bentonites which are layered compounds represented by montmorillonite and kaolinite, zeolites represented by clinoptilolite and mordenite, phosphates such as sepiolite, apatite and zirconium phosphate, hydrotalcites , Activated carbon, sulfur compounds such as polysulfides, sulfides, thiosulfates and sulfites, amalgams, iron compounds such as ferrous sulfate and ferrous chloride, water-soluble polymers such as celluloses, polyvinyl alcohol and chitosan , Dialkyldithiocarbamic acids, quinoline compounds, polyamines, and known harmful substance reducing materials such as sugars may be used alone or in combination.
本発明に用いるCaO成分を含む化合物、Al2O3成分を含む化合物、R2O成分を含む化合物等の形態は特に限定されず、溶液状態、粉末、顆粒状、ペレット、カラム、及びフィルター等のいずれの形態であってもよい。また、液状や粉末状や顆粒状の物質を汚水中に投入し、固液分離してもよく、水和物のカラムやフィルターとして、汚水を通水させてもよい。 Forms such as a compound containing a CaO component, a compound containing an Al 2 O 3 component, a compound containing an R 2 O component, etc. used in the present invention are not particularly limited, and include a solution state, a powder, a granule, a pellet, a column, a filter, and the like Either form may be sufficient. Further, a liquid, powdery or granular substance may be put into sewage for solid-liquid separation, or sewage may be passed as a hydrate column or filter.
各種のカルシウムアルミネート類と水酸化ナトリウムを表１に示すような割合で配合して有害重金属捕集材を調製した。この有害重金属捕集材1.5ｇをCr濃度が1,000mg/リットルのクロム標準溶液250ccに入れて室温で７日間振とうし、液相中のクロム濃度をICPによって定量した。粉末Ｘ線回折法により水和生成物を同定した。結果を表１に併記した。 Various calcium aluminates and sodium hydroxide were blended in proportions as shown in Table 1 to prepare harmful heavy metal scavengers. 1.5 g of this hazardous heavy metal scavenger was placed in 250 cc of a chromium standard solution having a Cr concentration of 1,000 mg / liter and shaken at room temperature for 7 days, and the chromium concentration in the liquid phase was determined by ICP. The hydrated product was identified by powder X-ray diffraction. The results are also shown in Table 1.
＜使用材料＞
水酸化ナトリウム ：試薬１級。
カルシウムアルミネート類(1)：１モルの炭酸カルシウムと１モルの酸化アルミニウムを混合粉砕し、1,500℃で3時間焼成する工程を2回繰り返して合成した。CaO・Al2O3を主体、ブレーン比表面積5,000cm2/g。
カルシウムアルミネート類(2)：12モルの炭酸カルシウムと７モルの酸化アルミニウムを混合粉砕し、1,350℃で3時間焼成する工程を2回繰り返して合成した。結晶質の12CaO・7Al2O3を主体、ブレーン比表面積5,000cm2/g。
カルシウムアルミネート類(3)：非晶質の12CaO・7Al2O3にシリカを3%添加し、1,650℃で溶融した後、急冷して合成した。ブレーン比表面積5,000cm2/g。
カルシウムアルミネート類(4)：3モルの炭酸カルシウムと１モルの酸化アルミニウムを混合粉砕し、1,350℃で3時間焼成する工程を２回繰り返して合成した。3CaO・Al2O3を主体、ブレーン比表面積5,000cm2/g。
カルシウムアルミネート類(5)：8モルの炭酸カルシウムと3モルの酸化アルミニウムと１モルの炭酸ナトリウムを混合粉砕し、1,350℃で3時間焼成する工程を2回繰り返して合成した。8CaO・3Al2O3・Na2Oを主体、Na2O含有量7.5％、ブレーン比表面積5,000cm2/g。
クロム(Cr)標準溶液 ：クロム標準溶液、クロム濃度1,000mg/リットル溶液、関東化学製
<Materials used>
Sodium hydroxide: Reagent grade 1.
Calcium aluminate (1): A process of mixing and grinding 1 mol of calcium carbonate and 1 mol of aluminum oxide and firing at 1,500 ° C. for 3 hours was repeated twice. Mainly CaO · Al 2 O 3 with a brain specific surface area of 5,000 cm 2 / g.
Calcium aluminate (2): A process of mixing and grinding 12 moles of calcium carbonate and 7 moles of aluminum oxide and firing at 1,350 ° C. for 3 hours was synthesized twice. Mainly crystalline 12CaO · 7Al 2 O 3 with a Blaine specific surface area of 5,000 cm 2 / g.
Calcium aluminate (3): 3% of silica was added to amorphous 12CaO · 7Al 2 O 3 and melted at 1,650 ° C., and then rapidly cooled to synthesize. Blaine specific surface area 5,000cm 2 / g.
Calcium aluminate (4): A process of mixing and grinding 3 moles of calcium carbonate and 1 mole of aluminum oxide and firing at 1,350 ° C. for 3 hours was repeated twice. Mainly 3CaO · Al 2 O 3 with a specific surface area of 5,000 cm 2 / g in branes.
Calcium aluminates (5): A process of mixing and grinding 8 moles of calcium carbonate, 3 moles of aluminum oxide and 1 mole of sodium carbonate and firing at 1,350 ° C. for 3 hours was synthesized twice. Mainly 8CaO · 3Al 2 O 3 · Na 2 O, Na 2 O content 7.5%, Blaine specific surface area 5,000cm 2 / g.
Chromium (Cr) standard solution: Chromium standard solution, chromium concentration 1,000 mg / liter solution, manufactured by Kanto Chemical
＜測定方法＞
有害重金属の濃度：環境庁告示第46号に従って測定した。
<Measurement method>
Hazardous heavy metal concentration: Measured according to Environmental Agency Notification No. 46.
注：(1)U*相はU相の硫酸イオンが有害重金属の酸化物イオンに置換されたU相であることを示す。
(2) AFmはハイドロカルマイト族に該当する水和物。
Notes: (1) The U * phase indicates that the U phase sulfate ion is replaced by a toxic heavy metal oxide ion.
(2) AFm is a hydrate corresponding to the hydrocalumite family.
カルシウムアルミネート類(4)を使用し、C3A50部と水酸化アルカリROHをR2O換算で50部を配合して有害重金属捕集材を調製し、水酸化ナトリウムの代わりに、表２に示すアルカリ金属の水酸化物を用いたこと以外は実施例１と同様に行った。結果を表２に示す。 Using calcium aluminates (4), 50 parts of C 3 A and alkali hydroxide ROH are mixed with 50 parts of R 2 O to prepare hazardous heavy metal collectors. Table 2 instead of sodium hydroxide The same procedure as in Example 1 was conducted except that the alkali metal hydroxide shown in FIG. The results are shown in Table 2.
＜使用材料＞
水酸化カリウム：試薬１級
水酸化リチウム：試薬１級
<Materials used>
Potassium hydroxide: Reagent grade 1 Lithium hydroxide: Reagent grade 1
注：(1)U*相はU相の硫酸イオンが有害重金属の酸化物イオンに置換されたU相であることを示す。
Notes: (1) The U * phase indicates that the U phase sulfate ion is replaced by a toxic heavy metal oxide ion.
カルシウムアルミネート類(4)を使用し、カルシウムアルミネート類(4)50部と水酸化ナトリウムを、Na2O換算で50部を配合して有害重金属捕集材を調製し、クロム標準溶液の代わりに、表３に示す重金属の標準溶液を用いたこと以外は実施例１と同様に行った。結果を表３に示す。 Use calcium aluminate (4), mix 50 parts of calcium aluminate (4) and sodium hydroxide, 50 parts in terms of Na 2 O to prepare a hazardous heavy metal scavenger. Instead, it carried out like Example 1 except having used the standard solution of the heavy metal shown in Table 3. The results are shown in Table 3.
＜使用材料＞
ヒ素(As)標準溶液 ：試薬１級、ヒ素濃度1,000mg/リットル、pH=2.5。
セレン(Se)標準溶液 ：試薬１級、セレン濃度1,000mg/リットル、pH=2.4。
モリブデン(Mo)標準溶液：試薬１級、モリブデン濃度1,000mg/リットル、pH=2.4。
<Materials used>
Arsenic (As) standard solution: grade 1 reagent, arsenic concentration 1,000 mg / liter, pH = 2.5.
Selenium (Se) standard solution: reagent grade 1, selenium concentration 1,000 mg / liter, pH = 2.4.
Molybdenum (Mo) standard solution: reagent grade 1, molybdenum concentration 1,000 mg / liter, pH = 2.4.
注：(1)U*相（M）はU相の硫酸イオンが有害重金属（M）の酸化物イオンに置換されたU相であることを示す。
(2)NaOHの配合量は、Na2O換算の部
Note: (1) The U * phase (M) indicates that the U phase sulfate ion is replaced by an oxide ion of a toxic heavy metal (M).
(2) The amount of NaOH is part of Na 2 O conversion
CaO成分として水酸化カルシウムを使用し、Al2O3成分及びR2O成分を含有する化合物としてアルミン酸ナトリウムを用いた。水酸化カルシウムとアルミン酸ナトリウムの混合比をCaO/Al2O3モル比が表４に示した値となるようにした。更に水酸化ナトリウムを添加してNa2O換算で40部となるように有害重金属捕集材100部を調製した。この有害重金属捕集材2gを、クロム濃度が1,000mg/リットルのクロム標準溶液250ccに入れて7日間振とうし、液相中のクロム濃度をICPによって定量した。水和生成物を粉末Ｘ線回折法により同定した。結果を表４に併記した。 Calcium hydroxide was used as the CaO component, and sodium aluminate was used as the compound containing the Al 2 O 3 component and the R 2 O component. The mixing ratio of calcium hydroxide and sodium aluminate was such that the CaO / Al 2 O 3 molar ratio was the value shown in Table 4. Further, sodium hydroxide was added to prepare 100 parts of a harmful heavy metal scavenger so as to be 40 parts in terms of Na 2 O. 2 g of this hazardous heavy metal scavenger was placed in 250 cc of a chromium standard solution having a chromium concentration of 1,000 mg / liter and shaken for 7 days, and the chromium concentration in the liquid phase was quantified by ICP. The hydrated product was identified by powder X-ray diffraction. The results are also shown in Table 4.
＜使用材料＞
水酸化カルシウム ：試薬１級。
アルミン酸ナトリウム ：試薬１級、1.5Na2O・Al2O3・4.7H2O。
<Materials used>
Calcium hydroxide: Grade 1 reagent.
Sodium aluminate: reagent grade 1, 1.5Na 2 O · Al 2 O 3 · 4.7H 2 O.
注：(1)U*相はU相の硫酸イオンが有害重金属の酸化物イオンに置換されたU相であることを示す。
Notes: (1) The U * phase indicates that the U phase sulfate ion is replaced by a toxic heavy metal oxide ion.
本発明の有害重金属捕集材は、化学産業、電子産業、医療施設、及び各種研究施設等から廃棄される、クロム、セレン、ヒ素、フッ素、ホウ素、硝酸態窒素、及びリン等多くの有害重金属を、その種類によらず、迅速かつ効率良く捕集することができる等の効果を奏するため、多様な有害重金属を含有する処理水中に含まれる有害重金属捕集用途に適する。
The hazardous heavy metal collector of the present invention is a lot of harmful heavy metals such as chromium, selenium, arsenic, fluorine, boron, nitrate nitrogen, and phosphorus, which are discarded from the chemical industry, electronics industry, medical facilities, and various research facilities. Therefore, it is suitable for collecting harmful heavy metals contained in treated water containing various harmful heavy metals.
Claims (2)
R 2 O—CaO—Al 2 O 3 —MO x hydrate (M is Cr, As, Se, Mo, x is a positive number) is generated using the hazardous heavy metal scavenger according to claim 1. A method for collecting harmful heavy metals.
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