TWI597243B - Hazardous material handling materials and methods of their manufacture, handling of hazardous materials - Google Patents
Hazardous material handling materials and methods of their manufacture, handling of hazardous materials Download PDFInfo
- Publication number
- TWI597243B TWI597243B TW102139123A TW102139123A TWI597243B TW I597243 B TWI597243 B TW I597243B TW 102139123 A TW102139123 A TW 102139123A TW 102139123 A TW102139123 A TW 102139123A TW I597243 B TWI597243 B TW I597243B
- Authority
- TW
- Taiwan
- Prior art keywords
- harmful substance
- magnesium
- calcium silicate
- porous calcium
- treatment material
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/06—Inorganic material, e.g. asbestos fibres, glass beads or fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本發明係關於一種去除水中的砷、鎘、硒、鉻、銫、鋅、鉛等重金屬元素以及磷酸、氟等的有害物質的處理材料及其製造方法。 The present invention relates to a treatment material for removing heavy metal elements such as arsenic, cadmium, selenium, chromium, antimony, zinc, lead, and harmful substances such as phosphoric acid, fluorine, and the like, and a method for producing the same.
在水中添加熟石灰粉或泥漿是常用的去除水中有害物質的方法。該方法的藥劑成本低，有害物質的處理效果也較佳，但若水中含有大量的硫酸離子與鐵離子時，隨著pH值的升高，鐵離子會作為氫氧化鐵的膠體被析出，且熟石灰與硫酸離子會反應生成不溶性的石膏，與作為中和材料使用的熟石灰的未反應物一起，形成高含水且脫水性差的黏稠物而沉澱。該黏稠物是脫水性差，且含有有害物質的高含水性泥漿，為了處理這種泥漿，必須配備高價的固液分離設備、沉澱池、需要較多人手的壓濾機等黏稠物的脫水減量設備，並需要建設作為最後處理設施的黏稠物堆積用堤堰，處理費用的增加及對環境的影響成為了一個難題。且反應生成物的穩定性差，隨著時間流逝或氧化，氫氧化鐵上吸附的砷等重金屬物質有重新溶出的危險。 Adding slaked lime powder or mud to water is a common method of removing harmful substances from water. The method has low drug cost and good treatment effect of harmful substances, but if the water contains a large amount of sulfate ions and iron ions, the iron ions are precipitated as colloids of iron hydroxide as the pH value increases, and The slaked lime and the sulfate ion react to form insoluble gypsum, and together with the unreacted material of the slaked lime used as the neutralizing material, form a high-water-containing and poorly dehydrated viscous substance and precipitate. The viscous material is a high-water-containing mud which is poor in dehydration and contains harmful substances. In order to handle such a slurry, it is necessary to provide a high-priced solid-liquid separation device, a sedimentation tank, and a dewatering and reducing device for a viscous material such as a filter press that requires a large number of human hands. It is also necessary to construct a dike for the accumulation of viscous materials as the final treatment facility, and the increase in treatment costs and the impact on the environment have become a problem. Further, the stability of the reaction product is poor, and as time passes or oxidizes, heavy metal species such as arsenic adsorbed on the iron hydroxide may be re-dissolved.
為了降低成本並提高生成黏稠物的脫水性能，人們也嘗試使用碳酸鈣粉末和石灰石顆粒等作為中和材料，但其表面會被生成的石膏所覆蓋，阻礙中和反應的繼續，產生中和材料利用率低的問題。且碳酸鈣類的中和材料由於pH的上升效果小，有時候需要事先進行氧化處理。 In order to reduce the cost and improve the dewatering performance of the resulting viscous material, calcium carbonate powder and limestone granules have been tried as neutralizing materials, but the surface thereof is covered by the generated gypsum, hindering the continuation of the neutralization reaction, and producing a neutralizing material. Low utilization rate. Further, the calcium carbonate-based neutralizing material has a small effect of increasing the pH, and sometimes it is necessary to perform an oxidation treatment in advance.
相關的現有技術，在WO 02/79100號公報(專利文獻1)、日本 特開2003-112162號公報(專利文獻2)、日本特開2003-334526號公報(專利文獻3)、日本特開2008-188484號公報(專利文獻4)、日本特開2007-268409號公報(專利文獻5)、日本特開平9-299962號公報(專利文獻6)中有所揭露。 Related related art, in WO 02/79100 (Patent Document 1), Japan JP-A-2003-112162 (Patent Document 2), JP-A-2003-334526 (Patent Document 3), JP-A-2008-188484 (Patent Document 4), and JP-A-2007-268409 ( Patent Document 5) and JP-A-9-299962 (Patent Document 6) are disclosed.
其中，專利文獻1中公開的是使用石棉等礦物纖維與高爐水泥等無機黏合劑的顆粒狀固化物的酸性廢水處理材料。但專利文獻1中公開的材料僅僅適用於含有大量鐵離子的酸性廢水的處理，不適用於含有砷等有害物質的水的處理。 Among them, Patent Document 1 discloses an acidic wastewater treatment material using a particulate solidified product of an inorganic binder such as mineral fiber such as asbestos and blast furnace cement. However, the material disclosed in Patent Document 1 is only applicable to the treatment of acidic wastewater containing a large amount of iron ions, and is not suitable for the treatment of water containing harmful substances such as arsenic.
此外，市場上還有一種石棉等的礦物纖維的表面附著活性氫氧化鐵的廢水處理材料，它能夠吸附去除砷、鉛、鎘等重金屬離子。此外，還有一種使用以矽酸鈣水合物為主要成分的多孔處理材料，對含磷污水進行脫磷處理的方法，但這種方法不適用於含有砷等有害物質的水的處理。 In addition, there is a waste water treatment material on the surface of mineral fibers such as asbestos which adheres to active iron hydroxide, which can adsorb and remove heavy metal ions such as arsenic, lead and cadmium. Further, there is a method of dephosphorization treatment of phosphorus-containing sewage using a porous treatment material containing calcium citrate hydrate as a main component, but this method is not suitable for treatment of water containing harmful substances such as arsenic.
專利文獻2中揭露的方法是在含砷或重金屬的受污染土壤中添加化學合成的施氏礦物、針鐵礦、黃鉀鐵礬、水合氧化鐵中的任一種鐵化合物，結合砷或重金屬，使其不活動，從而淨化受污染土壤，或從含有砷或重金屬的受污染土壤中將砷或重金屬抽出，讓抽出液接觸上述鐵化合物，讓上述鐵化合物結合砷或重金屬，將其淨化。專利文獻3中揭露的方法是在受污染土壤中添加或混合氧化鎂，使受污染土壤固化，使污染物質不溶的方法。 The method disclosed in Patent Document 2 is to add a chemically synthesized iron compound of any of Shih's mineral, goethite, jarosite, and hydrated iron oxide to contaminated soil containing arsenic or heavy metals, in combination with arsenic or heavy metals. Inactivate it to purify contaminated soil, or extract arsenic or heavy metals from contaminated soil containing arsenic or heavy metals, let the extract contact the iron compound, and combine the iron compound with arsenic or heavy metal to purify it. The method disclosed in Patent Document 3 is a method in which magnesium oxide is added or mixed in a contaminated soil to solidify the contaminated soil to make the pollutant insoluble.
此外還有使用矽酸鈣作為有害物質處理材料的方法。專利文獻4中揭露的方法是在含氟廢水中添加矽酸鈣與磷酸原，使之生成氟磷灰石一二氧化矽複合材料，吸附固定氟，從而去除廢水中的氟的方法，但該方法不適用於去除重金屬的目的。專利文獻5中揭露的是讓含磷廢水接觸矽酸鈣水合物，從而去除磷的方法。專利文獻6中揭露的是在進行含鉛離子廢水處理時，將pH值調 整到5.6~12之間，再添加重量比為鉛的75倍以上的矽酸鈣，使鉛離子成為不溶物進行分離的方法。 There is also a method of using calcium citrate as a material for treating harmful substances. The method disclosed in Patent Document 4 is a method of adding calcium citrate and phosphoric acid to a fluorine-containing wastewater to form a fluoroapatite-cerium oxide composite material, adsorbing and fixing fluorine, thereby removing fluorine in the wastewater, but the method The method is not suitable for the purpose of removing heavy metals. Patent Document 5 discloses a method of removing phosphorus by contacting phosphorus-containing wastewater with calcium ruthenate hydrate. Patent Document 6 discloses that the pH is adjusted when the lead-containing ion wastewater is treated. Between 5.6 and 12, a calcium citrate having a weight ratio of more than 75 times that of lead is added, and the lead ion is insoluble as a method for separation.
鋁碳酸鎂代表性的分子式為Mg6Al2(OH)16CO3‧4H2O，是具有層狀的晶體結構。該鋁碳酸鎂具有陰離子交換性，可將陰離子嵌入。因此人們正在研究使用鋁碳酸鎂吸附去除有害物質的方法。例如正在試驗吸附去除硒、鉻等含氧陰離子與磷酸離子等。但存在的問題是，如果有共存的陰離子，這些含氧陰離子與磷酸離子的吸附量便會減少。另有報告顯示，陽離子的金屬離子也可以透過與鋁碳酸鎂中的金屬離子置換去除，或隨著pH值升高，部分金屬離子變成氫化物而被沉澱去除，但其去除能力不強。鋁碳酸鎂可以在Mg或Al等2價或3價金屬鹽的混合水溶液中添加鹼溶液共同沉澱後合成，但用這種方法合成的鋁碳酸鎂價格很高，不適合於用作廢水處理等。 A representative molecular formula of magnesium aluminum carbonate is Mg 6 Al 2 (OH) 16 CO 3 ‧4H 2 O, which has a layered crystal structure. The magnesium aluminum carbonate has an anion exchange property and can embed an anion. Therefore, methods for adsorbing and removing harmful substances using magnesium aluminum carbonate are being studied. For example, it is being tested to remove oxyanions such as selenium and chromium, and phosphate ions. However, there is a problem in that if there are coexisting anions, the adsorption amount of these oxyanions and phosphate ions is reduced. It has also been reported that cationic metal ions can also be removed by displacement with metal ions in magnesium aluminum carbonate, or as the pH increases, some of the metal ions become hydride and are precipitated and removed, but their removal ability is not strong. The aluminum magnesium carbonate can be synthesized by adding an alkali solution to a mixed aqueous solution of a divalent or trivalent metal salt such as Mg or Al, and the aluminum magnesium carbonate synthesized by this method is expensive, and is not suitable for use as a wastewater treatment.
如上所述，去除水中或土壤中的重金屬離子、磷與氟等的方法雖有很多，但效果令人滿意的很少，且價格很高。 As described above, although there are many methods for removing heavy metal ions, phosphorus, fluorine, and the like in water or soil, the effect is satisfactory and the price is high.
本發明的目的就在於提供能夠有效且無需維護去除水中的砷、鉛、鎘、硒、鉻、銫、鋅等重金屬類以及磷酸、氟等元素，吸附重金屬後的穩定性好，不會隨時間流逝或因氧化重新溶出有害物質，且無需大量後續處理的有害物質處理材料及其製造方法。 The object of the present invention is to provide effective and maintenance-free removal of heavy metals such as arsenic, lead, cadmium, selenium, chromium, antimony and zinc, as well as elements such as phosphoric acid and fluorine, and the stability after adsorption of heavy metals is not good with time. A hazardous substance treatment material that lapses or re-dissolves harmful substances due to oxidation, and does not require a large amount of subsequent treatment, and a method of manufacturing the same.
本發明提供的有害物質處理材料，是一種從含有重金屬離子的有害物質的水中吸附去除有害物質的處理材料，它是以在活性多孔矽酸鈣顆粒中，附著固定有鋁碳酸鎂為特徵的有害物質處理材料。 The harmful substance treatment material provided by the invention is a treatment material for adsorbing and removing harmful substances from water containing harmful substances of heavy metal ions, which is harmful in the case of adhering and fixing aluminum magnesium carbonate in the active porous calcium silicate particles. Material handling material.
較佳地，有害物質處理材料是一種將活性多孔矽酸鈣顆粒與選 自氧化鎂、氫氧化鎂、碳酸鎂以及鋁碳酸鎂的一種或兩種以上的鎂化合物在有水的情況下混合，透過水合反應後而得到為特徵的有害物質處理材料。 Preferably, the hazardous material treatment material is an active porous calcium silicate particle and an optional One or two or more kinds of magnesium compounds of magnesium oxide, magnesium hydroxide, magnesium carbonate, and aluminum magnesium carbonate are mixed in the presence of water, and a toxic reaction product is obtained by passing through a hydration reaction.
上述重金屬離子具有選自砷、鎘、硒、鉻、銫、鋅、鉛的一種或兩種以上的重金屬離子。此外，上述有害物質處理材料除了上述重金屬離子外，還能吸附去除含有選自磷酸、氟的離子的有害物質。 The heavy metal ions have one or two or more heavy metal ions selected from the group consisting of arsenic, cadmium, selenium, chromium, antimony, zinc, and lead. Further, in addition to the heavy metal ions described above, the harmful substance treating material can adsorb and remove harmful substances containing ions selected from phosphoric acid and fluorine.
較佳地，上述活性多孔矽酸鈣顆粒是以選自雪矽鈣石、硬矽鈣石以及鈣矽酸鹽水合物(CSH凝膠)的一種或兩種以上為主要成分。 Preferably, the above-mentioned active porous calcium silicate particles are mainly composed of one or two or more selected from the group consisting of slaked feldspar, hard ettringite, and calcium citrate hydrate (CSH gel).
較佳地，上述活性多孔矽酸鈣顆粒是在以矽酸質原料及石灰質原料為主要成分的泥漿中，添加作為發泡劑的金屬鋁粉末，在高壓釜中進行水熱反應而得到的水合物或成形物，其空隙率為50~90%。 Preferably, the activated porous calcium silicate particles are hydrated by adding a metal aluminum powder as a foaming agent to a slurry containing a phthalic acid raw material and a calcareous raw material as a main component in a hydrothermal reaction in an autoclave. The material or the molded article has a void ratio of 50 to 90%.
較佳地，上述活性多孔矽酸鈣顆粒的粒徑為0.05~10mm。 Preferably, the active porous calcium silicate particles have a particle diameter of 0.05 to 10 mm.
較佳地，上述鎂化合物，為其直徑比上述活性多孔矽酸鈣顆粒的粒徑小的粉體。 Preferably, the magnesium compound is a powder having a smaller particle diameter than the active porous calcium silicate particles.
較佳地，上述活性多孔矽酸鈣顆粒中的鎂化合物的附著固定量為100重量單位的活性多孔矽酸鈣顆粒對應10~150重量單位的鎂化合物。 Preferably, the magnesium compound in the activated porous calcium silicate particles is adhered and fixed in an amount of 100 parts by weight of the active porous calcium silicate particles corresponding to 10 to 150 parts by weight of the magnesium compound.
本發明還提供一種有害物質的處理方法，其特徵是讓上述有害物質處理材料接觸含有重金屬離子的有害物質的水。此外還提供一種有害物質的處理方法，其特徵是讓這種有害物質處理材料接觸可能會產生含有重金屬離子有害物質的水的土壤、岩石，進行配置或混合。 The present invention also provides a method for treating a harmful substance, which is characterized in that the harmful substance treating material is brought into contact with water containing a harmful substance of heavy metal ions. Further, a method for treating a harmful substance is provided, which is characterized in that the harmful substance treating material is brought into contact with soil or rock which may generate water containing a harmful substance of heavy metal ions, and is disposed or mixed.
另外，本發明還提供一種上述有害物質處理材料的製造方法，其特徵是，在活性多孔矽酸鈣顆粒與從氧化鎂、氫氧化鎂、碳酸鎂以及鋁碳酸鎂中選擇出的一種或兩種以上的鎂化合物粉末的混合物中，添加含有從硫酸鋁、氯化 鋁、硫酸鐵、氯化鐵、硫酸鎂、氯化鎂、硫酸鈣、氯化鈣中選擇出的一種或兩種以上的pH值調整劑及水分，在常壓和100℃以下使其進行水合反應，讓鎂化合物粉末附著固定在活性多孔矽酸鈣顆粒中。 In addition, the present invention also provides a method for producing the above-mentioned harmful substance treating material, characterized in that the active porous calcium silicate particles and one or two selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium carbonate and aluminum magnesium carbonate The above mixture of magnesium compound powders is added to contain aluminum sulfate, chlorinated One or more kinds of pH adjusters and water selected from aluminum, iron sulfate, ferric chloride, magnesium sulfate, magnesium chloride, calcium sulfate, and calcium chloride, and hydrated at normal pressure and below 100 ° C, The magnesium compound powder is attached and fixed to the active porous calcium silicate particles.
採用本發明的有害物質處理材料，便能夠有效地去除水中的砷、鎘、硒、鉛、銫、鋅等重金屬類以及磷酸、氟等物質，而且使用後仍可維持其透水性能，可長時間重複使用。 By using the harmful substance treatment material of the invention, heavy metals such as arsenic, cadmium, selenium, lead, antimony and zinc, as well as phosphoric acid, fluorine and the like can be effectively removed, and the water permeability can be maintained after use for a long time. reuse.
第1圖係表示有害物質處理材料表面層的結晶構造的顯微鏡照片。 Fig. 1 is a photomicrograph showing the crystal structure of the surface layer of the hazardous substance treatment material.
第2圖係表示有害物質處理材料表面層的結晶構造的顯微鏡放大照片。 Fig. 2 is a microscopic enlarged photograph showing the crystal structure of the surface layer of the harmful substance treating material.
本發明的有害物質處理材料，是在活性多孔矽酸鈣顆粒中附著固定選自氧化鎂、氫氧化鎂、碳酸鎂以及鋁碳酸鎂的一種或兩種以上鎂化合物而得來的。或者是將活性多孔矽酸鈣顆粒與鎂化合物在有水的環境下混合，使其產生水合反應而得來的。 The harmful substance treatment material of the present invention is obtained by adhering one or two or more kinds of magnesium compounds selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium carbonate, and aluminum magnesium carbonate to the activated porous calcium silicate particles. Alternatively, the activated porous calcium silicate particles and the magnesium compound are mixed in an aqueous environment to produce a hydration reaction.
活性多孔矽酸鈣顆粒是在以矽酸質原料及石灰質原料為主要成分的泥漿中，添加作為發泡劑的金屬鋁粉末，在高壓釜中進行水熱反應而得到的水合物或成形物，其空隙率為50~90%。此外還可使用粒狀高爐礦渣、雪矽鈣石、硬矽鈣石、CSH凝膠、以及輕量氣泡混凝土板、矽酸鈣板的碎片等。最好是含有以雪矽鈣石、硬矽鈣石或CSH凝膠為主要成分的東西。這裡所說的作為主要成分含有，是指其含量應達到50wt%以上，甚至最好是70wt%以上。 The active porous calcium silicate granule is a hydrate or a molded product obtained by hydrothermally reacting a metal aluminum powder as a foaming agent in a slurry containing a phthalic acid raw material and a calcareous raw material as a main component. The void ratio is 50 to 90%. In addition, granular blast furnace slag, slaked calcareous stone, hard calcareous stone, CSH gel, and lightweight concrete slabs, pieces of calcium silicate board, and the like can be used. It is best to contain something mainly composed of sillimanite, hard calcite or CSH gel. The term "containing as a main component" as used herein means that the content thereof should be 50% by weight or more, and even more preferably 70% by weight or more.
此外，作為建材使用的矽酸鈣板或輕量氣泡混凝土板在拆卸工程中會大量產生，如果能有效利用它們就更好了。建築物中使用的矽酸鈣板與輕量氣泡混凝土板的表面是非活性的，但將它們粉碎以後便會出現活性面，成為活性多孔質矽酸鈣。粉碎矽酸鈣板或輕量氣泡混凝土板時，應將其粉碎為數mm~10mm左右的顆粒狀。像矽酸鈣板或輕量氣泡混凝土板這樣的多孔質矽酸鈣容易加工成顆粒狀產品，且透水性與保水性好，適合形成顆粒。 In addition, calcium silicate plates or lightweight concrete slabs used as building materials are produced in large quantities in demolition work, and it is even better if they can be effectively utilized. The surface of the calcium silicate board and the lightweight blister concrete board used in the building are inactive, but after they are pulverized, the active surface appears to become the active porous calcium silicate. When crushing calcium silicate board or lightweight concrete slab, it should be pulverized into particles of several mm to 10 mm. Porous calcium citrate such as calcium citrate plate or lightweight concrete slab is easy to process into a granulated product, and has good water permeability and water retention, and is suitable for forming granules.
活性多孔質矽酸鈣顆粒只要具有吸附能力就可以，但如果是多孔質的，與酸的反應性較高就更好。與酸的反應性低的結晶質天然矽灰石由於鎂化合物吸附性差，難以大量附著固定。同樣，混凝土、灰漿、風冷式高爐渣、有色金屬渣、粉煤灰、混泥土碎塊等由於空隙率太低，活性不好，也不宜使用。 The active porous calcium citrate particles may have an adsorption ability, but if they are porous, the reactivity with an acid is higher. The crystalline natural limestone having low reactivity with acid has poor adsorption property of the magnesium compound and is difficult to adhere and fix in a large amount. Similarly, concrete, mortar, air-cooled blast furnace slag, non-ferrous metal slag, fly ash, concrete fragments, etc., due to low void ratio, poor activity, should not be used.
將煉鐵廠副產品高爐渣在熔融狀態下投入水中快速冷卻生成的粒狀高爐礦渣是具有活性的矽酸鈣材料，但其空隙率低，因此最好能與矽酸鈣板或輕量氣泡混凝土板等敲碎後得到的粉末混合使用。該情況下，混合比例最好是粒狀高爐礦渣20~80wt%。 The granulated blast furnace slag produced by rapidly cooling the blast furnace slag of the ironmaking plant by injecting into molten water is an active calcium silicate material, but its void ratio is low, so it is better to be combined with calcium silicate board or lightweight bubble concrete. The powder obtained after the board is broken or the like is mixed and used. In this case, the mixing ratio is preferably 20 to 80% by weight of the granulated blast furnace slag.
活性多孔質矽酸鈣顆粒的粒徑為0.05~10mm，0.1~7mm更佳，0.1~5mm最佳。粒徑越小則越有可能流出或堵塞裝置，太大則無法獲得足夠的鎂化合物附著固定量。上述粒徑為平均粒徑，最好是整體重量90%以上的顆粒位於上述範圍內。 The active porous calcium citrate particles have a particle size of 0.05 to 10 mm, preferably 0.1 to 7 mm, and most preferably 0.1 to 5 mm. The smaller the particle size, the more likely it is to flow out or block the device, and if it is too large, a sufficient amount of magnesium compound adhesion cannot be obtained. The above particle diameter is an average particle diameter, and it is preferable that particles having a total weight of 90% or more are in the above range.
附著固定於活性多孔矽酸鈣顆粒中的鎂化合物，有選自氧化鎂、氫氧化鎂、碳酸鎂、以及鋁碳酸鎂之的鎂化合物。此外，含有上述鎂化合物50wt%以上的黏土礦物類也適合作為鎂化合物。該鎂化合物成為有害物質處理材料的活性成分，將有害物質吸附去除。 The magnesium compound adhered and fixed to the active porous calcium silicate particles has a magnesium compound selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium carbonate, and magnesium aluminum carbonate. Further, clay minerals containing 50% by weight or more of the above magnesium compound are also suitable as the magnesium compound. The magnesium compound is an active component of a harmful substance treating material, and adsorbs and removes harmful substances.
為了讓鎂化合物附著固定於活性多孔矽酸鈣顆粒中，最好是採用粒徑比活性多孔矽酸鈣顆粒小的粉末，以粒徑為活性多孔矽酸鈣顆粒的1/10以下為佳。 In order to attach and immobilize the magnesium compound to the active porous calcium silicate particles, it is preferable to use a powder having a particle diameter smaller than that of the active porous calcium silicate particles, and it is preferable that the particle diameter is 1/10 or less of the active porous calcium silicate particles.
活性多孔矽酸鈣顆粒中的鎂化合物的附著固定量為，100重量單位的活性多孔矽酸鈣顆粒對應10~150重量單位的鎂化合物，最好為20~150重量單位的鎂化合物。 The amount of the magnesium compound adhered to the activated porous calcium silicate particles is such that 100 parts by weight of the active porous calcium silicate particles correspond to 10 to 150 parts by weight of the magnesium compound, preferably 20 to 150 parts by weight of the magnesium compound.
本發明的有害物質處理材料的製造方法，採用將上述活性多孔矽酸鈣顆粒與鎂化合物或其前驅物的粉末在有水存在的條件下進行混合的方法。本發明中所述的附著固定，包括活性多孔矽酸鈣顆粒與鎂化合物或其前驅物處於被混合的狀態。 The method for producing a harmful substance treatment material of the present invention comprises a method of mixing the above-mentioned active porous calcium niobate particles with a powder of a magnesium compound or a precursor thereof in the presence of water. The adhesion fixation described in the present invention includes a state in which the active porous calcium silicate particles and the magnesium compound or a precursor thereof are mixed.
作為一種較佳的技術方案，是一種在活性多孔矽酸鈣顆粒與鎂化合物粉末的混合物中，添加選自硫酸鋁、氯化鋁、硫酸鐵、氯化鐵、硫酸鎂、氯化鎂、硫酸鈣、或氯化鈣的pH調整劑與水之後進行混合，在常壓及100℃以下使其進行水合反應的方法。該水合反應為發熱反應，雖然在反應過程中會發熱，但通常最好保持在100℃以下。水的用量是，對於100重量單位的活性多孔矽酸鈣顆粒與鎂化合物粉末的混合物添加10~50重量單位的水，但若加入過多，有時會需要進行乾燥處理。在混合，進行水合反應後，根據需要進行乾燥、成形、粉碎、劃分等之後，製成有害物質處理材料。 As a preferred technical solution, a mixture of activated porous calcium silicate particles and magnesium compound powder is selected from the group consisting of aluminum sulfate, aluminum chloride, iron sulfate, ferric chloride, magnesium sulfate, magnesium chloride, calcium sulfate, Or a method in which a pH adjuster of calcium chloride is mixed with water and then subjected to a hydration reaction at normal pressure and at 100 ° C or lower. The hydration reaction is an exothermic reaction, and although it generates heat during the reaction, it is usually preferably kept below 100 °C. The amount of water used is 10 to 50 parts by weight of water added to a mixture of 100 parts by weight of the active porous calcium silicate particles and the magnesium compound powder, but if it is added too much, it may be required to be dried. After mixing, the hydration reaction is carried out, and if necessary, drying, molding, pulverization, division, and the like are carried out to prepare a harmful substance treatment material.
讓活性多孔矽酸鈣顆粒與氧化鎂、氫氧化鎂、碳酸鎂等鹼性鎂化合物在pH值調整劑與水存在的條件下發生水合反應後，部分生成像鋁碳酸鎂一樣的層狀鎂化合物。然後隨著時間的流逝，像鋁碳酸鎂一樣的結晶礦物就不斷生長。在製造、使用本發明的有害物質處理材料期間，像鋁碳酸鎂一樣的層狀鎂化 合物充分生長，這對有害物質的處理能產生有效作用。 The active porous calcium citrate particles are hydrated with a basic magnesium compound such as magnesium oxide, magnesium hydroxide or magnesium carbonate in the presence of a pH adjuster and water, and a layered magnesium compound such as magnesium aluminocarbonate is partially formed. . Then, as time goes by, crystalline minerals like magnesium aluminum carbonate continue to grow. Layered magnesiumation like aluminum magnesium carbonate during the manufacture and use of the hazardous materials treatment material of the present invention The compound grows sufficiently, which can have an effective effect on the treatment of harmful substances.
使用本發明的有害物質處理材料進行有害物質處理的方法是讓有害物質處理材料接觸含有被看成有害物質的重金屬離子的水。此時，有害物質處理材料會吸附去除水中含有的重金屬離子。接觸方法是，讓含有有害物質的水透過或滯留於填充了有害物質處理材料的容器或水槽中。 The method of treating a harmful substance using the harmful substance treating material of the present invention is to bring the harmful substance treating material into contact with water containing a heavy metal ion regarded as a harmful substance. At this time, the hazardous substance treatment material adsorbs and removes heavy metal ions contained in the water. The contact method is such that water containing harmful substances is permeated or retained in a container or a sink filled with the hazardous substance treatment material.
作為其它的有害物質的處理方法，還可以讓其接觸有可能產生含有重金屬離子有害物質的水的土壤或岩石。讓其接觸土壤時，可以讓其分散混合在土壤中，也可重點將其配置在下游端的土壤周邊。讓其接觸土壤或岩石時，僅放入有害物質處理材料是沒有效果的，要等雨水等將土壤或岩石淋濕後，土壤或岩石中含有的重金屬離子等有害物質含在水中，該水與有害物質處理材料接觸，才能將重金屬離子吸附去除。 As a treatment method for other harmful substances, it is also possible to contact soil or rock which is likely to generate water containing harmful substances of heavy metal ions. When it is exposed to the soil, it can be dispersed and mixed in the soil, or it can be placed in the vicinity of the soil at the downstream end. When it is exposed to soil or rock, it is ineffective to place only the hazardous material treatment material. After the soil or rock is wetted by rain, the harmful substances such as heavy metal ions contained in the soil or rock are contained in the water. The contact of hazardous materials with the material can remove the heavy metal ions.
用本發明的有害物質處理材料能夠去除的有害物質為重金屬離子，尤其是去除砷、鎘、硒、鉻、銫、鋅、鉛等的能力極佳。此外，除上述重金屬離子外，還具有優異的吸附去除磷酸及氟等有害物質的能力，因此也可作為磷酸或氟離子等的有害物質處理材料使用。 The harmful substances which can be removed by the harmful substance treatment material of the present invention are heavy metal ions, and in particular, the ability to remove arsenic, cadmium, selenium, chromium, antimony, zinc, lead, etc. is excellent. Further, in addition to the above-mentioned heavy metal ions, it has excellent ability to adsorb and remove harmful substances such as phosphoric acid and fluorine, and therefore can be used as a harmful substance treatment material such as phosphoric acid or fluoride ion.
本發明的有害物質處理材料，其活性多孔質矽酸鈣與其表面的鎂化合物或由它們生成的層狀鎂化合物具有出色的吸附重金屬且不溶的能力。因此，將其與含有污染物質的土壤混合，便能吸收污染物質且不溶，吸附且不溶之後，可保持結晶結構，從而防止重金屬的再次溶出，保持穩定。因此，既能應對砷、鉛、鎘、銫、鋅等多種污染物質，也可應對與金屬鐵粉等具有還原性的輔助材料複合形成的6價硒等難淨化物質。由於其具有pH緩衝能力，不容易受到土壤pH值等的影響，與原有的氧化鎂類的單獨的不溶性材料相比，能夠迅速、 切實且穩定地進行重金屬的處理。 The harmful substance treating material of the present invention has an active porous calcium citrate and a magnesium compound on its surface or a layered magnesium compound formed therefrom, which has an excellent ability to adsorb heavy metals and be insoluble. Therefore, by mixing it with soil containing contaminants, it can absorb pollutants and be insoluble, and after adsorption and insolubility, the crystal structure can be maintained, thereby preventing re-dissolution of heavy metals and maintaining stability. Therefore, it can cope with various pollutants such as arsenic, lead, cadmium, antimony, and zinc, and can also deal with difficult-to-purify substances such as hexavalent selenium formed by recombination with a reducing auxiliary material such as metal iron powder. Because of its pH buffering capacity, it is not easily affected by soil pH and the like, and can be quickly and compared with the original insoluble materials of the original magnesium oxide. The treatment of heavy metals is carried out reliably and steadily.
這種效果是在有害物質處理材料中的鋁碳酸鎂等層狀鎂化合物與活性多孔質矽酸鈣的複合作用下，鉛、鎘、銫、鋅等與處理材料中的陽離子置換，砷、硒、氟等與處理材料中的陰離子置換，與受污染土壤相互反應，從而改善土壤的化學性溶出特性而得到的。 This effect is a combination of a layered magnesium compound such as aluminum magnesium carbonate and an active porous calcium citrate in a hazardous material treatment material, and cation replacement in the treatment material such as lead, cadmium, antimony, zinc, etc., arsenic, selenium And fluorine and the like are replaced with anions in the treatment material, and react with the contaminated soil to improve the chemical dissolution characteristics of the soil.
以下就本發明對含有有害物質的廢水進行處理的有害物質處理材料(以下稱“處理材料”)與其製造方法進行詳細說明。 Hereinafter, the hazardous substance treatment material (hereinafter referred to as "treatment material") for treating waste water containing harmful substances according to the present invention and a method for producing the same will be described in detail.
活性多孔矽酸鈣顆粒，使用將市面銷售的輕量氣泡混凝土板(Clion株式會社製造，SiO2：49.5%、CaO：35.3%、Al2O3：4.4%、Fe2O3：2.6%。SiO2/CaO比=1.4)乾燥、粉碎後，調整成粒徑1.2mm以下、0.1mm以上的矽酸鈣顆粒。此外，鎂原料使用市面銷售的輕質煅燒氧化鎂(宇部Material株式會社製造)，pH調整劑使用市面銷售的硫酸鋁粉末(商品名稱：硫酸鋁)。 For the active porous calcium silicate particles, a commercially available lightweight bubble concrete slab (manufactured by Clion Co., Ltd., SiO 2 : 49.5%, CaO: 35.3%, Al 2 O 3 : 4.4%, Fe 2 O 3 : 2.6%) was used. After drying and pulverization, the SiO 2 /CaO ratio = 1.4) was adjusted to a calcium citrate particle having a particle diameter of 1.2 mm or less and 0.1 mm or more. In addition, the commercially available magnesium calcined magnesia (manufactured by Ube Material Co., Ltd.) and the commercially available aluminum sulfate powder (trade name: aluminum sulfate) were used as the pH adjuster.
用混合攪拌機，將40重量單位的矽酸鈣顆粒、30重量單位的輕質煅燒氧化鎂、10重量單位的硫酸鋁與8重量單位的水在室溫下攪拌混合5分鐘後，放入密閉容器中靜置12小時，使其進行水合反應，得到平均粒徑0.3mm(0.1~2.0mm的99wt%)、容積比0.80的粉粒狀反應物(處理材料1)。 40 parts by weight of calcium citrate particles, 30 parts by weight of light calcined magnesia, 10 parts by weight of aluminum sulfate and 8 parts by weight of water were stirred and mixed at room temperature for 5 minutes in a mixing mixer, and then placed in a closed container. After standing for 12 hours, it was subjected to a hydration reaction to obtain a powdery granular reactant (treated material 1) having an average particle diameter of 0.3 mm (99 wt% of 0.1 to 2.0 mm) and a volume ratio of 0.80.
該粉粒狀反應物的化學組成為SiO2：14.5%、Al2O3：1.4%、CaO：11.9%、MgO：52.9%、Fe2O3：1.4%、SO3：7.4%、水分：10.0%。此外，將該顆粒狀反應物微粉碎後，用X射線粉末分析裝置分析後，發現了反映有氫氧化鎂、二水石膏、矽酸鈣水合物、二氧化矽等存在的峰值(peak)。 The chemical composition of the powdery granular reactant is SiO 2 : 14.5%, Al 2 O 3 : 1.4%, CaO: 11.9%, MgO: 52.9%, Fe 2 O 3 : 1.4%, SO 3 : 7.4%, moisture: 10.0%. Further, the particulate reactant was finely pulverized, and after analysis by an X-ray powder analyzer, it was found that peaks reflected by magnesium hydroxide, dihydrate gypsum, calcium citrate hydrate, cerium oxide, and the like were observed.
第1圖與第2圖為處理材料1保存1個月後的顯微鏡照片。第 1圖為表面層，以鋁碳酸鎂為主的層狀鎂化合物的結晶幾乎覆蓋了整個面，可以看到結晶的生長。第2圖為放大照片，是露出的活性多孔質矽酸鈣的結晶。且在製造出處理材料1之後，由於鋁碳酸鎂剛生成，結晶度尚低，尚不會出現明顯的峰值。但每個實施例均在數日後出現了明顯的峰值。 Fig. 1 and Fig. 2 are micrographs of the treated material 1 after storage for one month. First 1 is a surface layer, and the crystal of the layered magnesium compound mainly composed of magnesium aluminum carbonate covers almost the entire surface, and crystal growth can be seen. Fig. 2 is an enlarged photograph showing the crystal of the exposed porous calcium silicate. And after the treatment material 1 was produced, since the aluminum magnesium carbonate was newly formed, the crystallinity was still low, and no significant peak appeared. However, each of the examples showed a significant peak after several days.
使用與實施例1相同的矽酸鈣顆粒、鎂原料、硫酸鋁，用混合攪拌機將10重量單位的矽酸鈣顆粒、3重量單位的輕質煅燒氧化鎂、1重量單位的硫酸鋁與2重量單位的水在室溫下攪拌混合5分鐘後，放入密閉容器中靜置12小時，使其進行水合反應，得到平均粒徑0.3mm、容積比0.76的粉粒狀反應物(處理材料2)。該粉粒狀反應物的化學組成為SiO2：21.3%、Al2O3：2.4%、CaO：16.5%、MgO：35.8%、Fe2O3：1.6%、SO3：7.5%、水分：14.3%。此外，將該粉粒狀反應物微粉碎後，用X射線粉末分析裝置分析後，發現了反應有氧化鎂、氫氧化鎂、二水石膏、矽酸鈣水合物、二氧化矽等存在的峰值。 Using the same calcium citrate particles, magnesium raw material, aluminum sulfate as in Example 1, 10 parts by weight of calcium silicate particles, 3 parts by weight of light calcined magnesia, 1 part by weight of aluminum sulfate and 2 parts by weight using a mixing mixer The unit of water was stirred and mixed at room temperature for 5 minutes, and then left to stand in a closed container for 12 hours to carry out a hydration reaction to obtain a powdery granular reactant having an average particle diameter of 0.3 mm and a volume ratio of 0.76 (treatment material 2). . The chemical composition of the powdery granular reactant is SiO 2 : 21.3%, Al 2 O 3 : 2.4%, CaO: 16.5%, MgO: 35.8%, Fe 2 O 3 : 1.6%, SO 3 : 7.5%, moisture: 14.3%. Further, the powdery reactant was finely pulverized, and after analysis by an X-ray powder analyzer, it was found that there were peaks in the reaction such as magnesium oxide, magnesium hydroxide, dihydrate gypsum, calcium citrate hydrate, and cerium oxide. .
使用與實施例1相同的，將市面銷售的輕量氣泡混凝土板粉碎後調整為粒徑4.0~1.2mm的矽酸鈣顆粒。並使用與實施例1中相同的鎂原料和硫酸鋁。 Using the same as in Example 1, the commercially available lightweight bubble concrete slab was pulverized and adjusted to a calcium citrate particle having a particle diameter of 4.0 to 1.2 mm. The same magnesium raw material and aluminum sulfate as in Example 1 were used.
用混合攪拌機，將4重量單位的多孔質矽酸鈣、3重量單位的輕質煅燒氧化鎂、1重量單位的硫酸鋁與3重量單位的水在室溫下攪拌混合2分鐘後，放入密閉容器中靜置12小時，使其進行水合反應，得到平均粒徑4mm、容積比0.91的粒狀反應物(處理材料3)。該粒狀反應物的化學組成為SiO2：20.4%、Al2O3：5.1%、CaO：16.0%、MgO：39.6%、Fe2O3：1.8%、SO3：16.7%、 水分：25.2%。此外，將該顆粒狀反應物微粉碎後，用X射線粉末分析裝置分析後，發現了反映有氫氧化鎂、二水石膏、矽酸鈣水合物、二氧化矽等存在的峰值。 4 parts by weight of porous calcium citrate, 3 parts by weight of light calcined magnesia, 1 part by weight of aluminum sulfate and 3 parts by weight of water were stirred and mixed at room temperature for 2 minutes in a mixing mixer, and then placed in a sealed state. The container was allowed to stand for 12 hours, and subjected to a hydration reaction to obtain a particulate reactant (treated material 3) having an average particle diameter of 4 mm and a volume ratio of 0.91. The chemical composition of the granular reactant was SiO 2 : 20.4%, Al 2 O 3 : 5.1%, CaO: 16.0%, MgO: 39.6%, Fe 2 O 3 : 1.8%, SO 3 : 16.7%, moisture: 25.2 %. Further, the particulate reactant was finely pulverized, and after analysis by an X-ray powder analyzer, it was found that peaks reflected by magnesium hydroxide, dihydrate gypsum, calcium citrate hydrate, cerium oxide, and the like were observed.
使用與實施例3相同的矽酸鈣顆粒和鎂原料，用混合攪拌機，將10重量單位的多孔質矽酸鈣、3重量單位的輕質煅燒氧化鎂、1重量單位的硫酸鋁與3重量單位的水在室溫下攪拌混合2分鐘後，放入密閉容器中靜置12小時，使其進行水合反應，得到平均粒徑4mm、容積比0.82的粒狀反應物(處理材料4)。該粒狀反應物的化學組成為SiO2：26.8%、Al2O3：4.9%、CaO：21.8%、MgO：28.0%、Fe2O3：2.1%、SO3：15.7%、水分：27.9%。此外，將該粒狀反應物微粉碎後，用X射線粉末分析裝置分析後，發現了反映有氧化鎂、氫氧化鎂、二水石膏、矽酸鈣水合物、二氧化矽等存在的峰值。 Using the same calcium citrate particles and magnesium raw material as in Example 3, 10 parts by weight of porous calcium citrate, 3 parts by weight of light calcined magnesia, 1 part by weight of aluminum sulfate and 3 parts by weight were mixed with a mixer. The water was stirred and mixed at room temperature for 2 minutes, and then left to stand in a closed container for 12 hours to carry out a hydration reaction to obtain a particulate reactant (treated material 4) having an average particle diameter of 4 mm and a volume ratio of 0.82. The chemical composition of the granular reactant was SiO 2 : 26.8%, Al 2 O 3 : 4.9%, CaO: 21.8%, MgO: 28.0%, Fe 2 O 3 : 2.1%, SO 3 : 15.7%, moisture: 27.9. %. Further, the particulate reaction product was finely pulverized, and after analysis by an X-ray powder analyzer, it was found that peaks reflected by magnesium oxide, magnesium hydroxide, dihydrate gypsum, calcium citrate hydrate, cerium oxide, and the like were observed.
在100ml含有用表1所示市面銷售的特級試劑調製的各種重金屬的水溶液中，添加實施例1~4中獲得的處理材料1~4各1g，將該試驗液體倒入500ml的聚乙烯容器中，在常溫中振動24小時。振動後進行離心分離，用1μm玻璃杯過濾器吸引清液過濾。然後取30ml濾液，添加5ml的HNO3，微波分解後，用超純水定容成50ml。從中取走10ml的分解液後，再在剩餘的分解液中加超純水定容成50ml，然後用ICP-MS測定。表2顯示的是從此時的濾液中的重金屬濃度中求得的去除率。 1 ml of each of the treatment materials 1 to 4 obtained in Examples 1 to 4 was added to 100 ml of an aqueous solution containing various heavy metals prepared by using a special grade agent sold in the market shown in Table 1, and the test liquid was poured into a 500 ml polyethylene container. , vibrate at room temperature for 24 hours. After shaking, the mixture was centrifuged, and the supernatant was filtered with a 1 μm glass filter. Then, 30 ml of the filtrate was taken, 5 ml of HNO 3 was added , and after microwave decomposition, it was made up to 50 ml with ultrapure water. After removing 10 ml of the decomposing solution, the remaining decomposing liquid was added with ultrapure water to a volume of 50 ml, which was then measured by ICP-MS. Table 2 shows the removal rate obtained from the concentration of heavy metals in the filtrate at this time.
調製重金屬溶液使用的試劑 Modulating reagents for heavy metal solutions
‧As溶液：砷酸鈉+亞砷酸鈉(摩爾比：1：1) ‧As solution: sodium arsenate + sodium arsenite (molar ratio: 1:1)
‧Pb溶液：醋酸鉛 ‧Pb solution: lead acetate
‧F溶液：氟化鈉 ‧F solution: sodium fluoride
‧Se溶液：亞硒酸鈉+硒酸鈉(摩爾比：1：1) ‧Se solution: sodium selenite + sodium selenate (molar ratio: 1:1)
‧Cd溶液：硫酸鎘 ‧Cd solution: cadmium sulfate
在含有使用市面銷售的氯化銫特級試劑調製的銫210mg/L的水溶液200ml中，添加實施例1與2中獲得的處理材料1、處理材料2各0.5g，將該試驗液體倒入500ml的聚乙烯容器中，在常溫中振動24小時。振動後進行離心分離，用1μm玻璃杯過濾器吸引清液過濾。用原子吸光分析設備測定濾液。從此時的濾液中的濃度求取銫的吸附能力。吸附能力用每1g處理材料的Cs原子換算的吸附量(mg)來表示，處理材料1為8mg/g，處理材料2為6mg/g。 To 200 ml of an aqueous solution of ruthenium 210 mg/L prepared by using a commercially available ruthenium chloride-based special reagent, 0.5 g of each of the treatment material 1 and the treatment material 2 obtained in Examples 1 and 2 was added, and the test liquid was poured into 500 ml. In a polyethylene container, it was shaken at room temperature for 24 hours. After shaking, the mixture was centrifuged, and the supernatant was filtered with a 1 μm glass filter. The filtrate was measured by an atomic absorption spectrometer. From the concentration in the filtrate at this time, the adsorption capacity of hydrazine was determined. The adsorption capacity is expressed by the amount of adsorption (mg) per Cg atom of the treated material, and the treatment material 1 is 8 mg/g, and the treatment material 2 is 6 mg/g.
在酸性的鋅處理液100ml中，添加實施例2與3中獲得的處理材料2、處理材料3各1g，將該試驗液體倒入300ml的聚乙烯容器中，在常溫中振動24小時。振動後進行離心分離，用1μm玻璃杯過濾器吸引清液過濾。用ICP-AES分析設備測定濾液。從此時的濾液中的濃度求取鋅的去除率。鋅的去除率為，處理材料2是95%，處理材料3是98%。且處理前的鋅處理廢液水質的鋅濃度為：730mg/L、pH：3.8。 To 100 ml of the acidic zinc treatment liquid, 1 g of each of the treatment material 2 and the treatment material 3 obtained in Examples 2 and 3 was added, and the test liquid was poured into a 300 ml polyethylene container and shaken at room temperature for 24 hours. After shaking, the mixture was centrifuged, and the supernatant was filtered with a 1 μm glass filter. The filtrate was measured using an ICP-AES analytical apparatus. The removal rate of zinc was determined from the concentration in the filtrate at this time. The removal rate of zinc was 95% for treated material 2 and 98% for treated material 3. The zinc concentration of the zinc treated waste liquid before the treatment was 730 mg/L and pH: 3.8.
在10g土壤中加入400ml純水，振動24小時後進行離心分離與過濾，獲得土壤浸出水。在該液體中添加市面銷售的醋酸(特級試劑)和重金屬原子吸光分析用標準液，製作pH4.3、重金屬濃度為As：0.3mg/L、Se：0.3mg/L、Cd：0.2mg/L、Pb：1.5mg/L的人工廢水。將100ml該試驗液體放入聚乙烯容器中，添加實施例3與4中獲得的處理材料3與4各5g，振動24小時。振動後進行離心分離，用1μm玻璃杯過濾器吸引清液過濾。然後取30ml濾液，添加5ml的HNO3，微波分解後，用超純水定容成50ml。從中取走10ml的分解液後，再在剩餘的分解液中加超純水定容成50ml，然後用ICP-MS測定。表2顯示的是從此時濾液中的重金屬濃度中求得的去除率(%)。 400 ml of pure water was added to 10 g of soil, and after shaking for 24 hours, centrifugation and filtration were carried out to obtain soil leaching water. A commercially available acetic acid (special grade reagent) and a standard liquid for heavy metal atomic absorption analysis were added to the liquid to prepare a pH 4.3, a heavy metal concentration of As: 0.3 mg/L, Se: 0.3 mg/L, and Cd: 0.2 mg/L. , Pb: 1.5mg / L of artificial wastewater. 100 ml of this test liquid was placed in a polyethylene container, and 5 g of each of the treatment materials 3 and 4 obtained in Examples 3 and 4 was added, and shaken for 24 hours. After shaking, the mixture was centrifuged, and the supernatant was filtered with a 1 μm glass filter. Then, 30 ml of the filtrate was taken, 5 ml of HNO 3 was added , and after microwave decomposition, it was made up to 50 ml with ultrapure water. After removing 10 ml of the decomposing solution, the remaining decomposing liquid was added with ultrapure water to a volume of 50 ml, which was then measured by ICP-MS. Table 2 shows the removal rate (%) obtained from the concentration of heavy metals in the filtrate at this time.
在1kg重金屬汚染土壤中加入10L純水，振動24小時後進行離心分離與過濾，獲得土壤浸出水。該土壤浸出水的重金屬濃度為As：0.19mg/L、Se：0.03mg/L。將1L該試驗液體放入聚乙烯容器中，添加1g實施例1中獲得的處理材料1，振動24小時。振動後進行離心分離，用1μm玻璃杯過濾器吸引清液過濾。然後取30ml濾液，添加5ml的HNO3，微波分解後，用超純水定容成50ml。取出10ml的分解液，定容成50ml後，用ICP-MS測定。此時濾液中的重金屬濃度為As：小於0.001mg/L、Se：0.009mg/L。 10 L of pure water was added to 1 kg of heavy metal contaminated soil, and after shaking for 24 hours, centrifugation and filtration were carried out to obtain soil leaching water. The concentration of heavy metals in the soil leaching water was As: 0.19 mg/L and Se: 0.03 mg/L. 1 L of this test liquid was placed in a polyethylene container, and 1 g of the treatment material 1 obtained in Example 1 was added and shaken for 24 hours. After shaking, the mixture was centrifuged, and the supernatant was filtered with a 1 μm glass filter. Then, 30 ml of the filtrate was taken, 5 ml of HNO 3 was added , and after microwave decomposition, it was made up to 50 ml with ultrapure water. 10 ml of the decomposing solution was taken out and made up to 50 ml, and then measured by ICP-MS. At this time, the concentration of heavy metals in the filtrate was As: less than 0.001 mg/L, and Se: 0.009 mg/L.
在1kg重金屬汚染土壤中加入10L純水，振動24小時後進行離心分離與過濾，獲得土壤浸出水。該土壤浸出水的重金屬濃度為As：0.05mg/L。將1L該試驗液體放入聚乙烯容器中，添加1g實施例1中獲得的處理材料1，振動24小時。振動後進行離心分離，用1μm玻璃杯過濾器吸引清液過濾。然後取30ml濾液，添加5ml的HNO3，微波分解後，用超純水定容成50ml。從中取走10ml的分解液後，再在剩餘的分解液中加超純水定容成50ml，然後用ICP-MS測定。此時濾液中的重金屬濃度為As：小於0.001mg/L。 10 L of pure water was added to 1 kg of heavy metal contaminated soil, and after shaking for 24 hours, centrifugation and filtration were carried out to obtain soil leaching water. The concentration of heavy metals in the soil leaching water was As: 0.05 mg/L. 1 L of this test liquid was placed in a polyethylene container, and 1 g of the treatment material 1 obtained in Example 1 was added and shaken for 24 hours. After shaking, the mixture was centrifuged, and the supernatant was filtered with a 1 μm glass filter. Then, 30 ml of the filtrate was taken, 5 ml of HNO 3 was added , and after microwave decomposition, it was made up to 50 ml with ultrapure water. After removing 10 ml of the decomposing solution, the remaining decomposing liquid was added with ultrapure water to a volume of 50 ml, which was then measured by ICP-MS. At this time, the concentration of heavy metals in the filtrate was As: less than 0.001 mg/L.
在100g重金屬污染土壤中，添加7g實施例2中獲得的處理材料2與8ml純水，攪拌混合製成處理土壤，放到聚乙烯容器中，在常溫下密封保存24小時。在115g該處理土壤中添加1L純水，放入聚乙烯容器中振動6小時。振動後進行離心分離，用1μm玻璃杯過濾器吸引清液過濾。然後取30ml濾液，添加5ml的HNO3，微波分解後，用超純水定容成50ml。從中取走10ml的分解液後，再在剩餘的分解液中加超純水定容成50ml，然後用ICP-MS測定。 此時濾液中的鉛濃度為0.1mg/L。 In 100 g of heavy metal contaminated soil, 7 g of the treatment material 2 obtained in Example 2 and 8 ml of pure water were added, stirred and mixed to prepare a treated soil, placed in a polyethylene container, and sealed and stored at room temperature for 24 hours. 1 L of pure water was added to 115 g of the treated soil, and shaken in a polyethylene container for 6 hours. After shaking, the mixture was centrifuged, and the supernatant was filtered with a 1 μm glass filter. Then, 30 ml of the filtrate was taken, 5 ml of HNO 3 was added , and after microwave decomposition, it was made up to 50 ml with ultrapure water. After removing 10 ml of the decomposing solution, the remaining decomposing liquid was added with ultrapure water to a volume of 50 ml, which was then measured by ICP-MS. At this time, the lead concentration in the filtrate was 0.1 mg/L.
省略製作處理土壤的操作，在100g重金屬污染土壤中添加1L純水，與上述操作相同，獲得濾液的鉛濃度為0.8mg/L。 The operation of treating the soil was omitted, and 1 L of pure water was added to 100 g of the heavy metal contaminated soil, and the lead concentration of the filtrate was 0.8 mg/L as in the above operation.
使用與實施例11中相同的污染土壤，加入市面銷售的鎂類重金屬不溶材料“denight”(太平洋混凝土株式會社製造)7g與8ml純水，攪拌混合後製成處理土壤，放在聚乙烯容器中常溫密封保存24小時。在1份該處理土壤中添加10份純水，放入聚乙烯容器中振動6小時。振動後進行離心分離，用1μm玻璃杯過濾器吸引清液過濾。然後取30ml濾液，添加5ml的HNO3，微波分解後，用超純水定容成50ml。從中取走10ml的分解液後，再在剩餘的分解液中加超純水定容成50ml，然後用ICP-MS測定。此時濾液中的鉛濃度為0.4mg/L。 Using the same contaminated soil as in Example 11, a commercially available magnesium heavy metal insoluble material "denight" (manufactured by Pacific Concrete Co., Ltd.) 7 g and 8 ml of pure water were added, and the mixture was stirred and mixed to prepare a treated soil, which was placed in a polyethylene container. Store at room temperature for 24 hours. 10 parts of pure water was added to 1 part of the treated soil, and shaken in a polyethylene container for 6 hours. After shaking, the mixture was centrifuged, and the supernatant was filtered with a 1 μm glass filter. Then, 30 ml of the filtrate was taken, 5 ml of HNO 3 was added , and after microwave decomposition, it was made up to 50 ml with ultrapure water. After removing 10 ml of the decomposing solution, the remaining decomposing liquid was added with ultrapure water to a volume of 50 ml, which was then measured by ICP-MS. At this time, the lead concentration in the filtrate was 0.4 mg/L.
Claims (12)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210419212.4A CN103785348B (en) | 2012-10-29 | 2012-10-29 | Harmful-substance processing material, its manufacturing method and harmful-substance processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201416328A TW201416328A (en) | 2014-05-01 |
| TWI597243B true TWI597243B (en) | 2017-09-01 |
Family
ID=50626490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102139123A TWI597243B (en) | 2012-10-29 | 2013-10-29 | Hazardous material handling materials and methods of their manufacture, handling of hazardous materials |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN103785348B (en) |
| TW (1) | TWI597243B (en) |
| WO (1) | WO2014067444A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040169A (en) * | 2016-06-08 | 2016-10-26 | 芜湖市长江起重设备制造有限公司 | Wear-resistant crane electroplating wastewater treating agent and production method thereof |
| CN107381705B (en) * | 2017-08-28 | 2020-04-28 | 华南理工大学 | Method for separating and recovering multiple cationic heavy metals in water through phase change regulation |
| CN107473319B (en) * | 2017-08-28 | 2020-04-28 | 华南理工大学 | Method for recovering cationic heavy metals in water through phase change regulation |
| CN109097568B (en) * | 2018-09-21 | 2020-06-26 | 中南大学 | Method for separating selenium and arsenic from alkaline leaching solution containing selenium and arsenic |
| CN109607947A (en) * | 2018-12-25 | 2019-04-12 | 贵州省分析测试研究院 | A method of removing coal washery heavy metal in waste water arsenic |
| CN110180492B (en) * | 2019-04-17 | 2022-09-23 | 中节能（合肥）可再生能源有限公司 | Active filter material for removing magnesium ions, and preparation method and application thereof |
| CN110180495B (en) * | 2019-05-29 | 2022-04-12 | 北京化工大学常州先进材料研究院 | Method for preparing magnesium silicate based composite adsorption material by multi-coprecipitation method |
| CN110560473B (en) | 2019-08-21 | 2020-07-07 | 生态环境部环境规划院 | Method for stabilizing soil fluoride and arsenic |
| CN114259977A (en) * | 2021-12-10 | 2022-04-01 | 太原理工大学 | Preparation method and application of fly ash-loaded hydrated magnesium carbonate composite material |
| CN114873649B (en) * | 2022-04-26 | 2023-06-23 | 广州大学 | Method for synthesizing nano Schlemen mineral for repairing arsenic-polluted soil |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08215560A (en) * | 1995-02-15 | 1996-08-27 | Asahi Chem Ind Co Ltd | Adsorption removing material for heavy metallic component contained in gas and method for cleaning gas |
| US6271173B1 (en) * | 1999-11-01 | 2001-08-07 | Phillips Petroleum Company | Process for producing a desulfurization sorbent |
| WO2002076577A2 (en) * | 2001-02-06 | 2002-10-03 | Watervisions International, Inc. | Compositions of insoluble magnesium containing minerals for use in fluid filtration |
| CN1795979B (en) * | 2004-12-23 | 2010-11-10 | 韩国电力公社 | High strength drying regeneration CO2 adsorbent |
| JP4892231B2 (en) * | 2005-12-08 | 2012-03-07 | 荏原実業株式会社 | Deodorizing filter and deodorizing system |
| CN100467095C (en) * | 2006-12-28 | 2009-03-11 | 中国科学院南京土壤研究所 | Porous calcium silicate filter material for water treatment |
-
2012
- 2012-10-29 CN CN201210419212.4A patent/CN103785348B/en active Active
-
2013
- 2013-10-29 TW TW102139123A patent/TWI597243B/en active
- 2013-10-29 WO PCT/CN2013/086125 patent/WO2014067444A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014067444A1 (en) | 2014-05-08 |
| CN103785348A (en) | 2014-05-14 |
| CN103785348B (en) | 2017-03-22 |
| TW201416328A (en) | 2014-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI597243B (en) | Hazardous material handling materials and methods of their manufacture, handling of hazardous materials | |
| JP5905669B2 (en) | Hazardous material treatment material and method | |
| Chen et al. | Precipitation of heavy metals from wastewater using simulated flue gas: sequent additions of fly ash, lime and carbon dioxide | |
| Mangialardi | Disposal of MSWI fly ash through a combined washing-immobilisation process | |
| JP2005040685A (en) | Heavy metal adsorbent material and heavy metal treatment method | |
| WO2007062062A2 (en) | Method and composition to reduce the amounts of arsenic in water | |
| JP2003225640A (en) | Solidifying and insolubilizing agent for contaminated soil | |
| KR20090107063A (en) | Process for treating substances contaminated by heavy metals | |
| CN101774669B (en) | Composite dephosphorizing agent for treating acidic wastewater containing phosphorus and preparation and application methods thereof | |
| JP2016117050A (en) | Inorganic polymer-made adsorbent and method for production thereof | |
| JP2005254077A (en) | Method for manufacturing heavy metal adsorbent and adsorbent obtained thereby | |
| JP4709498B2 (en) | Crystalline layered double hydroxide powder, method for producing the same, molded product, and method for immobilizing harmful substances | |
| CN101516780A (en) | Hydrotalcite-like particulate material and method for production thereof | |
| KR101235251B1 (en) | Cement using waterworks sludge and mathod for manufacturing the same | |
| JP5768293B2 (en) | Method for producing soil-solidifying material using fluorine-containing inorganic waste, obtained soil-solidifying material, and method for solidifying soft soil using the soil-solidifying material | |
| JP4420636B2 (en) | Hazardous material treatment material and its manufacturing method | |
| Min et al. | Arsenic Pollution Control Technologies for Arsenic-Bearing Solid Wastes | |
| CN114149063A (en) | Silicate-carbonate composite mineral material, preparation method thereof and application thereof in precipitating heavy metal ions | |
| JP4006584B2 (en) | Fluorine adsorbent and method for treating fluorine in water | |
| JP3724062B2 (en) | Waste treatment material and waste treatment method | |
| Falaciński et al. | The use of extraction methods to assess the immobilization of metals in hardening slurries | |
| JP5077777B2 (en) | Elution reduction material and elution reduction treatment method | |
| JP2015196146A (en) | Phosphorus recovery material for phosphorus-containing water and phosphorus recovery method using the phosphorus recovery material | |
| JP4824434B2 (en) | Oil and fat adsorbent, method for producing fat and oil adsorbent, inorganic flocculant, and method for producing inorganic flocculant | |
| JP4061253B2 (en) | Method for producing heavy metal treatment agent |