JPH06154594A - Volcanic ash adsorbent and manufacture of the same - Google Patents
Volcanic ash adsorbent and manufacture of the sameInfo
- Publication number
- JPH06154594A JPH06154594A JP31886592A JP31886592A JPH06154594A JP H06154594 A JPH06154594 A JP H06154594A JP 31886592 A JP31886592 A JP 31886592A JP 31886592 A JP31886592 A JP 31886592A JP H06154594 A JPH06154594 A JP H06154594A
- Authority
- JP
- Japan
- Prior art keywords
- volcanic ash
- adsorbent
- adsorption
- water
- soil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、排水中のホスフィン酸
イオン、ホスホン酸イオン、テトラフルオロホウ酸イオ
ン、重金属イオン(鉛イオン)等の有害イオンを吸着除去
するために有効な吸着用火山灰土壌及びその製造方法に
関する。The present invention relates to a volcanic ash soil for adsorption which is effective for adsorbing and removing harmful ions such as phosphinate ion, phosphonate ion, tetrafluoroborate ion and heavy metal ion (lead ion) in wastewater. And a manufacturing method thereof.
【０００２】[0002]
【従来の技術・課題】電子部品等に広く利用されている
金属めっき処理において、排水の浄化が問題となってい
る。例えば、富栄養化現象の原因物質の１つであるリン
酸を含む化学薬品等が各種めっき工程で使用されてい
る。特に化学ニッケルめっきではホスフィン酸イオンは
ニッケルイオンを還元してホスホン酸イオンとなり、ニ
ッケルが析出する。従って、この排水中には、ホスフィ
ン酸イオン、ホスホン酸イオン等が存在している。これ
らのイオンは酸化処理してオルトリン酸イオンとし、更
に化学薬品等を添加して沈澱除去する方法や吸着除去す
る方法が行われている。2. Description of the Related Art Purification of waste water has become a problem in metal plating treatment widely used for electronic parts and the like. For example, chemicals containing phosphoric acid, which is one of the causative substances of the eutrophication phenomenon, are used in various plating processes. Particularly in chemical nickel plating, phosphinate ions reduce nickel ions to phosphonate ions, and nickel is deposited. Therefore, phosphinate ions, phosphonate ions, etc. are present in this waste water. Oxidation treatment of these ions to orthophosphate ions is followed by a method of adding a chemical agent or the like to remove by precipitation or a method of removing by adsorption.
【０００３】吸着除去に使用する吸着剤として、リン吸
着特性を有する火山灰土壌について検討がなされてい
る。火山灰土壌自身は水中で容易に破壊してしまう欠点
があり、その改善策として、火山灰土壌を(１)造粒後高
温で熱処理したり、(２)結合剤を添加して造粒する方法
や、(３)湿式粉砕後圧縮成形してこれを解砕造粒する方
法が採られている。As an adsorbent used for adsorption removal, a volcanic ash soil having a phosphorus adsorption property has been studied. Volcanic ash soil itself has a drawback that it is easily destroyed in water. To improve it, (1) heat treat the volcanic ash soil at high temperature after granulation, or (2) granulate by adding a binder. (3) A method of wet-grinding, compression-molding, and then crushing and granulating is adopted.
【０００４】例えば、(３)湿式粉砕後圧縮成形してこれ
を解砕造粒する方法として特公平４−21538号公報に
は、膠質土をミックスマラー型混練機により線圧１０ｔ
／ｃｍまで加圧力で加圧混練して予備圧縮し、この予備
圧縮した原料を自然風乾により水分を５〜２５％にコン
トロールし、もって造粒原料とし、該造粒原料をブリケ
ットマシンにより線圧２.０〜５.０ｔ／ｃｍの加圧力で
加圧成形して１ｍｍ以上の大きさに造粒するか、若しく
は造粒原料を平滑ロールにより線圧２.０〜５.０ｔ／ｃ
ｍの加圧力で平板上に成形した後粉砕機にかけて粉砕
し、０.５ｍｍ以上の大きさのものを篩別することを特
徴とするリン化合物吸着用粒土の製造方法が開示されて
いる。For example, (3) as a method of crushing and granulating by compression-molding after wet-milling, Japanese Patent Publication No. 4-21538 discloses a colloidal soil with a mix muller type kneader at a linear pressure of 10 t.
/ Cm to be kneaded with a pressing force and pre-compressed, and the pre-compressed raw material is controlled to have a water content of 5 to 25% by natural air-drying to be used as a granulating raw material, and the granulating raw material is linearly compressed by a briquette machine. Press-mold with a pressure of 2.0 to 5.0 t / cm to granulate to a size of 1 mm or more, or granulate raw material with a smooth roll at a linear pressure of 2.0 to 5.0 t / c.
Disclosed is a method for producing a granular soil for adsorbing a phosphorus compound, which comprises molding on a flat plate with a pressing force of m, crushing with a crusher, and sieving one having a size of 0.5 mm or more.
【０００５】しかし、上記(１)の方法は多量のエネルギ
ーを消費し、(２)は余分な資材を必要とし、更に結合剤
により使用範囲が限定されるという欠点がある。また、
(３)による造粒物はバリを有し、割れ易く不規則な形状
のため流動性が悪く、吸着設備等を傷付け易く、カラム
法等に適さないという欠点がある。However, the method (1) consumes a large amount of energy, the method (2) requires extra materials, and has a drawback that the range of use is limited by the binder. Also,
The granulated product according to (3) has deficiencies in that it has burrs, is easily broken, and has an irregular shape and thus has poor fluidity, which easily damages adsorption equipment and the like and is not suitable for a column method or the like.
【０００６】上述のようにホスフィン酸イオン、ホスホ
ン酸イオン等についての経済的に有利かつ有効な除去方
法は見出されておらず、従って、排水による富栄養化現
象は更に促進されているのが現状である。As described above, an economically advantageous and effective method for removing phosphinate ions, phosphonate ions, etc. has not been found, and therefore, the phenomenon of eutrophication by waste water is further promoted. The current situation.
【０００７】従って、本発明の目的は、上述の課題を解
決すると共に嵩比重が小さくても水中破壊が少なく、低
コストの球状であることを特徴とする吸着用火山灰土壌
及びその製造方法を提供し、この吸着用火山灰土壌を使
用することによりカラム法等でのホスフィン酸イオン、
ホスホン酸イオン等の吸着除去ができ、排水処理を簡易
化することにある。Therefore, an object of the present invention is to solve the above-mentioned problems and to provide a volcanic ash soil for adsorption which is characterized in that it has a spherical shape at a low cost with less destruction in water even if the bulk specific gravity is small, and a method for producing the same. However, by using this adsorption volcanic ash soil, phosphinate ions in the column method,
The purpose is to adsorb and remove phosphonate ions, etc., and to simplify wastewater treatment.
【０００８】[0008]
【課題を解決するための手段】本発明に係る吸着用火山
灰土壌は、Ｓｉ１８〜２４％、Ａｌ２３〜２９％、Ｆｅ
１〜５％の化学組成を有し、アロフェンを主成分とする
火山灰土壌を造粒して得られる実質上添加剤を含まない
嵩比重０.５〜０.７、水中破壊率２５％以下の球状造粒
物よりなることを特徴とする。The volcanic ash soil for adsorption according to the present invention is composed of Si 18 to 24%, Al 23 to 29%, and Fe.
It has a chemical composition of 1 to 5% and is obtained by granulating a volcanic ash soil containing allophane as a main component, and practically does not contain any additive, has a bulk specific gravity of 0.5 to 0.7, and a water destruction rate of 25% or less. It is characterized in that it is composed of spherical granules.
【０００９】また、上記吸着用火山灰土壌は、Ｓｉ１８
〜２４％、Ａｌ２３〜２９％、Ｆｅ１〜５％の化学組成
を有し、アロフェンを主成分とする火山灰土壌の水分を
２４〜３７％に調整して混合撹拌型造粒機により造粒
し、その後乾燥することを特徴として製造することがで
きる。The adsorbed volcanic ash soil is Si18
-24%, Al23-29%, Fe1-5% chemical composition, and adjust the water content of the volcanic ash soil containing allophane as the main component to 24-37% and granulate with a mixing and stirring granulator, It can be manufactured by being characterized by being dried thereafter.
【００１０】[0010]
【作用】本発明の吸着用火山灰土壌は、風乾または強制
乾燥した火山灰土壌を原料とし、水分を２４〜３７％に
調整し、または必要に応じて水分を補給し混合撹拌型造
粒機により最大周速４０ｍ／秒以下で造粒し、得られた
造粒物の嵩比重が０.５〜０.７で、水中破壊率が２５％
以下の球状で実質上添加剤を含まないことを特徴とする
ものである。The adsorbed volcanic ash soil of the present invention is prepared by using air-dried or forced-dried volcanic ash soil as a raw material, adjusting the water content to 24 to 37%, or replenishing the water if necessary, and using a mixing and stirring granulator to maximize the content. Granulated at a peripheral speed of 40 m / sec or less, the obtained granulated product has a bulk specific gravity of 0.5 to 0.7 and a destruction rate in water of 25%.
It is characterized by having the following spherical shape and containing substantially no additive.
【００１１】本発明の吸着用火山灰土壌の製造方法にお
いて、水分が上述の範囲を超える場合には収率が極端に
低下し、または付着等の問題により所望する嵩比重の火
山灰球状土壌が得られなくなる。また、得られた火山灰
球状土壌の嵩比重が０.５より小さいと、水中破壊が極
端に増加してくることによが実験結果により判り、０.
７より大きいものは混合撹拌型造粒機での造粒操作が難
しくなるために好ましくない。In the method for producing a volcanic ash soil for adsorption of the present invention, when the water content exceeds the above range, the yield is extremely decreased, or due to problems such as adhesion, volcanic ash spherical soil having a desired bulk density can be obtained. Disappear. In addition, it was found from the experimental results that the underwater destruction would increase extremely when the bulk specific gravity of the obtained volcanic ash spherical soil was less than 0.5.
If it is larger than 7, the granulation operation by the mixing and stirring type granulator becomes difficult, which is not preferable.
【００１２】[0012]
実施例１〜２及び比較例１ 火山灰土壌は、山梨県八ケ岳山麓の地表面下１.５〜２.
５ｍの黄褐色土壌(Ｓｉ２２％、Ａｌ２６％、Ｆｅ３％)
を用い、多量に含んだ水分を風乾し、水分を２３〜３３
％に調整してヘンシェル型ミキサーにより造粒した。こ
れを乾燥してその中から篩分けした吸着用火山灰土壌に
ついて諸特性を測定した結果を表１に示す。Examples 1 and 2 and Comparative Example 1 Volcanic ash soils are 1.5-2. Below the ground surface at the foot of Yatsugatake, Yamanashi Prefecture.
5m yellowish brown soil (Si22%, Al26%, Fe3%)
Air-dry a large amount of water using
% And granulated with a Henschel mixer. Table 1 shows the results of measuring various characteristics of the adsorbed volcanic ash soil which was dried and sieved from the dried soil.
【００１３】比較例２ 造粒時にＰＴＦＥ樹脂を結合剤として外掛で３％添加
し、乾燥後焼成して得られたものである。Comparative Example 2 This was obtained by adding 3% of PTFE resin as a binder to the outside during granulation, drying and firing.
【００１４】参考例 乾燥した火山灰土壌の中から３ｍｍ以下のものを篩分け
し、その諸特性を測定した。Reference Example From the dried volcanic ash soil, one having a size of 3 mm or less was sieved and various properties were measured.
【００１５】[0015]
【表１】 [Table 1]
【００１６】＊１：造粒時水分は、造粒後の吸着用火山
灰土壌を１２０℃で３時間処理して求めたものである。 ＊２：吸着量１は、Ｈ3ＰＯ3及びＨ3ＰＯ2を用いてリン
として１００ｍｇ／リットルの試験液を調製し、直径１
〜３ｍｍの吸着用火山灰土壌３ｇを充填したカラムに試
験液を１ｍＬ／分の流速で通してフラクションコレクタ
ーで流出液を採取した。この流出液は高周波プラズマ発
光分光分析装置により検量線法で分析してリンの吸着量
を求めた。 ＊３：吸着量２は、Ｈ3ＰＯ3及びＨ3ＰＯ2を用いてリン
として５００ｍｇ／リットルの試験液を調製し、直径１
〜３ｍｍの吸着用火山灰土壌３ｇを充填したカラムに試
験液１ｍＬ／分の流速で通してフラクションコレクター
で流出液を採取した。この流出液は高周波プラズマ発光
分光分析装置により検量線法で分析してリンの吸着量を
求めた。 ＊４：水中破壊率は、２００ｍｌ共栓付三角フラスコに
４〜５ｍｍの吸着用火山灰土壌１５ｇを分取し、１００
ｇの蒸留水を加えて振幅５ｃｍ、３００サイクル／分で
２時間処理後、６メッシュの篩上に取り水洗して１５０
℃で乾燥して秤量し、破壊重量率を算出した。 ＊５：圧壊強度は、直径３〜５ｍｍの吸着用火山灰土壌
について直径６ｍｍのロッド棒で圧縮し、破壊した時の
荷重である。 ＊６：この吸着量は、Ｈ3ＰＯ3及びＨ3ＰＯ2を用いてリ
ンとして１００ｍｇ／リットル、５００ｍｇ／リットル
の試験液を調製し、乾燥した火山灰土壌０.５ｇを共栓
付三角フラスコに取り、試験液を加えて撹拌しながら４
８時間処理した。次に、上澄みを濾過して高周波プラズ
マ発光分光分析装置により分析してリンの吸着量を求め
た。* 1: The water content during granulation is obtained by treating the adsorbed volcanic ash soil after granulation at 120 ° C. for 3 hours. * 2: Adsorption amount 1 was 100 mg / liter of phosphorus as a test solution prepared using H 3 PO 3 and H 3 PO 2 and had a diameter of 1
The test liquid was passed through a column filled with 3 g of a 3 mm adsorption volcanic ash soil at a flow rate of 1 mL / min to collect the effluent with a fraction collector. This effluent was analyzed by a calibration curve method using a high-frequency plasma emission spectrophotometer to determine the adsorption amount of phosphorus. * 3: Adsorption amount 2 was 500 mg / liter of phosphorus as a test liquid prepared using H 3 PO 3 and H 3 PO 2 , and the diameter was 1
The effluent was collected with a fraction collector by passing it through a column filled with 3 g of a 3 mm adsorption volcanic ash soil at a flow rate of 1 mL / min of the test solution. This effluent was analyzed by a calibration curve method using a high-frequency plasma emission spectrophotometer to determine the adsorption amount of phosphorus. * 4: Destruction rate in water is 100 for 100g of 4-5mm adsorption volcanic ash soil in a 200ml Erlenmeyer flask with stopper.
Distilled water (g) was added, and the mixture was treated at an amplitude of 5 cm and 300 cycles / min for 2 hours, and then taken on a 6-mesh sieve and washed with water to 150
It was dried at ℃ and weighed to calculate the breaking weight ratio. * 5: The crushing strength is the load when a volcanic ash soil for adsorption having a diameter of 3 to 5 mm is compressed with a rod rod having a diameter of 6 mm and destroyed. * 6: For this adsorption amount, test solutions of 100 mg / l and 500 mg / l as phosphorus were prepared using H 3 PO 3 and H 3 PO 2, and 0.5 g of dried volcanic ash soil was placed in an Erlenmeyer flask with a stopper. Take, add the test solution and stir 4
Treated for 8 hours. Next, the supernatant was filtered and analyzed by a high-frequency plasma emission spectrophotometer to determine the adsorption amount of phosphorus.
【００１７】[0017]
【発明の効果】本発明の吸着用火山灰土壌は、嵩比重が
小さくても水中崩壊が少なく、更に、火山灰土壌を原料
としているために低コストであり、この吸着用火山灰土
壌を使用することによりカラム法等でのホスフィン酸イ
オン、ホスホン酸イオン等の効率的な吸着除去ができ、
排水処理を簡易化することができる。The adsorbed volcanic ash soil of the present invention is less likely to collapse in water even if it has a low bulk specific gravity, and is low in cost because it is made from volcanic ash soil. Efficient adsorption removal of phosphinate ion, phosphonate ion, etc. by column method etc.
Wastewater treatment can be simplified.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年４月１２日[Submission date] April 12, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 火山灰吸着剤及びその製造方法 Title : Volcanic ash adsorbent and method for producing the same
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、排水中のホスフィン酸
イオン、ホスホン酸イオン、テトラフルオロホウ酸イオ
ン、重金属イオン(鉛イオン)等の有害イオンを吸着除去
するために有効な火山灰吸着剤及びその製造方法に関す
る。TECHNICAL FIELD The present invention relates to a volcanic ash adsorbent which is effective for adsorbing and removing harmful ions such as phosphinate ions, phosphonate ions, tetrafluoroborate ions, and heavy metal ions (lead ions) in wastewater. The manufacturing method is related.
【０００２】[0002]
【従来の技術・課題】電子部品等に広く利用されている
金属めっき処理において、排水の浄化が問題となってい
る。例えば、富栄養化現象の原因物質の１つであるリン
酸を含む化学薬品等が各種めっき工程で使用されてい
る。特に化学ニッケルめっきではホスフィン酸イオンは
ニッケルイオンを還元してホスホン酸イオンとなり、ニ
ッケルが析出する。従って、この排水中には、ホスフィ
ン酸イオン、ホスホン酸イオン等が存在している。これ
らのイオンは酸化処理してオルトリン酸イオンとし、更
に化学薬品等を添加して沈澱除去する方法や吸着除去す
る方法が行われている。2. Description of the Related Art Purification of waste water has become a problem in metal plating treatment widely used for electronic parts and the like. For example, chemicals containing phosphoric acid, which is one of the causative substances of the eutrophication phenomenon, are used in various plating processes. Particularly in chemical nickel plating, phosphinate ions reduce nickel ions to phosphonate ions, and nickel is deposited. Therefore, phosphinate ions, phosphonate ions, etc. are present in this waste water. Oxidation treatment of these ions to orthophosphate ions is followed by a method of adding a chemical agent or the like to remove by precipitation or a method of removing by adsorption.
【０００３】吸着除去に使用する吸着剤として、リン吸
着特性を有する火山灰土壌について検討がなされてい
る。火山灰土壌自身は水中で容易に破壊してしまう欠点
があり、その改善策として、火山灰土壌を(１)造粒後高
温で熱処理したり、(２)結合剤を添加して造粒する方法
や、(３)湿式粉砕後圧縮成形してこれを解砕造粒する方
法が採られている。As an adsorbent used for adsorption removal, a volcanic ash soil having a phosphorus adsorption property has been studied. Volcanic ash soil itself has a drawback that it is easily destroyed in water. To improve it, (1) heat treat the volcanic ash soil at high temperature after granulation, or (2) granulate by adding a binder. (3) A method of wet-grinding, compression-molding, and then crushing and granulating is adopted.
【０００４】例えば、(３)湿式粉砕後圧縮成形してこれ
を解砕造粒する方法として特公平４−21538号公報に
は、膠質土をミックスマラー型混練機により線圧１０ｔ
／ｃｍまで加圧力で加圧混練して予備圧縮し、この予備
圧縮した原料を自然風乾により水分を５〜２５％にコン
トロールし、もって造粒原料とし、該造粒原料をブリケ
ットマシンにより線圧２.０〜５.０ｔ／ｃｍの加圧力で
加圧成形して１ｍｍ以上の大きさに造粒するか、若しく
は造粒原料を平滑ロールにより線圧２.０〜５.０ｔ／ｃ
ｍの加圧力で平板上に成形した後粉砕機にかけて粉砕
し、０.５ｍｍ以上の大きさのものを篩別することを特
徴とするリン化合物吸着用粒土の製造方法が開示されて
いる。For example, (3) as a method of crushing and granulating by compression-molding after wet-milling, Japanese Patent Publication No. 4-21538 discloses a colloidal soil with a mix muller type kneader at a linear pressure of 10 t.
/ Cm to be kneaded with a pressing force and pre-compressed, and the pre-compressed raw material is controlled to have a water content of 5 to 25% by natural air-drying to be used as a granulating raw material, and the granulating raw material is linearly compressed by a briquette machine. Press-mold with a pressure of 2.0 to 5.0 t / cm to granulate to a size of 1 mm or more, or granulate raw material with a smooth roll at a linear pressure of 2.0 to 5.0 t / c.
Disclosed is a method for producing a granular soil for adsorbing a phosphorus compound, which comprises molding on a flat plate with a pressing force of m, crushing with a crusher, and sieving one having a size of 0.5 mm or more.
【０００５】しかし、上記(１)の方法は多量のエネルギ
ーを消費し、(２)は余分な資材を必要とし、更に結合剤
により使用範囲が限定されるという欠点がある。また、
(３)による造粒物はバリを有し、割れ易く不規則な形状
のため流動性が悪く、吸着設備等を傷付け易く、カラム
法等に適さないという欠点がある。However, the method (1) consumes a large amount of energy, the method (2) requires extra materials, and has a drawback that the range of use is limited by the binder. Also,
The granulated product according to (3) has deficiencies in that it has burrs, is easily broken, and has an irregular shape and thus has poor fluidity, which easily damages adsorption equipment and the like and is not suitable for a column method or the like.
【０００６】上述のようにホスフィン酸イオン、ホスホ
ン酸イオン等についての経済的に有利かつ有効な除去方
法は見出されておらず、従って、排水による富栄養化現
象は更に促進されているのが現状である。As described above, an economically advantageous and effective method for removing phosphinate ions, phosphonate ions, etc. has not been found, and therefore, the phenomenon of eutrophication by waste water is further promoted. The current situation.
【０００７】従って、本発明の目的は、上述の課題を解
決すると共に嵩比重が小さくても水中破壊が少なく、低
コストの球状であることを特徴とする火山灰吸着剤及び
その製造方法を提供し、この火山灰吸着剤を使用するこ
とによりカラム法等でのホスフィン酸イオン、ホスホン
酸イオン等の吸着除去ができ、排水処理を簡易化するこ
とにある。Therefore, an object of the present invention is to solve the above-mentioned problems and to provide a volcanic ash adsorbent characterized by having a spherical shape at a low cost with less destruction in water even if the bulk specific gravity is small , and a manufacturing method thereof. By using this volcanic ash adsorbent, it is possible to adsorb and remove phosphinate ions, phosphonate ions, etc. by a column method and the like, and to simplify wastewater treatment.
【０００８】[0008]
【課題を解決するための手段】本発明に係る火山灰吸着
剤は、Ｓｉ１８〜２４％、Ａｌ２３〜２９％、Ｆｅ１〜
５％の化学組成を有し、アロフェンを主成分とする火山
灰土壌を造粒して得られる実質上添加剤を含まない嵩比
重０.５〜０.７、水中破壊率２５％以下の球状造粒物よ
りなることを特徴とする。Means for Solving the Problems Volcanic ash adsorption according to the present invention
The agents are Si 18 to 24%, Al 23 to 29%, Fe 1 to
Spherical structure with a chemical composition of 5%, obtained by granulating volcanic ash soil containing allophane as the main component, and having a bulk density of 0.5 to 0.7 and virtually no additives, and a water destruction rate of 25% or less. It is characterized by being composed of granules.
【０００９】また、上記火山灰吸着剤は、Ｓｉ１８〜２
４％、Ａｌ２３〜２９％、Ｆｅ１〜５％の化学組成を有
し、アロフェンを主成分とする火山灰土壌の水分を２４
〜３７％に調整して混合撹拌型造粒機により造粒し、そ
の後乾燥することを特徴として製造することができる。The above-mentioned volcanic ash adsorbent is made of Si18-2
It has a chemical composition of 4%, Al23-29%, and Fe1-5%, and the water content of volcanic ash soil containing allophane as the main component is 24%.
It can be manufactured by adjusting the content to ˜37%, granulating with a mixing and stirring granulator, and then drying.
【００１０】[0010]
【作用】本発明の火山灰吸着剤は、風乾または強制乾燥
した火山灰土壌を原料とし、水分を２４〜３７％に調整
し、または必要に応じて水分を補給し混合撹拌型造粒機
により最大周速４０ｍ／秒以下で造粒し、得られた造粒
物の嵩比重が０.５〜０.７で、水中破壊率が２５％以下
の球状で実質上添加剤を含まないことを特徴とするもの
である。The volcanic ash adsorbent of the present invention is prepared by using air-dried or forcedly-dried volcanic ash soil as a raw material, adjusting the water content to 24 to 37%, or replenishing the water as necessary, and using a mixing and agitation granulator to produce the maximum circumference. Granules at a speed of 40 m / sec or less, the obtained granules have a bulk specific gravity of 0.5 to 0.7, and a water fracture rate of 25% or less are spherical and substantially do not contain an additive. To do.
【００１１】本発明の火山灰吸着剤の製造方法におい
て、水分が上述の範囲を超える場合には収率が極端に低
下し、または付着等の問題により所望する嵩比重の火山
灰球状土壌が得られなくなる。また、得られた火山灰球
状土壌の嵩比重が０.５より小さいと、水中破壊が極端
に増加してくることによが実験結果により判り、０.７
より大きいものは混合撹拌型造粒機での造粒操作が難し
くなるために好ましくない。In the method for producing a volcanic ash adsorbent according to the present invention, when the water content exceeds the above range, the yield is extremely reduced, or due to problems such as adhesion, volcanic ash spherical soil having a desired bulk specific gravity cannot be obtained. . In addition, it was found from the experimental results that the underwater destruction would increase extremely when the bulk specific gravity of the obtained volcanic ash spherical soil was less than 0.5,
The larger one is not preferable because the granulation operation by the mixing and stirring type granulator becomes difficult.
【００１２】[0012]
【実施例】 実施例１〜２及び比較例１ 火山灰土壌は、山梨県八ケ岳山麓の地表面下１.５〜２.
５ｍの黄褐色土壌(Ｓｉ２２％、Ａｌ２６％、Ｆｅ３％)
を用い、多量に含んだ水分を風乾し、水分を２３〜３３
％に調整してヘンシェル型ミキサーにより造粒した。こ
れを乾燥してその中から篩分けした火山灰吸着剤につい
て諸特性を測定した結果を表１に示す。[Examples] Examples 1 and 2 and Comparative Example 1 Volcanic ash soil is 1.5-2. Below the surface of the ground at the foot of Mt.
5m yellowish brown soil (Si22%, Al26%, Fe3%)
Air-dry a large amount of water using
% And granulated with a Henschel mixer. Table 1 shows the results of measuring various characteristics of the ash adsorbent that was dried and sieved from the dried ash adsorbent .
【００１３】比較例２ 造粒時にＰＴＦＥ樹脂を結合剤として外掛で３％添加
し、乾燥後焼成して得られたものである。Comparative Example 2 This was obtained by adding 3% of PTFE resin as a binder to the outside during granulation, drying and firing.
【００１４】参考例 乾燥した火山灰土壌の中から３ｍｍ以下のものを篩分け
し、その諸特性を測定した。Reference Example From the dried volcanic ash soil, one having a size of 3 mm or less was sieved and various properties were measured.
【００１５】[0015]
【表１】 [Table 1]
【００１６】＊１：造粒時水分は、造粒後の火山灰吸着
剤を１２０℃で３時間処理して求めたものである。 ＊２：吸着量１は、Ｈ3ＰＯ3及びＨ3ＰＯ2を用いてリン
として１００ｍｇ／リットルの試験液を調製し、直径１
〜３ｍｍの火山灰吸着剤３ｇを充填したカラムに試験液
を１ｍＬ／分の流速で通してフラクションコレクターで
流出液を採取した。この流出液は高周波プラズマ発光分
光分析装置により検量線法で分析してリンの吸着量を求
めた。 ＊３：吸着量２は、Ｈ3ＰＯ3及びＨ3ＰＯ2を用いてリン
として５００ｍｇ／リットルの試験液を調製し、直径１
〜３ｍｍの火山灰吸着剤３ｇを充填したカラムに試験液
１ｍＬ／分の流速で通してフラクションコレクターで流
出液を採取した。この流出液は高周波プラズマ発光分光
分析装置により検量線法で分析してリンの吸着量を求め
た。 ＊４：水中破壊率は、２００ｍｌ共栓付三角フラスコに
４〜５ｍｍの火山灰吸着剤１５ｇを分取し、１００ｇの
蒸留水を加えて振幅５ｃｍ、３００サイクル／分で２時
間処理後、６メッシュの篩上に取り水洗して１５０℃で
乾燥して秤量し、破壊重量率を算出した。 ＊５：圧壊強度は、直径３〜５ｍｍの火山灰吸着剤につ
いて直径６ｍｍのロッド棒で圧縮し、破壊した時の荷重
である。 ＊６：この吸着量は、Ｈ3ＰＯ3及びＨ3ＰＯ2を用いてリ
ンとして１００ｍｇ／リットル、５００ｍｇ／リットル
の試験液を調製し、乾燥した火山灰土壌０.５ｇを共栓
付三角フラスコに取り、試験液を加えて撹拌しながら４
８時間処理した。次に、上澄みを濾過して高周波プラズ
マ発光分光分析装置により分析してリンの吸着量を求め
た。* 1: The water content during granulation is the adsorption of volcanic ash after granulation.
It is determined by treating the agent at 120 ° C. for 3 hours. * 2: Adsorption amount 1 was 100 mg / liter of phosphorus as a test solution prepared using H 3 PO 3 and H 3 PO 2 and had a diameter of 1
The test liquid was passed through a column packed with 3 g of a volcanic ash adsorbent of ˜3 mm at a flow rate of 1 mL / min, and the effluent was collected by a fraction collector. This effluent was analyzed by a calibration curve method using a high-frequency plasma emission spectrophotometer to determine the adsorption amount of phosphorus. * 3: Adsorption amount 2 was 500 mg / liter of phosphorus as a test liquid prepared using H 3 PO 3 and H 3 PO 2 , and the diameter was 1
The effluent was collected by a fraction collector by passing it through a column packed with 3 g of a volcanic ash adsorbent of ˜3 mm at a flow rate of 1 mL / min of the test solution. This effluent was analyzed by a calibration curve method using a high-frequency plasma emission spectrophotometer to determine the adsorption amount of phosphorus. * 4: Destruction rate in water is as follows: 15g of 4-5mm volcanic ash adsorbent is collected in a 200ml Erlenmeyer flask with stopper, 100g of distilled water is added, and the amplitude is 5cm, 300 cycles / min for 2 hours, and then 6 mesh. On the sieve, washed with water, dried at 150 ° C., weighed, and the breaking weight ratio was calculated. * 5: Crush strength is a load when a volcanic ash adsorbent having a diameter of 3 to 5 mm is compressed by a rod rod having a diameter of 6 mm and broken. * 6: For this adsorption amount, test solutions of 100 mg / l and 500 mg / l as phosphorus were prepared using H 3 PO 3 and H 3 PO 2, and 0.5 g of dried volcanic ash soil was placed in an Erlenmeyer flask with a stopper. Take, add the test solution and stir 4
Treated for 8 hours. Next, the supernatant was filtered and analyzed by a high-frequency plasma emission spectrophotometer to determine the adsorption amount of phosphorus.
【００１７】[0017]
【発明の効果】本発明の火山灰吸着剤は、嵩比重が小さ
くても水中崩壊が少なく、更に、火山灰土壌を原料とし
ているために低コストであり、この火山灰吸着剤を使用
することによりカラム法等でのホスフィン酸イオン、ホ
スホン酸イオン等の効率的な吸着除去ができ、排水処理
を簡易化することができる。Effects of the Invention ash adsorbent of the present invention, even with a small bulk density less water disintegration, further, low cost because of the volcanic ash soil and feed, column method by using this ash adsorbent It is possible to efficiently adsorb and remove phosphinate ions, phosphonate ions, etc., etc., and simplify wastewater treatment.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平栗 寛治 山梨県甲府市山宮町2947−７ (72)発明者 坂本 和夫 山梨県西八代郡市川大門町1527 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Kanji Hiraguri 2947-7 Yamamiya-cho, Kofu-shi, Yamanashi Prefecture (72) Kazuo Sakamoto 1527 Kawadaimon-cho, Nishiyatsushiro-gun, Yamanashi Prefecture
Claims (2)
Ｆｅ１〜５％の化学組成を有し、アロフェンを主成分と
する火山灰土壌を造粒して得られる実質上添加剤を含ま
ない嵩比重０.５〜０.７、水中破壊率２５％以下の球状
造粒物よりなることを特徴とする吸着用火山灰土壌。1. Si 18 to 24%, Al 23 to 29%,
Fe with a chemical composition of 1 to 5%, obtained by granulating volcanic ash soil containing allophane as a main component, and having a bulk specific gravity of 0.5 to 0.7 substantially free of additives and a water destruction rate of 25% or less. A volcanic ash soil for adsorption characterized by comprising a spherical granulated material.
方法において、Ｓｉ１８〜２４％、Ａｌ２３〜２９％、
Ｆｅ１〜５％の化学組成を有し、アロフェンを主成分と
する火山灰土壌の水分を２４〜３７％に調整して混合撹
拌型造粒機により造粒し、その後乾燥することを特徴と
する吸着用火山灰土壌の製造方法。2. The method for producing a volcanic ash soil for adsorption according to claim 1, wherein Si 18 to 24%, Al 23 to 29%,
Adsorption characterized by having a chemical composition of Fe 1 to 5%, adjusting the water content of volcanic ash soil containing allophane as the main component to 24 to 37%, granulating with a mixing and stirring type granulator, and then drying. Method for manufacturing volcanic ash soil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4318865A JP3064127B2 (en) | 1992-11-27 | 1992-11-27 | Volcanic ash adsorbent and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4318865A JP3064127B2 (en) | 1992-11-27 | 1992-11-27 | Volcanic ash adsorbent and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06154594A true JPH06154594A (en) | 1994-06-03 |
| JP3064127B2 JP3064127B2 (en) | 2000-07-12 |
Family
ID=18103829
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4318865A Expired - Fee Related JP3064127B2 (en) | 1992-11-27 | 1992-11-27 | Volcanic ash adsorbent and method for producing the same |
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| Country | Link |
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| JP (1) | JP3064127B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002263640A (en) * | 2001-03-08 | 2002-09-17 | Yamanashi Prefecture | Method of removing boron in water |
| CN115301201A (en) * | 2022-08-22 | 2022-11-08 | 昆明理工大学 | Volcanic ash soil-based adsorbent for enriching phosphorus in water body and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108609788A (en) * | 2018-04-23 | 2018-10-02 | 浙江奇彩环境科技股份有限公司 | A kind for the treatment of process of phosphorus flame retardant waste water |
-
1992
- 1992-11-27 JP JP4318865A patent/JP3064127B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002263640A (en) * | 2001-03-08 | 2002-09-17 | Yamanashi Prefecture | Method of removing boron in water |
| CN115301201A (en) * | 2022-08-22 | 2022-11-08 | 昆明理工大学 | Volcanic ash soil-based adsorbent for enriching phosphorus in water body and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3064127B2 (en) | 2000-07-12 |
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