JP6656964B2 - Granular earthwork material and method for producing the same - Google Patents
Granular earthwork material and method for producing the same Download PDFInfo
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- JP6656964B2 JP6656964B2 JP2016053727A JP2016053727A JP6656964B2 JP 6656964 B2 JP6656964 B2 JP 6656964B2 JP 2016053727 A JP2016053727 A JP 2016053727A JP 2016053727 A JP2016053727 A JP 2016053727A JP 6656964 B2 JP6656964 B2 JP 6656964B2
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- 239000000463 material Substances 0.000 title claims description 79
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 33
- 150000002910 rare earth metals Chemical class 0.000 claims description 33
- 239000008187 granular material Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000011810 insulating material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004567 concrete Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000010426 asphalt Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002285 radioactive effect Effects 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
- 238000005728 strengthening Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
本発明は、レアアースを含有する泥を原料として用いた、粒状の土工資材（例えば、埋め戻し材等）、およびその製造方法に関する。 The present invention relates to a granular earthwork material (for example, backfill material) using a rare earth-containing mud as a raw material, and a method for producing the same.
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 earths are indispensable elements in cutting-edge technology industries as raw materials used for neodymium / iron / boron magnets, LED bulbs, fuel cells, and the like, and in recent years, their demand has been rapidly increasing. On the other hand, under the circumstances that China, which was an oligopolistic producer of rare earths, changed its policy from an export promotion policy to a policy of strengthening regulations, there is a concern that there will be a shortage of rare earth supplies and soaring prices. Securing a supply source is an issue.
Under such circumstances, deep-sea mud containing a high content of rare earths widely distributed in the Pacific Ocean has attracted attention as a new source of rare earths.
Mud containing a high content of rare earths (eg, deep sea mud in the Pacific Ocean) has a huge amount of resources, and can be extracted by a simple method of immersing in dilute acid for 1 to 3 hours. It has a number of advantages such as almost no radioactive elements such as uranium and uranium.
一方、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する際に、多量の酸性の泥が発生するという問題がある。
また、この酸性の泥は、大きな水分含有率を有し、扱い難いという問題もある。
On the other hand, 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 ocean floor of the Pacific Ocean, which is known to have a high rare earth content. For this reason, there is a problem that a large amount of acidic mud is generated when extracting rare earth from dirt containing rare earth using dilute acid.
In addition, the acidic mud has a problem that it has a large water content and is difficult to handle.
上述の事情下において、レアアースを含有する泥を処理して、埋め立て等の用途に利用可能な土工資材を得るための方法が知られている。
例えば、特許文献１に、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（例えば、セメント）を混合して、固化体（例えば、埋め立て資材として利用可能なもの）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が記載されている。
また、特許文献２に、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及び／又は該酸性の残渣の中和物を、コンクリートまたはモルタルの原料の一部（例えば、セメントの原料の一部）として使用して、コンクリート構造物を構築するコンクリート構造物構築工程を含むことを特徴とする、レアアースを含有する泥の処理方法が記載されている。
さらに、特許文献３に、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を含む焼成物製造用原料を加熱してなる、圧壊強度が１，０００Ｎ以上の人工骨材が記載されている。
Under the circumstances described above, there is known a method for treating mud containing a rare earth to obtain an earthwork material that can be used for landfills and the like.
For example, in Patent Document 1, an acidic residue generated after treating a rare earth-containing mud with an acid and an alkaline solidifying material (for example, cement) are mixed to form a solidified material (for example, a material that can be used as a landfill material). ), A method for solidifying a residue containing a rare earth.
Patent Document 2 discloses that an acidic residue generated after treating a rare earth-containing mud with an acid and / or a neutralized product of the acidic residue is used as a part of a raw material of concrete or mortar (for example, a raw material of cement). The method for treating a mud containing a rare earth is described, comprising a concrete structure construction step of constructing a concrete structure by using the method as a part of a concrete structure.
Further, Patent Literature 3 describes an artificial aggregate having a crushing strength of 1,000 N or more, which is obtained by heating a raw material for producing a fired product containing an acidic residue generated after treating a mud containing a rare earth with an acid. ing.
レアアースを含有する泥を酸で処理した後に発生する残渣を原料として用いてなる焼成物として、例えば、軽量な粒状物を製造することができれば、この軽量な粒状物を軽量骨材等として利用することができ、焼成物の用途を広げることができる。
本発明の目的は、レアアースを含有する泥を酸で処理した後に発生する残渣を用いた土工資材であって、軽量であるため、軽量骨材等の用途に利用することができる粒状の土工資材、およびその製造方法を提供することである。
As a fired product using a residue generated after treating a rare earth-containing mud with an acid as a raw material, for example, if a lightweight granular material can be manufactured, this lightweight granular material is used as a lightweight aggregate or the like. And the use of the fired product can be expanded.
An object of the present invention is an earthwork material using a residue generated after treating a mud containing a rare earth with an acid, and since it is lightweight, a granular earthwork material that can be used for applications such as lightweight aggregate. , And a method of manufacturing the same.
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残渣を、造粒することなく、脱水ケーキまたはスラリーとして焼成し、次いで、必要に応じて破砕等を行って、粒状物を得た場合、この粒状物を軽量骨材等として用いうることを見出し、本発明を完成した。 The present inventors have conducted intensive studies to solve the above-described problems, and as a result, the residue generated after treating the rare earth-containing mud with acid, without granulating, firing as a dewatered cake or slurry, The present inventors have found that when a granular material is obtained by crushing or the like according to the method, the granular material can be used as a lightweight aggregate or the like, and the present invention has been completed.
すなわち、本発明は、以下の［１］〜［５］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残渣からなる、脱水ケーキまたはスラリーを焼成してなることを特徴とする粒状の土工資材。
［２］ 上記粒状の土工資材の見かけ密度が、０．７〜１．６ｇ／ｃｍ３である、上記［１］に記載の粒状の土工資材。
［３］ 上記［１］又は［２］に記載の粒状の土工資材を製造するための方法であって、上記脱水ケーキまたはスラリーを焼成して、焼成物を得る焼成工程と、上記焼成物を破砕、切断または分級して、上記粒状の土工資材を得る粒状化工程、を含むことを特徴とする粒状の土工資材の製造方法。
［４］ 上記焼成の最高温度が、１，０７０〜１，１３０℃である、上記［３］に記載の粒状の土工資材の製造方法。
［５］ 上記粒状の土工資材が、埋め戻し材、埋め立て材、軽量盛り土材、エアーモルタル用骨材、路盤の下方の緩衝層用の緩衝材、軽量骨材、または、防音壁、断熱材、遮熱材もしくは防犯用の砂利である、上記［３］又は［４］に記載の粒状の土工資材の製造方法。
That is, the present invention provides the following [1] to [5].
[1] A granular earthwork material obtained by baking a dewatered cake or a slurry, the residue being formed after treating a rare earth-containing mud with an acid.
[2] The apparent density of earthwork materials of the granular is 0.7~1.6g / cm 3, granular earthwork materials according to the above [1].
[3] A method for producing the granular earthwork material according to the above [1] or [2], wherein the dehydration cake or slurry is fired to obtain a fired product; A granulating step of crushing, cutting or classifying the granular earthwork material to obtain the above-mentioned granular earthwork material.
[4] The method for producing a granular earthwork material according to the above [3], wherein the maximum temperature of the firing is 1,070 to 1,130 ° C.
[5] The granular earthwork material is a backfill material, a landfill material, a lightweight embankment material, an aggregate for air mortar, a buffer material for a buffer layer below a roadbed, a lightweight aggregate, or a soundproof wall, a heat insulating material, The method for producing a granular earthwork material according to the above [3] or [4], which is a heat shield or a gravel for crime prevention.
本発明の粒状の土工資材は、軽量であるため、軽量骨材等として利用することができる。
また、本発明の粒状の土工資材は、レアアースを含有する泥を酸で処理した後に発生する残渣以外の材料（ただし、少量の水酸化ナトリウム等を用いることはある。）を用いなくてよいため、低コストでかつ容易に製造することができる。
Since the granular earthwork material of the present invention is lightweight, it can be used as a lightweight aggregate or the like.
In addition, the granular earthwork material of the present invention does not need to use materials other than residues generated after treating rare earth-containing mud with acid (however, a small amount of sodium hydroxide or the like may be used). , Low cost and easy to manufacture.
本発明の粒状の土工資材は、レアアースを含有する泥を酸で処理した後に発生する残渣からなる、脱水ケーキまたはスラリーを焼成してなるものである。
本発明において、「レアアースを含有する泥を酸で処理した後に発生する残渣」（以下、「残渣」と略すことがある。）とは、レアアースを含有する泥を酸（例えば、希塩酸）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）からＬｕ（ルテチウム））に、Ｓｃ（スカンジウム）とＹ（イットリウム）を加えた１７元素をいう。
The granular earthwork material of the present invention is obtained by firing a dewatered cake or slurry consisting of residues generated after treating a rare earth-containing mud with acid.
In the present invention, "residue generated after treating a rare earth-containing mud with an acid" (hereinafter sometimes abbreviated as "residue") refers to treating a rare earth-containing mud with an acid (eg, dilute hydrochloric acid). And is an acidic residue generated after extracting the rare earth into the liquid.
The rare earths are 17 elements obtained by adding Sc (scandium) and Y (yttrium) to lanthroids of the third group of the periodic table (La (lanthanum) to Lu (lutetium)).
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；固形分）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。
As an example of mud containing a rare earth, the mud is distributed in a layered manner (for example, the ground from the seabed to a depth of about several tens of meters) on the deep sea floor (for example, a region of 3,500 to 6,000 m as the sea depth). And mud having a high rare earth content.
In the present invention, the content (by mass) of the rare earth in the mud containing the rare earth (dry matter; solid content) is preferably 1 or less from the viewpoint of economical efficiency when mining the rare earth as a resource. It is at least 2,000 ppm, more preferably at least 2,000 ppm.
残渣の含水比（残渣の固形分１００質量％に対する水分の割合）は、特に限定されないが、加熱炉等の加熱手段の負荷を軽減する観点から、好ましくは２００質量％以下、より好ましくは１５０質量％以下、特に好ましくは１００質量％以下である。
残渣の含水比を低減させる方法（方式）としては、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が挙げられる。
中でも、低コストで簡易に脱水することができる点で、沈澱方式およ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 residue (the ratio of water to 100% by mass of the solid content of the residue) is not particularly limited, but is preferably 200% by mass or less, more preferably 150% by mass, from the viewpoint of reducing the load on a heating means such as a heating furnace. %, Particularly preferably 100% by mass or less.
As a method (method) for reducing the water content of the residue, the mud is stored in a container such as a tank, and the solid content of the mud is precipitated, and the supernatant is collected. Examples include a separation method and a pressure dehydration method using a device such as a filter press.
Among them, the precipitation method and the centrifugal separation method are preferable, and the precipitation method is more preferable, since dehydration can be easily performed at low cost.
The degree of dehydration increases in the order of precipitation, centrifugation, and pressure dehydration.
本発明において、「残渣からなる、脱水ケーキまたはスラリー」とは、（ａ）残渣のみからなる、脱水ケーキまたはスラリー、（ｂ）残渣と、本発明の効果に大きな悪影響を与えない程度の小さな量で配合される、残渣以外の材料との混合物からなる、脱水ケーキまたはスラリー、のいずれかを意味する。
前記（ｂ）の場合、残渣以外の材料の例としては、水酸化ナトリウム、水酸化カルシウム、フライアッシュ等が挙げられる。
残渣以外の材料の形態としては、水溶液、懸濁液、粉状、粒状等が挙げられる。
残渣と残渣以外の材料の合計量１００質量部（残渣に含まれている水分や、残渣以外の材料として水溶液を用いる場合における当該水溶液中の水分を含む質量）に対する残渣以外の材料（水分を含まないもの；固形分）の配合量は、本発明の粒状の土工資材の軽量性を高める観点から、好ましくは５質量部未満、より好ましくは３質量部以下、さらに好ましくは２質量部以下、特に好ましくは１質量部以下である。
本発明において、「残渣からなる、脱水ケーキまたはスラリーを焼成してなるもの」とは、加熱による熔融によって減容するような過度の高温ではない、適度に高い温度での加熱によって、部分的にもしくは全体的に熔融が生じたものである。
In the present invention, “a dehydrated cake or slurry composed of a residue” means (a) a dehydrated cake or slurry composed of only a residue, and (b) a residue in a small amount that does not significantly affect the effects of the present invention. Means either a dewatered cake or a slurry, consisting of a mixture with materials other than the residue.
In the case of the above (b), examples of the material other than the residue include sodium hydroxide, calcium hydroxide, fly ash and the like.
Examples of the form of the material other than the residue include an aqueous solution, a suspension, a powder, and a granule.
The material other than the residue (including the water contained in the residue and the amount of water contained in the aqueous solution when an aqueous solution is used as the material other than the residue) is 100 parts by mass of the residue and the material other than the residue. The amount of the solid matter) is preferably less than 5 parts by mass, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, particularly from the viewpoint of increasing the lightness of the granular earthwork material of the present invention. It is preferably at most 1 part by mass.
In the present invention, "residues, which are obtained by firing a dewatered cake or slurry" are not excessively high temperatures, such as being reduced in volume by melting by heating, and are partially heated by moderately high temperatures. Alternatively, the entirety has been melted.
本発明の粒状の土工資材の見かけ密度は、好ましくは０．７〜１．６ｇ／ｃｍ３、より好ましくは０．８〜１．５ｇ／ｃｍ３、さらに好ましくは０．９〜１．４ｇ／ｃｍ３、特に好ましくは０．９〜１．２ｇ／ｃｍ３である。該値が０．７ｇ／ｃｍ３未満では、本発明の粒状の土工資材が脆くなり、埋め戻し材等の用途への適用が困難になることがある。該値が１．６ｇ／ｃｍ３を超えると、本発明の目的である軽量性を十分に達成することができない。なお、見かけ密度が１．０ｇ／ｃｍ３未満では、本発明の粒状の土工資材が水に浮くようになるため、用途が、コンクリートまたはモルタル用の軽量骨材以外のものに限定される。 The apparent density of the granular earthwork material of the present invention is preferably 0.7 to 1.6 g / cm 3 , more preferably 0.8 to 1.5 g / cm 3 , and still more preferably 0.9 to 1.4 g / cm 3 . cm 3 , particularly preferably 0.9 to 1.2 g / cm 3 . If the value is less than 0.7 g / cm 3 , the granular earthwork material of the present invention may become brittle, and it may be difficult to apply it to applications such as backfill materials. When the value exceeds 1.6 g / cm 3 , the light weight, which is the object of the present invention, cannot be sufficiently achieved. If the apparent density is less than 1.0 g / cm 3 , the granular earthwork material of the present invention floats on water, so that the application is limited to those other than lightweight aggregates for concrete or mortar.
本発明の粒状の土工資材は、埋め戻し材、埋め立て材、軽量盛り土材、エアーモルタル用骨材、路盤の下方の緩衝層用の緩衝材、軽量骨材（例えば、モルタル用の軽量細骨材や、コンクリート用の軽量細骨材もしくは軽量粗骨材や、アスファルト用の軽量骨材）、上記軽量骨材（エアーモルタル用骨材、軽量骨材）以外の特定の用途の砂利（例えば、防音壁、断熱材、遮熱材もしくは防犯用の砂利）等として用いることができる。 The granular earthwork material of the present invention includes backfill material, landfill material, lightweight embankment material, aggregate for air mortar, cushioning material for a buffer layer below a roadbed, lightweight aggregate (for example, lightweight fine aggregate for mortar). Gravel for specific applications other than the above-mentioned lightweight aggregates (eg, aggregates for air mortar, lightweight aggregates), lightweight fine aggregates or lightweight coarse aggregates for concrete, and lightweight aggregates for asphalt). It can be used as a wall, a heat insulating material, a heat shielding material or a gravel for crime prevention).
次に、本発明の粒状の土工資材の製造方法について説明する。
本発明の粒状の土工資材の製造方法は、レアアースを含有する泥を酸で処理した後に発生する残渣からなる、脱水ケーキまたはスラリーを焼成して、焼成物を得る焼成工程と、この焼成物を破砕、切断または分級して、粒状の土工資材を得る粒状化工程、を含む。
以下、工程毎に説明する。
Next, a method for producing a granular earthwork material of the present invention will be described.
The method for producing a granular earthwork material of the present invention comprises a firing step of firing a dehydrated cake or slurry consisting of a residue generated after treating a mud containing a rare earth with acid to obtain a fired product, A granulation step of crushing, cutting or classifying to obtain a granular earthwork material.
Hereinafter, each step will be described.
［焼成工程］
焼成工程は、レアアースを含有する泥を酸で処理した後に発生する残渣（通常、酸性のもの）からなる、脱水ケーキまたはスラリー（以下、「焼成原料」ともいう。）を焼成して、焼成物を得る工程である。
残渣は、上述のとおり、含水比を小さくするための処理を予め施しておくことが望ましい。
残渣以外の材料を用いる場合、造粒の前に、残渣と、残渣以外の材料を混合して、混合物を調製しておく。
焼成原料は、製造の目的物である土工資材の種類（例えば、粗骨材）に応じて、適宜の大きさの粒状物に形成してもよい。
また、焼成原料は、加熱の前に乾燥させてもよい。
[Firing step]
In the baking step, a dehydrated cake or slurry (hereinafter, also referred to as “baking raw material”) composed of a residue (usually acidic) generated after treating a rare earth-containing mud with an acid is fired to obtain a fired product. This is the step of obtaining
As described above, the residue is desirably subjected to a treatment for reducing the water content in advance.
When a material other than the residue is used, the mixture is prepared by mixing the residue and the material other than the residue before granulation.
The firing raw material may be formed into a granular material having an appropriate size in accordance with the type (for example, coarse aggregate) of the earthwork material that is the object of production.
Further, the firing raw material may be dried before heating.
焼成原料を適宜の大きさの粒状物に形成する場合、用途に応じた焼成原料の好ましい粒度は、以下のとおりである。
焼成物の用途が、軽量粗骨材、または、防音壁、断熱材、遮熱材もしくは防犯用の砂利である場合、加熱前の造粒物は、好ましくは、５〜４０ｍｍの粒度を有する粒体を、５０質量％以上の割合で含むものであり、より好ましくは、７〜３０ｍｍの粒度を有する粒体を、５０質量％以上の割合で含むものである。
焼成物の用途が、軽量細骨材、または、エアーモルタル用骨材である場合、加熱前の造粒物は、好ましくは、３〜５ｍｍの粒度を有する粒体を、５０質量％以上の割合で含むものである。
焼成物の用途が、埋め戻し材、埋め立て材、または、軽量盛り土材である場合、加熱前の造粒物は、好ましくは、５〜３０ｍｍの粒度を有する粒体を、５０質量％以上の割合で含むものである。
焼成物の用途が、路盤の下方の緩衝層用の緩衝材である場合、加熱前の造粒物は、好ましくは、３〜１０ｍｍの粒度を有する粒体を、５０質量％以上の割合で含むものである。
本発明では、通常、造粒機や成形機を用いた造粒方法を採用するので、上述の好ましい粒度分布を有する造粒物は、容易に得ることができる。
When the firing raw material is formed into a granular material having an appropriate size, preferred particle sizes of the firing raw material according to the application are as follows.
When the use of the fired product is a lightweight coarse aggregate, or a soundproof wall, a heat insulating material, a heat shield or a gravel for crime prevention, the granulated material before heating is preferably a granule having a particle size of 5 to 40 mm. It contains the particles in a proportion of 50% by mass or more, and more preferably contains particles having a particle size of 7 to 30 mm in a ratio of 50% by mass or more.
When the use of the fired product is a lightweight fine aggregate or an aggregate for air mortar, the granulated material before heating is preferably a granule having a particle size of 3 to 5 mm by a ratio of 50% by mass or more. Is included.
When the use of the fired product is a backfill material, a landfill material, or a lightweight embankment material, the granulated material before heating is preferably a granule having a particle size of 5 to 30 mm by a ratio of 50% by mass or more. Is included.
When the use of the fired product is a buffer material for a buffer layer below a roadbed, the granulated material before heating preferably contains granules having a particle size of 3 to 10 mm in a proportion of 50% by mass or more. It is a thing.
In the present invention, since a granulation method using a granulator or a molding machine is usually employed, a granulated product having the above preferable particle size distribution can be easily obtained.
焼成物を得るための加熱温度（加熱時の最高温度）は、好ましくは１，０７０〜１，１３０℃、より好ましくは１，０８０〜１，１２０℃、特に好ましくは１，０９０〜１，１１０℃である。該温度が１，０７０℃以上であると、発泡による十分な軽量性を焼成物に与えることが容易になる。該温度が１，１３０℃以下であると、過度な溶融が生じて、減容し、密度が高い焼成物となるのを防ぐことができる。 The heating temperature (the maximum temperature during heating) for obtaining a fired product is preferably 1,070 to 1,130 ° C, more preferably 1,080 to 1,120 ° C, and particularly preferably 1,090 to 1,110 ° C. ° C. When the temperature is 1,070 ° C. or higher, it becomes easy to give the fired product sufficient lightness due to foaming. When the temperature is 1,130 ° C. or less, excessive melting occurs, the volume is reduced, and it is possible to prevent a fired product having a high density.
焼成工程における最高温度での加熱時間は、好ましくは１５〜４０分間、より好ましくは１５〜３０分間、特に好ましくは２０〜２５分間である。該加熱時間が１５分間以上であると、造粒物が十分に膨張しながら焼成されるので、焼成物に軽量性を与えることが容易となる。該加熱時間が４０分間以下であると、処理効率（本発明の粒状の土工資材の製造効率）の点で好ましい。なお、小径の造粒物と異なり、大塊の状態で焼成する場合には、大塊の内部への十分な熱伝導に多くの時間を要するため、最高温度での加熱時間は、長くなる。 The heating time at the highest temperature in the firing step is preferably 15 to 40 minutes, more preferably 15 to 30 minutes, and particularly preferably 20 to 25 minutes. When the heating time is 15 minutes or more, the granulated material is fired while expanding sufficiently, and thus it is easy to give the fired product light weight. It is preferable that the heating time is 40 minutes or less in terms of processing efficiency (production efficiency of the granular earthwork material of the present invention). In addition, unlike the small-diameter granulated material, when firing in a large lump, a large amount of time is required for sufficient heat conduction to the inside of the large lump, so that the heating time at the maximum temperature becomes long.
焼成物を得るための加熱手段としては、特に限定されるものではなく、連続式の手段とバッチ式の手段のいずれも用いることができる。
連続式の加熱手段としては、例えば、ロータリーキルン、トンネル炉等が挙げられる。
バッチ式の加熱手段としては、例えば、焼却炉（ガス等を燃料として用いるもの）、電気炉、マイクロ波加熱装置等が挙げられる。
中でも、処理の効率を高める観点から、ロータリーキルンを用いることが好ましい。
焼成工程で得られる焼成物は、通常、独立した粒体と、複数の粒体が連なった塊（２個以上の塊が融着部分を介して結合したもの）の混合物である。焼成物の全量中の独立した粒体の割合は、通常、２０質量％以下である。このため、本発明において、焼成工程の後に、粒状化工程が必要である。
The heating means for obtaining the fired product is not particularly limited, and either a continuous means or a batch means can be used.
Examples of the continuous heating means include a rotary kiln and a tunnel furnace.
Examples of batch-type heating means include an incinerator (using gas or the like as fuel), an electric furnace, a microwave heating device, and the like.
Among them, it is preferable to use a rotary kiln from the viewpoint of increasing the processing efficiency.
The calcined product obtained in the calcining step is usually a mixture of independent granules and a mass of a plurality of continuous granules (a mass in which two or more masses are connected via a fused portion). The proportion of independent granules in the total amount of the fired product is usually 20% by mass or less. For this reason, in the present invention, a granulation step is required after the firing step.
［粒状化工程］
粒状化工程は、焼成工程で得た焼成物を破砕、切断または分級して、粒状の土工資材を得る工程である。
破砕または切断のための手段としては、焼成工程で得られた焼成物を破砕または切断することができるものであればよく、特に限定されないが、例えば、破砕のための手段としては、ジョークラッシャー、インパクトクラッシャ等が挙げられ、また、切断のための手段としては、ワイヤーソー、ダイヤモンドカッター等が挙げられる。
また、分級のための手段としては、篩等が挙げられる。なお、分級で得られた粗粒分については、さらに、破砕または切断を行って、粒状物を得て、この粒状物を、細粒分（本発明の粒状の土工資材）と共に、または、細粒分（本発明の粒状の土工資材）とは別の用途で、本発明の粒状の土工資材として用いることができる。
[Granulation step]
The granulation step is a step of crushing, cutting or classifying the fired material obtained in the firing step to obtain a granular earthwork material.
The means for crushing or cutting is not particularly limited as long as it can crush or cut the fired product obtained in the firing step, and examples thereof include, for example, jaw crushers, An impact crusher and the like can be mentioned, and as a means for cutting, a wire saw, a diamond cutter and the like can be mentioned.
As a means for classification, a sieve or the like can be used. The coarse particles obtained by the classification are further crushed or cut to obtain granules, and the granules are mixed with the fine particles (the granular earthwork material of the present invention) or It can be used as the granular earthwork material of the present invention for a purpose other than the particle (the granular earthwork material of the present invention).
以下、本発明を実施例によって具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
［材料］
以下の材料を使用した。
（１）レアアースを含有する泥（太平洋の水深４，０００ｍ以上の深海の泥；該泥の固形分中のレアアースの含有率：質量基準で２，０００ｐｐｍ以上）
（２）水酸化カルシウム（試薬）
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
[material]
The following materials were used:
(1) Mud containing rare earth (mud in the deep sea with a water depth of 4,000 m or more in the Pacific Ocean; rare earth content in solid content of the mud: 2,000 ppm or more by mass)
(2) Calcium hydroxide (reagent)
［実施例１］
レアアースを含有する泥を、０．１Ｎの塩酸に１時間浸漬し、次いで、含水比が１００質量％になるように、遠心分離装置で脱水して、残渣を得た。
この残渣を、凹部の大きさが異なる複数の種類の製氷皿を用いて、造粒（成型）し、造粒物（粒度：５〜３０ｍｍ）を得た。
この造粒物を、１０５℃で１２時間乾燥後、電気炉内で１０℃／分で昇温し、最高温度１，１００℃で２０分間、加熱した。
得られた焼成物（粒度：焼成後に５〜３５ｍｍ）について、見かけ密度の測定、および、外観観察を行った。
その結果を表１に示す。
次いで、得られた焼成物を、破砕手段（ハンマー）を用いて破砕することによって、焼成物に含まれている、複数の粒体が連なった塊を、独立した粒体とし、本発明の粒状の土工資材を得た。
[Example 1]
The mud containing the rare earth was immersed in 0.1 N hydrochloric acid for 1 hour, and then dehydrated with a centrifugal separator so as to have a water content of 100% by mass to obtain a residue.
The residue was granulated (molded) using a plurality of types of ice trays having different recess sizes to obtain a granulated product (particle size: 5 to 30 mm).
The granulated product was dried at 105 ° C. for 12 hours, then heated in an electric furnace at a rate of 10 ° C./min, and heated at a maximum temperature of 1,100 ° C. for 20 minutes.
With respect to the obtained fired product (particle size: 5 to 35 mm after firing), the apparent density was measured and the appearance was observed.
Table 1 shows the results.
Next, the obtained calcined material is crushed using a crushing means (hammer), so that a mass of a plurality of continuous granules contained in the calcined material is converted into an independent granule, and the granular material of the present invention is obtained. Earthwork material was obtained.
［比較例１〜２］
表１に示すように最高温度を変更したこと以外は、実施例１と同様にして実験した。
ただし、比較例１では、造粒物同士の融着が生じなかったため、破砕等は、行わなかった。比較例２では、破砕によって、独立した粒体をほぼ１００％の割合で得ることができた。
［比較例３〜４］
残渣（１００質量部）に代えて、残渣８０質量部と水酸化カルシウム２０質量部の混合物を用いたこと、および、最高温度を表１に示す温度に変更したこと以外は、実施例１と同様にして実験した。
ただし、比較例３では、造粒物同士の融着が生じなかったため、破砕等は、行わなかった。比較例４では、破砕の後、得られた土工資材の全量中、粒状物（大塊以外のもの）の割合は、目視で観察したところ、１０質量％以下であった。
比較例１〜４における見かけ密度および外観観察の結果を、表１に示す。
[Comparative Examples 1-2]
The experiment was performed in the same manner as in Example 1 except that the maximum temperature was changed as shown in Table 1.
However, in Comparative Example 1, crushing and the like were not performed because no fusion of the granulated materials occurred. In Comparative Example 2, independent granules could be obtained at a rate of almost 100% by crushing.
[Comparative Examples 3 and 4]
Same as Example 1 except that a mixture of 80 parts by mass of the residue and 20 parts by mass of calcium hydroxide was used instead of the residue (100 parts by mass), and the maximum temperature was changed to the temperature shown in Table 1. And experimented.
However, in Comparative Example 3, crushing and the like were not performed because no fusion of the granules occurred. In Comparative Example 4, after crushing, the proportion of particulate matter (other than large lumps) in the total amount of the obtained earthwork material was 10% by mass or less when visually observed.
Table 1 shows the results of the apparent density and the appearance observation in Comparative Examples 1 to 4.
表１から、実施例１では、比較例１〜４に比べて、優れた軽量性（小さな見かけ密度）を有する粒状の土工資材を得ていることがわかる。
一方、比較例１〜２では、実施例１に比べて最高温度が低いため、実施例１に比べて軽量性が劣ることがわかる。また、比較例３〜４では、水酸化カルシウムを大きな割合（２０質量％）で配合しているため、実施例１と同等以上の最高温度で加熱を行ったにもかかわらず、実施例１に見られるような優れた軽量性が得られておらず、また、加熱温度の増大（比較例３の１，１００℃から比較例４の１，２００℃への増大）による軽量性の向上の効果も得られていないことがわかる。
From Table 1, it can be seen that in Example 1, a granular earthwork material having excellent lightness (small apparent density) was obtained as compared with Comparative Examples 1 to 4.
On the other hand, in Comparative Examples 1 and 2, since the maximum temperature is lower than that in Example 1, it can be seen that the lightness is inferior to that in Example 1. Further, in Comparative Examples 3 and 4, since calcium hydroxide was blended in a large proportion (20% by mass), the heating was performed at the highest temperature equal to or higher than that of Example 1; As seen, excellent lightness is not obtained, and the effect of improving lightness by increasing the heating temperature (from 1,100 ° C. in Comparative Example 3 to 1,200 ° C. in Comparative Example 4). It can be seen that the same was not obtained.
Claims (3)
上記脱水ケーキまたはスラリーを、５〜４０ｍｍの粒度を有する粒体を、５０質量％以上の割合で含む造粒物に形成した後、焼成して、独立した粒体と、複数の粒体が連なった塊の混合物である焼成物を得る焼成工程と、
上記焼成物を破砕、切断または分級して、上記粒状の土工資材を得る粒状化工程、を含み、
上記焼成工程において、焼成の最高温度が１，０７０〜１，１３０℃で、かつ、１，０７０〜１，１３０℃の温度範囲内での加熱時間が１５〜４０分間であり、
上記粒状の土工資材の見かけ密度が、０．７〜１．６ｇ／ｃｍ ３ であることを特徴とする粒状の土工資材の製造方法。 A method for producing a granular earthwork material obtained by calcining a dehydrated cake or slurry, consisting of only residues generated after treating a rare earth-containing mud with acid ,
After forming the dewatered cake or slurry into granules containing granules having a particle size of 5 to 40 mm at a ratio of 50% by mass or more, the granules are fired, and the independent granules and a plurality of granules are connected. A firing step of obtaining a fired product that is a mixture of lumps,
Crushing the fired product, cutting or classifying, including a granulation step of obtaining the granular earthwork material,
In the firing step, the maximum firing temperature is 1,070 to 1,130 ° C, and the heating time in the temperature range of 1,070 to 1,130 ° C is 15 to 40 minutes,
Apparent density of the earthwork materials of the granular method for earthwork material particulate which is a 0.7~1.6g / cm 3.
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| JP3552173B2 (en) * | 1995-03-14 | 2004-08-11 | 三機工業株式会社 | Manufacturing method of lightweight aggregate using sewage sludge incineration ash |
| JP2006043678A (en) * | 2004-08-06 | 2006-02-16 | Kangen Yoyu Gijutsu Kenkyusho:Kk | Leachate sludge treating system for reclaimed land and leachate sludge treating method for reclaimed land |
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| JP6268583B2 (en) * | 2013-12-25 | 2018-01-31 | 太平洋セメント株式会社 | Method for producing fired product |
| JP6493719B2 (en) * | 2014-01-10 | 2019-04-03 | 太平洋セメント株式会社 | Method for treating mud containing rare earth |
| JP6633885B2 (en) * | 2015-10-22 | 2020-01-22 | 太平洋セメント株式会社 | Manufacturing method of earthwork material |
| JP6659303B2 (en) * | 2015-10-22 | 2020-03-04 | 太平洋セメント株式会社 | Manufacturing method of earthwork material |
| JP6654758B2 (en) * | 2016-01-20 | 2020-02-26 | 太平洋セメント株式会社 | Method for treating residue containing rare earth |
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