JP6303223B2 - Method for solidifying residue containing rare earth - Google Patents
Method for solidifying residue containing rare earth Download PDFInfo
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- JP6303223B2 JP6303223B2 JP2013265949A JP2013265949A JP6303223B2 JP 6303223 B2 JP6303223 B2 JP 6303223B2 JP 2013265949 A JP2013265949 A JP 2013265949A JP 2013265949 A JP2013265949 A JP 2013265949A JP 6303223 B2 JP6303223 B2 JP 6303223B2
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 39
- 150000002910 rare earth metals Chemical class 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 21
- 239000000463 material Substances 0.000 claims description 32
- 239000004568 cement Substances 0.000 claims description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 description 18
- 239000002253 acid Substances 0.000 description 10
- 239000011398 Portland cement Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000005304 optical glass Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000012669 compression test Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Treatment Of Sludge (AREA)
Description
本発明は、太平洋の深海の海底に分布する、レアアースを高含有率で含む泥を典型例とするレアアースを含有する泥を、酸で処理した後に発生する酸性の残渣の固化処理方法に関する。 The present invention relates to a method for solidifying an acidic residue generated after treating a mud containing rare earth, typically a mud containing a high content of rare earth, distributed on the deep sea floor of the Pacific Ocean with an acid.
レアアースは、ネオジム・鉄・ボロン磁石、ＬＥＤ電球、燃料電池等に用いられる原料として、最先端技術産業に不可欠な元素であり、近年、その需要も急増している。一方、レアアースの寡占的産出国であった中国が、輸出奨励政策から規制強化政策へと方針を変更するなどの事情下において、レアアースの供給不足や価格高騰が懸念されており、レアアースの新たな供給源の確保が課題となっている。
このような状況下において、太平洋の広範囲に分布しているレアアースを高含有率で含む深海の泥が、レアアースの新たな供給源として注目されている。
レアアースを高含有率で含む泥（例えば、太平洋の深海の泥）は、その資源量が膨大であること、希酸中に１〜３時間浸漬するという簡易な方法で抽出することができること、トリウムやウラン等の放射性元素をほとんど含まないこと、等の数々の利点を有している。
Rare earth is an indispensable element in the state-of-the-art technology industry as a raw material used for neodymium / iron / boron magnets, LED bulbs, fuel cells, and the like, and its demand is rapidly increasing in recent years. On the other hand, China, which was an oligopolistic producer of rare earths, is worried about a shortage of rare earth supplies and rising prices under circumstances such as changing its policy from an export incentive policy to a more restrictive policy. Securing supply sources is an issue.
Under such circumstances, deep-sea mud containing a high content of rare earth distributed over a wide area in the Pacific Ocean has attracted attention as a new source of rare earth.
Mud containing a high content of rare earths (for example, deep sea mud in the Pacific Ocean) has an enormous amount of resources and can be extracted by a simple method of immersing in dilute acid for 1 to 3 hours, thorium It has many advantages such as almost no radioactive elements such as uranium and uranium.
レアアースを含む泥を処理する方法として、例えば、特許文献１に、光学ガラス研磨・洗浄工程およびこれに付帯する排水処理装置から発生する光学ガラス汚泥に硫酸を加えて加熱処理し、汚泥中に含まれるレアアースメタル成分を溶解するとともに鉛、バリウム、シリカ等を沈殿とし、該沈殿を処理液から分離することによりレアアースメタル成分の溶液を取得することを特徴とする光学ガラス汚泥からレアアースメタル成分を回収する方法が記載されている。 As a method for treating mud containing rare earths, for example, in Patent Document 1, sulfuric acid is added to the optical glass sludge generated from the optical glass polishing / cleaning process and the wastewater treatment equipment incidental thereto, and the heat treatment is performed, and is contained in the sludge. The rare earth metal component is recovered from the optical glass sludge, in which the rare earth metal component is dissolved, and lead, barium, silica, etc. are precipitated, and the precipitate is separated from the treatment liquid to obtain a rare earth metal component solution. How to do is described.
レアアースを含有する泥の乾燥質量中のレアアースの質量の割合は、レアアースの含有率が高いことで知られる太平洋の深海底であっても、０．３質量％以下にすぎない。このため、レアアースを含有する泥から、希酸を用いてレアアースを抽出した後に、多量の酸性の残渣が発生するという問題がある。
この酸性の残渣の処理方法として、水酸化ナトリウム等のアルカリ剤で中和処理する方法が考えられる。しかし、中和処理後の残渣を例えば埋め立て資材として利用しようとしても、泥の水分含有率が大きいことから、軟弱な地盤になり、地盤を利用することができるまでに長期間が必要となったり、あるいは、別途、地盤の改良工事が必要となる。また、この残渣を土工資材として利用する場合には、泥を予め脱水処理しなければならないという問題がある。また、水分含有率が大きい泥は、移送や保管が困難であるという問題もある。
The ratio of the mass of the rare earth in the dry mass of the mud containing the rare earth is only 0.3% by mass or less even in the deep sea bottom of the Pacific Ocean, which is known to have a high content of the rare earth. For this reason, there is a problem that a large amount of acidic residue is generated after extracting rare earth from a mud containing rare earth using dilute acid.
As a method for treating this acidic residue, a method of neutralizing with an alkali agent such as sodium hydroxide can be considered. However, even if you try to use the residue after neutralization as landfill material, for example, the moisture content of the mud is large, so it becomes a soft ground and it may take a long time before you can use the ground. Or, ground improvement work is required separately. In addition, when this residue is used as earthwork material, there is a problem that the mud must be dehydrated in advance. Moreover, there is a problem that mud having a high moisture content is difficult to transport and store.
本発明の目的は、レアアースを含有する泥から、酸を用いてレアアースを抽出した後に発生する多量の酸性の残渣を、簡易に処理することができ、また、処理後に得られるものを埋め立て資材等として利用することができる方法を提供することにある。 The object of the present invention is to easily treat a large amount of acidic residue generated after extraction of rare earths using acid from mud containing rare earths, and to reclaim materials obtained after the treatment, etc. It is in providing the method which can be utilized as.
本発明者は、上記課題を解決するために鋭意検討した結果、レアアースを含有する泥を酸で処理した後に発生する酸性の残渣と、アルカリ性固化材を混合して、固化体を得るようにすれば、この操作を簡易に行うことができるとともに、得られた固化体を、埋め立て資材等として利用することができることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventor mixed an acidic residue generated after treating rare earth-containing mud with an acid and an alkaline solidifying material to obtain a solidified body. For example, the present invention was completed by finding that this operation can be easily performed and the obtained solidified body can be used as a landfill material or the like.
すなわち、本発明は、以下の［１］〜［３］を提供するものである。
［１］ レアアースを含有する泥を酸で処理した後に発生する酸性の残渣と、アルカリ性固化材を混合して、固化体を得ることを特徴とするレアアースを含有する残渣の固化処理方法。
［２］ 上記アルカリ性固化材が、セメント、石灰、または酸化マグネシウムを含む、上記［１］に記載のレアアースを含有する残渣の固化処理方法。
［３］ 上記レアアースを含有する泥は、海底の地盤に存在する、レアアースの含有率が１，０００ｐｐｍ以上の泥である、上記［１］又［２］に記載のレアアースを含有する残渣の固化処理方法。
That is, the present invention provides the following [1] to [3].
[1] A method for solidifying a residue containing a rare earth, comprising mixing an acidic residue generated after treating a mud containing rare earth with an acid and an alkaline solidifying material to obtain a solidified body.
[2] The method for solidifying a residue containing a rare earth according to [1], wherein the alkaline solidifying material contains cement, lime, or magnesium oxide.
[3] Solidification of residue containing rare earth according to [1] or [2], wherein the rare earth-containing mud is mud having a rare earth content of 1,000 ppm or more, which is present on the seabed ground. Processing method.
本発明によれば、レアアースを含有する泥を酸で処理した後に得られる多量の酸性の泥を、簡易に処理することができる。
特に、本発明では、酸性の残渣を得る前の酸性の泥の脱水を、アルカリ性固化材との混合によって固化体を得ることができる程度に行えばよいので、アルカリ性固化材を用いずに脱水して埋め立て資材を得る場合に比べて、脱水に要する負担（例えば、脱水手段の性能等）が軽減される。
また、本発明によれば、固化体を埋め立て資材等として利用することができる。
According to the present invention, a large amount of acidic mud obtained after treating mud containing rare earth with an acid can be easily treated.
In particular, in the present invention, dehydration of acidic mud before obtaining an acidic residue may be performed to such an extent that a solidified body can be obtained by mixing with an alkaline solidifying material. Compared with the case of obtaining landfill material, the burden required for dewatering (for example, the performance of the dewatering means) is reduced.
Moreover, according to this invention, a solidified body can be utilized as a reclamation material etc.
本発明のレアアースを含有する残渣の固化処理方法は、レアアースを含有する泥を酸で処理した後に発生する酸性の残渣と、アルカリ性固化材を混合して、固化体を得るものである。
本発明における固化処理の対象は、レアアースを含有する泥を酸で処理して、レアアースを液中に抽出した後に発生する酸性の残渣である。
レアアースとは、周期律表の第３族のランタロイド（Ｌａ（ランタン）〜Ｌｕ（ルテチウム）の計１５種の元素）に、同じく第３族のＳｃ（スカンジウム）とＹ（イットリウム）を加えた計１７種の元素をいう。
レアアースを含有する泥の一例として、深海底（例えば、海の深さとして、３，５００〜６，０００ｍの領域）に層状（例えば、海底から、深さが数１０ｍ程度までの地盤）に分布する、レアアースの含有率が大きい泥が挙げられる。
本発明において、レアアースを含有する泥（乾燥状態のもの）の中のレアアースの含有率（質量基準）は、資源であるレアアースを採掘する際の経済性の観点から、好ましくは１，０００ｐｐｍ以上、より好ましくは２，０００ｐｐｍ以上である。
The method for solidifying a residue containing rare earth according to the present invention is to obtain a solidified body by mixing an acidic residue generated after treating mud containing rare earth with an acid and an alkaline solidifying material.
The object of the solidification treatment in the present invention is an acidic residue generated after the rare earth-containing mud is treated with an acid and the rare earth is extracted into the liquid.
Rare earth is a total of 15 lanthanoids in the periodic table (a total of 15 elements from La (lanthanum) to Lu (lutetium)) plus Sc (scandium) and Y (yttrium). Refers to 17 elements.
As an example of mud containing rare earth, it is distributed in layers on the deep sea floor (for example, the area of 3,500 to 6,000 m as the depth of the sea) (for example, the ground from the sea floor to a depth of about several tens of meters). And mud with a high rare earth content.
In the present invention, the rare earth content (based on mass) in the mud containing rare earth (in a dry state) is preferably 1,000 ppm or more from the viewpoint of economy when mining the rare earth as a resource. More preferably, it is 2,000 ppm or more.
本発明における固化処理の対象である酸性の残渣の水分含有率は、埋め立て資材等の用途に好適な物性を有する固化体を得るなどの観点から、好ましくは２００質量％以下、より好ましくは５０〜１５０質量％、さらに好ましくは５０〜１００質量％、特に好ましくは５０〜８０質量％である。
なお、該水分含有率が５０質量％以上であると、脱水の負担を軽減することができる。
酸性の残渣の水分含有率が大きい場合は、泥をタンク等の容器に貯留して、泥の固形分を沈澱させ、その上澄みを回収する沈澱方式や、スクリューデカンター等の装置を用いる遠心分離方式や、フィルタープレス等の装置を用いる加圧脱水方式等の方法で脱水すればよい。
中でも、低コストで簡易に脱水することができる点で、沈澱方式及び遠心分離方式が好ましく、沈澱方式が、より好ましい。
なお、脱水の程度は、沈澱方式、遠心分離方式、加圧脱水方式の順に大きくなる。
The water content of the acidic residue that is the target of the solidification treatment in the present invention is preferably 200% by mass or less, more preferably 50 to 50%, from the viewpoint of obtaining a solidified material having physical properties suitable for uses such as landfill materials. 150 mass%, More preferably, it is 50-100 mass%, Most preferably, it is 50-80 mass%.
In addition, the load of dehydration can be reduced when the moisture content is 50% by mass or more.
If the water content of the acidic residue is large, the mud is stored in a container such as a tank, the solid content of the mud is settled, and the supernatant is recovered, or the centrifugal method using a device such as a screw decanter Alternatively, dehydration may be performed by a method such as a pressure dehydration method using an apparatus such as a filter press.
Among these, the precipitation method and the centrifugal separation method are preferable, and the precipitation method is more preferable because it can be easily dehydrated at low cost.
The degree of dehydration increases in the order of the precipitation method, the centrifugal separation method, and the pressure dehydration method.
本発明で用いるアルカリ性固化材とは、水に溶解するとｐＨがアルカリ性の領域となる固化材であり、例えば、セメント、石灰または酸化マグネシウムを含むものが挙げられる。
セメント、石灰または酸化マグネシウムを含むものとしては、例えば、セメント、セメント系固化材、石灰、石灰系固化材、マグネシア系固化材等が挙げられる。
中でも、固化体を埋め立て資材として用いた場合に、強固な地盤を得る観点から、セメントが好ましい。
The alkaline solidification material used in the present invention is a solidification material whose pH becomes an alkaline region when dissolved in water, and examples thereof include those containing cement, lime or magnesium oxide.
Examples of those containing cement, lime, or magnesium oxide include cement, cement-based solidified material, lime, lime-based solidified material, and magnesia-based solidified material.
Among these, cement is preferable from the viewpoint of obtaining a solid ground when the solidified body is used as a landfill material.
セメントとしては、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント等の各種ポルトランドセメントや、高炉セメント、フライアッシュセメント等の混合セメントや、エコセメント等が挙げられる。
中でも、廃棄物の利用の観点から、エコセメントが好ましい。
セメント系固化材とは、セメントを主成分（通常、５０質量％以上）として含み、かつ、各種の有効成分を副成分として含む固化材である。市販品としては、太平洋セメント社製の「ジオセット」（商品名）等が挙げられる。
石灰としては、生石灰、消石灰等が挙げられる。
石灰系固化材とは、石灰を主成分（通常、５０質量％以上）として含み、かつ、各種の有効成分を副成分として含む固化材である。
マグネシア系固化材としては、炭酸マグネシウムまたは水酸化マグネシウムを、低温（６００〜９００℃）で焼成して得られる軽焼マグネシア（軽焼酸化マグネシウムともいう。）等が挙げられる。
Examples of the cement include various portland cements such as ordinary portland cement, early-strength portland cement, medium heat portland cement, and low heat portland cement, mixed cements such as blast furnace cement and fly ash cement, and ecocement.
Among them, ecocement is preferable from the viewpoint of utilization of waste.
The cement-based solidifying material is a solidifying material containing cement as a main component (usually 50% by mass or more) and containing various active ingredients as subcomponents. Examples of commercially available products include “Geoset” (trade name) manufactured by Taiheiyo Cement.
Examples of lime include quick lime and slaked lime.
The lime-based solidified material is a solidified material containing lime as a main component (usually 50% by mass or more) and various active ingredients as subcomponents.
Examples of the magnesia-based solidifying material include light-burned magnesia (also referred to as light-burned magnesium oxide) obtained by baking magnesium carbonate or magnesium hydroxide at a low temperature (600 to 900 ° C.).
アルカリ性固化材の量は、酸性の残渣のｐＨによっても異なるが、酸性の残渣を中和して、中性または中性に近いｐＨ領域の固化体を得る観点から、酸性の残渣１ｍ３に対して、好ましくは３０〜４００ｋｇ、より好ましくは５０〜３００ｋｇ、特に好ましくは１００〜２００ｋｇである。
なお、本発明の固化処理においては、例えば、（１）酸性の残渣にアルカリ性固化材を添加して混合し、得られた混合物を埋め立て地等に打設して固化させる、（２）酸性の残渣を埋め立て地等に打設しておき、この打設した酸性の残渣に、アルカリ性固化材を添加して混合し、固化させる、（３）酸性の残渣にアルカリ性固化材を添加して混合し、粒状やブロック状の成形体を製造した後、該成形体を埋め立て資材等として利用する、等の実施形態を採用することができる。
The amount of the alkaline solidifying material varies depending pH of acidic residues, to neutralize the residual acid, from the viewpoint of obtaining a solidified body pH region close to neutrality or neutral, to the residue 1 m 3 of acidic And preferably 30 to 400 kg, more preferably 50 to 300 kg, particularly preferably 100 to 200 kg.
In the solidification treatment of the present invention, for example, (1) an alkaline residue is added to and mixed with an acidic residue, and the resulting mixture is placed in a landfill or the like to be solidified. The residue is placed in a landfill, etc., and an alkaline solidifying material is added to the cast acidic residue and mixed to solidify. (3) An alkaline solidifying material is added to the acidic residue and mixed. In addition, after manufacturing a granular or block shaped molded body, the molded body can be used as a landfill material or the like.
以下、実施例によって本発明を説明する。以下の文中の「％」は、特に断らない限り、質量基準の割合を表す。
（１）レアアースを含有する残渣の模擬試料の調製
太平洋の深海底から採取したレアアースを含有する泥の、公表されている化学成分及び公表されている含有鉱物から、レアアースを含有する残渣の模擬試料の鉱物組成を定めた。この鉱物組成を目標にして、珪砂２４％、酸化鉄（Ｆｅ２Ｏ３）１４％、酸化マンガン（ＭｎＯ)４％、酸化マグネシウム（ＭｇＯ）３％、ハイドロキシアパタイト６％、フィリップサイト４８％（以上の割合は、材料全量中の配合割合を表す。）を混合粉砕することによって、粘土（粒径：５μｍ以下）やシルト（粒径：５μｍを超え、７５μｍ以下）の粒度を有し、かつ、３２μｍ残分が５％以下の粉砕物を得た。
得られた粉砕物を、０．１Ｎの塩酸に１時間浸漬し、次いで、含水率（水分含有率）１００％になるように脱水して、レアアースを含有する残渣の模擬試料を得た。
また、比較用（比較例１〜３）に、含水率１００％のシルト（幸手産）を用意した。
Hereinafter, the present invention will be described by way of examples. Unless otherwise specified, “%” in the following text represents a mass-based ratio.
(1) Preparation of simulated samples of residues containing rare earths Simulated samples of residues containing rare earths from published chemical components and published minerals of mud containing rare earths collected from the deep sea bottom of the Pacific Ocean The mineral composition was determined. With this mineral composition as a target, silica sand 24%, iron oxide (Fe 2 O 3 ) 14%, manganese oxide (MnO) 4%, magnesium oxide (MgO) 3%, hydroxyapatite 6%, philipite 48% (above) The ratio of represents the blending ratio in the total amount of the material.) By mixing and pulverizing, the particle size of clay (particle size: 5 μm or less) or silt (particle size: more than 5 μm, 75 μm or less), and A pulverized product having a residue of 32 μm of 5% or less was obtained.
The obtained pulverized product was immersed in 0.1N hydrochloric acid for 1 hour, and then dehydrated to a moisture content (water content) of 100%, to obtain a simulated sample of a residue containing rare earth.
In addition, for comparison (Comparative Examples 1 to 3), a silt having a moisture content of 100% (Satte product) was prepared.
（２）固化体の作製
「地盤工学会基準（案）ＪＧＳ ０８２１（安定処理土の締固めをしない供試体作製方法」に準拠して、前記（１）の残渣の模擬試料を用いて、固化体の供試体を作製した。具体的には、残渣の模擬試料と、残渣の模擬試料１ｍ３当たり１５０ｋｇの量のセメントを、ハンドミキサーで混合した後、得られた混合物を、φ５ｃｍ×１０ｃｍの円柱モールド内に収容して、成形体を作製した。この成形体を２０℃の恒温室で７日間養生して、強度試験用の供試体である固化体を得た。この際、セメントとしては、普通ポルトランドセメント（実施例１、比較例１）、エコセメント（実施例２、比較例２）、エコセメント８０％と無水石膏２０％の混合物（実施例３、比較例３）を用いた。
（３）固化体の一軸圧縮試験
固化体の一軸圧縮試験を、「ＪＩＳ Ａ １２１６」に準拠して行った。
結果を表１に示す。表１中、「普通」、「エコ」は、各々、普通ポルトランドセメント、エコセメントを表す。
(2) Preparation of solidified body In accordance with “Geotechnical Society Standard (Draft) JGS 0821 (Method for Preparing Specimen without Compaction of Stabilized Soil”), solidified using the simulated residue sample of (1) above. Specifically, a simulated residue sample and cement in an amount of 150 kg per 1 m 3 residue simulated sample were mixed with a hand mixer, and the resulting mixture was mixed with a diameter of 5 cm × 10 cm. The molded body was housed in a cylindrical mold, and the molded body was cured for 7 days in a constant temperature room at 20 ° C. to obtain a solidified body as a specimen for strength test. Ordinary Portland cement (Example 1, Comparative Example 1), eco cement (Example 2, Comparative Example 2), and a mixture of 80% eco cement and 20% anhydrous gypsum (Example 3, Comparative Example 3) were used.
(3) Uniaxial compression test of solidified body A uniaxial compression test of the solidified body was performed according to "JIS A 1216".
The results are shown in Table 1. In Table 1, “ordinary” and “eco” represent ordinary portland cement and eco-cement, respectively.
（４）固化体の吸着性能試験
レアアースを含有する泥（例えば、深海泥）には、ゼオライトが含まれている。このため、固化体には、ＢＯＤや海水中のレアメタル等の吸着作用を期待することができる。そこで、実施例１及び比較例１の各固化体について、メチレンブルーの吸着量を測定した。測定は、セメント協会の「ＪＣＡＳ Ｉ−６１：２００８」（フライアッシュのメチレンブルー吸着量試験方法）に準拠して行った。具体的には、１００℃で乾燥した固化体の試料を適度に破砕して試験に供し、単位質量（ｇ）あたりのメチレンブルーの吸着量を求めた。
結果を表２に示す。表２から、実施例１の固化体は、比較例１の固化体に比べて、メチレンブルーの吸着量が非常に大きく、固化処理後も、周辺環境のＢＯＤや、海水中のレアメタル等の再吸着用の用途における利用を期待することができることがわかる。
(4) Adsorption performance test of solidified body Mud containing rare earth (for example, deep-sea mud) contains zeolite. For this reason, the solidified body can be expected to adsorb BOD and rare metals in seawater. Therefore, the adsorbed amount of methylene blue was measured for each solidified body of Example 1 and Comparative Example 1. The measurement was performed in accordance with “JCAS I-61: 2008” (Test method for methylene blue adsorption amount of fly ash) of Cement Association. Specifically, the solidified sample dried at 100 ° C. was appropriately crushed and subjected to the test, and the amount of methylene blue adsorbed per unit mass (g) was determined.
The results are shown in Table 2. From Table 2, the solidified body of Example 1 has a much larger amount of methylene blue adsorbed than the solidified body of Comparative Example 1, and after solidification treatment, BOD in the surrounding environment and re-adsorption of rare metals in seawater. It can be seen that it can be expected to be used in a specific application.
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