JPH084743B2 - Ceramic-based adsorption remover - Google Patents

Ceramic-based adsorption remover

Info

Publication number
JPH084743B2
JPH084743B2 JP18704793A JP18704793A JPH084743B2 JP H084743 B2 JPH084743 B2 JP H084743B2 JP 18704793 A JP18704793 A JP 18704793A JP 18704793 A JP18704793 A JP 18704793A JP H084743 B2 JPH084743 B2 JP H084743B2
Authority
JP
Japan
Prior art keywords
ceramic
adsorption
pesticides
removal
pesticide
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.)
Expired - Fee Related
Application number
JP18704793A
Other languages
Japanese (ja)
Other versions
JPH0716453A (en
Inventor
克己 上村
俊治 中村
功雄 丹羽
卓二 宮本
稔 平原
雅章 永野
文夫 瀬下
邦雄 野村
Original Assignee
三星礦業株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 三星礦業株式会社 filed Critical 三星礦業株式会社
Priority to JP18704793A priority Critical patent/JPH084743B2/en
Publication of JPH0716453A publication Critical patent/JPH0716453A/en
Publication of JPH084743B2 publication Critical patent/JPH084743B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Description

【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、ゴルフ場等で用いられ
ている農薬と肥料の流出防止などを目的とした有害成分
の吸着除去剤に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbent / removal agent for harmful components for the purpose of preventing outflow of agricultural chemicals and fertilizers used in golf courses and the like.

【0002】[0002]

【従来の技術】従来、ゴルフ場の芝を病虫害から守り、
育成するために多量の殺虫剤、除草剤、および殺菌剤な
らびに肥料が使用されている。都道府県の行政機関で
は、農薬による環境汚染を防止するために農薬の適正使
用と農薬の総量規制を指導している。一方、民間企業で
は、各種の農薬対策商品や除去システムを販売してい
る。このうち対策商品については、多種類の農薬を直ち
に除去でき、しかも永年にわたり除去効果を維持できる
ものは少ない。最近、二酸化珪素、酸化カルシウム、酸
化アルミニウム、酸化鉄、酸化マンガン、酸化マグネシ
ウム、酸化カリウムからなる金属酸化物を焼成してなる
多孔質焼結体に活性炭等の吸着物質を配合した農薬吸着
分解剤が見られる(特開平4−110035号公報)
が、多種類の農薬について必ずしも長期間にわたり除去
効果を期待することはできそうにない。
2. Description of the Related Art Conventionally, the lawn of a golf course is protected from pests,
Large amounts of insecticides, herbicides, and fungicides and fertilizers are used to grow. Prefectural governments provide guidance on proper use of pesticides and regulation of total amount of pesticides to prevent environmental pollution by pesticides. On the other hand, private companies sell various pesticide countermeasure products and removal systems. Among these, few of the countermeasure products can immediately remove many kinds of pesticides and can maintain the removal effect for many years. Recently, a pesticide adsorption decomposition agent in which an adsorbent such as activated carbon is mixed with a porous sintered body obtained by firing a metal oxide composed of silicon dioxide, calcium oxide, aluminum oxide, iron oxide, manganese oxide, magnesium oxide, and potassium oxide. Can be seen (JP-A-4-110035).
However, it is not always possible to expect a long-term removal effect for many types of pesticides.

【0003】現在、湖沼での富栄養化による水質悪化は
社会問題となっており、湖沼に処理排水を流入させてい
る事業所には窒素、リンの排出量が規制されているが、
農薬、栄養塩類の同時除去については全く対策商品がな
いのが現状である。また、除去システムについては、主
に懸濁物質と農薬の除去を目的としたものであり、シス
テムの導入とその維持管理に経済的な負荷も大きいのが
現状である。さらに、農薬やリン、窒素以外の有害成分
についても、排水中からの吸着・除去が望まれているも
のが多い。
At present, the deterioration of water quality due to eutrophication in lakes is becoming a social problem, and the emission of nitrogen and phosphorus is regulated at business establishments that introduce treated wastewater into lakes.
Currently, there is no countermeasure product for simultaneous removal of pesticides and nutrients. In addition, the removal system is mainly intended to remove suspended substances and pesticides, and the present situation is that the introduction of the system and the maintenance and management of it are economically heavy. In addition, it is often desired to adsorb and remove pesticides and harmful components other than phosphorus and nitrogen from wastewater.

【0004】[0004]

【発明が解決しようとする課題】本発明は、ゴルフ場等
からの農薬および肥料の流出防止等を目的として使用さ
れる有害成分のセラミック系吸着除去剤を提供するもの
である。
SUMMARY OF THE INVENTION The present invention provides a ceramic-based adsorptive remover of harmful components used for the purpose of preventing outflow of agricultural chemicals and fertilizers from golf courses and the like.

【0005】[0005]

【課題を解決するための手段】本発明のセラミック系吸
着除去剤は、炭酸カルシウムと粘土を含む石灰石水洗ケ
ーキを母材とし、これに海泡石およびシリカ系粉粒体を
配合し、この配合物を成形後に焼成してなることを特徴
とする。
The ceramic-based adsorptive remover of the present invention comprises a limestone wash cake containing calcium carbonate and clay as a base material, to which sepiolite and silica-based powder and granules are blended. It is characterized in that the product is fired after being molded.

【0006】[0006]

【発明の作用】本発明のセラミック系吸着除去剤は、農
薬、リンなどを吸着・除去する機能を有しており、吸着
された農薬等については生分解機能と加水分解機能があ
いまって、簡便な施工により多種類の農薬を効果的に除
去するものである。とりわけ、本発明のセラミック系吸
着除去剤は、農薬およびリンの除去機能に優れており、
吸着された農薬は分解・除去されるため、通常の使用に
おいては、吸着された農薬が破過容量に達することは稀
であるので、永年にわたり除去効果を発揮することが可
能になった。
The ceramic-based adsorption / removal agent of the present invention has a function of adsorbing / removing pesticides, phosphorus, etc., and the adsorbed pesticides have a simple biodegradation function and hydrolysis function. It effectively removes many kinds of pesticides by performing a simple construction. In particular, the ceramic-based adsorption remover of the present invention is excellent in the function of removing agricultural chemicals and phosphorus,
Since the adsorbed pesticides are decomposed and removed, it is rare that the adsorbed pesticides reach the breakthrough capacity in normal use, and therefore, the removal effect can be exerted for many years.

【0007】[0007]

【発明の実施態様】セラミック系吸着除去剤の原材料の
母材をなす石灰石水洗ケーキは、石灰石採掘後の水洗選
鉱工程より発生するものである。即ち、石灰石を水洗す
ると、微細粒の粘土、石灰石粉を含んだスラリーが発生
する。これをシックナー(沈澱槽)で沈澱させた後、フ
ィルタープレス(加圧脱水装置)等で脱水したものであ
り、約70%以上の石灰石粉と約30%以下の粘土粉を
含んでいる。一方、海泡石は、細孔を有するという特性
をもつ。
BEST MODE FOR CARRYING OUT THE INVENTION The limestone wash cake, which is the base material of the raw material for the ceramic-based adsorption remover, is generated in the water washing ore separation process after limestone mining. That is, when limestone is washed with water, a slurry containing fine-grained clay and limestone powder is generated. This is precipitated in a thickener (precipitation tank) and then dehydrated by a filter press (pressurized dehydrator) or the like, and contains about 70% or more of limestone powder and about 30% or less of clay powder. On the other hand, sepiolite has a characteristic of having pores.

【0008】シリカ系粉粒体としては、フライアッシ
ュ、ゼオライトなどが挙げられ、配合物中に不足するS
i分を補充する機能を有している。フライアッシュとし
ては、火力発電所等より発生する石炭系の普通のフライ
アッシュでよい。ゼオライトは天然ゼオライトでも合成
ゼオライトでもよい。
[0008] Examples of silica-based powder include fly ash, zeolite, and the like.
It has a function of replenishing i minutes. The fly ash may be ordinary coal-based fly ash generated from a thermal power plant or the like. The zeolite may be natural zeolite or synthetic zeolite.

【0009】石灰石水洗ケーキ(A)、海泡石(B)お
よびシリカ系粉粒体(C)の配合重量比は、(A):
(B):(C)=40〜60:10〜30:10〜40
が好適であり、より好ましくは45〜55:15〜2
5:25〜35である。上記の石灰石水洗ケーキ、海泡
石およびシリカ系粉粒体の各成分は混合された後、造粒
される。造粒には特にバインダーを必要とせず、適切量
の水分があれば普通の造粒機で造粒できる。
The blending weight ratio of the limestone wash cake (A), sepiolite (B) and silica-based powder (C) is (A):
(B): (C) = 40 to 60:10 to 30:10 to 40
Is preferred, and more preferably 45-55: 15-2
It is 5:25 to 35. The above components of the limestone wash cake, sepiolite and silica-based powder are mixed and then granulated. No particular binder is required for granulation, and an ordinary granulator can be used as long as there is an appropriate amount of water.

【0010】造粒されたものは、1100〜1300℃
位の温度で焼成され、ダイカルシウムシリケート(2C
aO・SiO2 )を骨格としたセラミックとなり、農
薬、リン等に対して優れた除去機能をもつセラミック系
吸着除去剤が得られる。
The granulated product is 1100 to 1300 ° C.
Calcined at about the same temperature, dicalcium silicate (2C
It becomes a ceramic with aO.SiO 2 skeleton as the skeleton, and a ceramic-based adsorption / removal agent having an excellent removal function for pesticides, phosphorus, etc. can be obtained.

【0011】本発明のセラミック系吸着除去剤の粒径
は、その使用場所に応じて適宜選定され、例えば、芝土
中に添加する場合は透水性を考慮して1.5〜5mm径
のものが好ましく、集水マンホールなどで用いられる場
合は5〜15mm径のものが好ましい。
The particle size of the ceramic-based adsorption / removal agent of the present invention is appropriately selected depending on the place of use. For example, when it is added to turf soil, it has a diameter of 1.5 to 5 mm in consideration of water permeability. Is preferable, and when used in a water collecting manhole or the like, those having a diameter of 5 to 15 mm are preferable.

【0012】本発明のセラミック系吸着除去剤の施工方
法としては、床土中に添加する方法、床土中に層状に設
置する方法、集水管や集水ピットに設置する方法、調整
池に設置する方法、カラムに充填して被処理水を通水す
る方法などがあり、これらの方法はいずれも簡便であ
る。
The method for applying the ceramic-based adsorption / removal agent of the present invention includes a method of adding it to the bed soil, a method of installing it in layers in the bed soil, a method of installing it in a water collecting pipe or a water collecting pit, and a method of installing it in a regulating pond. And a method of filling the column with water to pass the water to be treated, and these methods are all simple.

【0013】[0013]

【発明の効果】本発明のセラミック系吸着除去剤は、農
薬、リン等の有害成分を除去する機能を有しており、特
に加水分解機能に優れていることから、吸着した多種類
の農薬等を速やかに分解・除去する効果を有している。
また、農薬を長期にわたり生分解する機能を併せ有する
ものである。したがって、当初より農薬等の有害成分の
除去効果に変動がなく、長期にわたり効果が期待できる
ものである。
EFFECT OF THE INVENTION The ceramic-based adsorption / removal agent of the present invention has a function of removing harmful components such as agricultural chemicals and phosphorus, and is particularly excellent in hydrolysis function. It has the effect of rapidly decomposing and removing.
It also has the function of biodegrading pesticides over a long period of time. Therefore, the effect of removing harmful components such as pesticides does not change from the beginning, and the effect can be expected for a long period of time.

【0014】特に、本発明のセラミック系吸着除去剤は
後述の実験例1,2に示すように、農薬分解能が優れて
おり、吸着を主体とする市販品よりもはるかに長期にわ
たり、その除去効能を維持できるものである。また、実
験例3に示すように、リンに対して非常に優れた除去機
能を示す。さらに、保水力、通気性、透水性、保肥力等
の物理的、化学的性質に優れているので、床土の改良に
も効果があり、また、施工も簡便である。
In particular, as shown in Experimental Examples 1 and 2 described later, the ceramic-based adsorption / removal agent of the present invention has excellent pesticide decomposing ability, and its removal efficacy is far longer than that of a commercial product mainly composed of adsorption. Can be maintained. Further, as shown in Experimental Example 3, it has a very excellent removal function for phosphorus. Furthermore, since it has excellent physical and chemical properties such as water retention ability, air permeability, water permeability, and fertilizing ability, it is effective in improving the soil floor and is easy to construct.

【0015】また、カラムに充填して通水することによ
り、有害成分を含む排水を浄化することができる。以下
に本発明の実施例を挙げて具体的に説明するが、本発明
は、その主旨を超えない限りにおいて、以下の実施例に
限定されるものではない。
Further, by filling the column and passing water through it, it is possible to purify the waste water containing harmful components. EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

【0016】[0016]

【実施例】実施例1 石灰石水洗フィルターケーキ60重量部、海泡石20重
量部およびフライアッシュ20重量部を混合造粒したの
ち、1200℃で焼成して粒径0.75〜1mmの本発
明のセラミック系除去剤を得た。
EXAMPLE 1 60 parts by weight of limestone washed filter cake, 20 parts by weight of sepiolite and 20 parts by weight of fly ash were mixed and granulated, and then fired at 1200 ° C. to obtain a particle size of 0.75 to 1 mm according to the present invention. To obtain a ceramic-based removing agent.

【0017】実験例1:農薬除去機能(室内カラム試
験) ゴルフ場で汎用されている農薬を用いた。即ち、殺菌剤
としてクロロネブ、イソプロチオラン、フルトラニル、
イプロジオン、TPN、除草剤としてプロピザミド、シ
マジン(CAT)、殺虫剤としてフェニトロチオン(M
EP)、イソキサチオン、ダイアジノンを選定した。断
面積0.78cm2 のカラムに本発明の実施例1のセラ
ミック系吸着除去剤あるいは比較対照としての活性炭を
3g積層し、表1に示した流入液濃度の溶液を1時間当
たり25mlの速度で約520mlを連続的に流し、2
0.75時間中の流出液中の平均農薬濃度を測定し、そ
の結果を表1に示した。
Experimental Example 1: Pesticide removal function (indoor column test) A pesticide commonly used in golf courses was used. That is, as a fungicide, chloroneb, isoprothiolane, flutolanil,
Iprodione, TPN, propyzamide and simazine (CAT) as herbicides, fenitrothion (M
EP), isoxathion, and diazinon were selected. 3 g of the ceramic-based adsorption remover of Example 1 of the present invention or activated carbon as a comparative control was laminated on a column having a cross-sectional area of 0.78 cm 2 , and a solution having an influent concentration shown in Table 1 was added at a rate of 25 ml per hour. Continuously pour about 520 ml, 2
The average pesticide concentration in the effluent during 0.75 hours was measured, and the results are shown in Table 1.

【0018】[0018]

【表1】表1:農薬除去効果 流出液濃度(mg/l) 調査対象農薬名 流入液濃度(mg/l) 実施例1品 活 性 炭 クロロネブ 94.0 8.52 8.59 イソプラチオラン 328 7.11 31.2 フルトラニル 223 7.01 21.2 イプロジオン 2020 6.42 187 TPN 789 23.3 78.0 CAT 1325 23.6 127 プロピザミド 287 14.5 27.4 MEP 1040 20.3 100 イソキサチオン 1040 7.03 98.6 ダイアジノン 650 16.8 60.1 [Table 1] Table 1: Pesticide removal effect Outflow liquor concentration (mg / l) Investigation target pesticide name Influent concentration (mg / l) Example 1 product Activated carbon chloroneb 94.0 8.52 8.59 Isopratiolane 328 7.11 31.2 Flutolanil 223 7.01 21.2 Iprodione 2020 6.42 187 TPN 789 23.3 78.0 CAT 1325 23.6 127 Propizzamide 287 14.5 27.4 MEP 1040 20.3 100 Isoxathione 1040 7.03 98.6 Diazinon 650 16.8 60.1

【0019】以上の実験結果を見ても、本発明によるセ
ラミック系吸着除去剤は汎用されている活性炭に比べ農
薬除去に優れていることが分かる。
From the above experimental results, it can be seen that the ceramic-based adsorption / removal agent according to the present invention is superior in the removal of agricultural chemicals as compared with the commonly used activated carbon.

【0020】実験例2:農薬除去機能(室内カラム試
験) 断面積0.78cm2 のカラムに本発明の実施例1のセ
ラミック系吸着除去剤あるいは比較対照としての市販農
薬吸着剤を3g積層し、表2に示した流入液濃度の溶液
を1時間当たり32mlの速度で約720mlを連続的
に流し、22.5時間中の流出液中の平均農薬濃度を測
定し、その結果を表2に示した。
Experimental Example 2: Pesticide removal function (indoor column test) 3 g of the ceramic adsorption removal agent of Example 1 of the present invention or a commercially available pesticide adsorption agent as a comparative control was laminated on a column having a cross-sectional area of 0.78 cm 2 . About 720 ml of the solution having the influent concentration shown in Table 2 was continuously flown at a rate of 32 ml per hour, and the average pesticide concentration in the effluent during 22.5 hours was measured. The results are shown in Table 2. It was

【0021】[0021]

【表2】表2:農薬除去効果 流出液濃度(mg/l) 調査対象農薬名 流入液濃度(mg/l) 実施例2品 市販農薬吸着剤 クロロネブ 2.98 0.587 0.551 イソプラチオラン 2.67 0.398 0.429 フルトラニル 2.12 0.478 0.559 イプロジオン 1.50 0.293 0.391 TPN 5.26 1.02 1.86 CAT 11.1 4.26 4.12 プロピザミド 4.86 1.76 1.89 MEP 3.03 0.292 0.348 イソキサチオン 1.83 0.306 0.461 ダイアジノン 2.71 0.445 0.347 [Table 2] Table 2: Pesticide removal effect Effluent concentration (mg / l) Investigation target pesticide name Influent concentration (mg / l) Example 2 product Commercial pesticide adsorbent chloroneb 2.98 0.587 0.551 Isopratiolane 2.67 0.398 0.429 Flutolanil 2.12 0.478 0.559 Iprodione 1.50 0.293 0.391 TPN 5.26 1.02 1.86 CAT 11.1 4.26 4.12 Propizzamide 4.86 1.76 1.89 MEP 3.03 0.292 0.348 Isoxathione 1.83 0.306 0.461 Diazinon 2.71 0.445 0.347

【0022】以上の実験結果を見ても、本発明によるセ
ラミック系除去剤は市販の農薬吸着剤に比べ農薬除去に
優れていることが分かる。
From the above experimental results, it can be seen that the ceramic-based remover according to the present invention is superior to the commercially available pesticide adsorbent in removing pesticides.

【0023】実験例3:リン吸着能 断面積0.78cm2 のカラムに表3に示したそれぞれ
の試料を3g積層し、肥料成分としてPO4−P (リン
酸態リン)を含む肥料(芝グリーンP,大塚化学(株)
製)の溶液を695μg/cm2 の量で添加し、30m
mの降雨に相当する量の水を流し、流出液中の肥料成分
を測定して肥料成分の流出量を求め、その結果を表3に
示した。
Experimental Example 3: Phosphorus adsorption capacity 3 g of each sample shown in Table 3 was laminated on a column having a cross-sectional area of 0.78 cm 2 , and a fertilizer containing PO 4 -P (phosphorus phosphorus) as a fertilizer component (turf). Green P, Otsuka Chemical Co., Ltd.
30 μm, adding the solution of the above) in an amount of 695 μg / cm 2.
The amount of fertilizer components in the effluent was measured by pouring water in an amount corresponding to m rainfall, and the results are shown in Table 3.

【0024】[0024]

【表3】表3:リン吸着能 流出量(μg/cm2 試 料 肥 料 成 分 実施例2品 市販農薬吸着剤 活 性 炭 PO4−P <1 105 295 以上の実験結果を見ても、本発明のセラミック系除去剤
によるリン吸着能は、市販の農薬吸着剤および活性炭に
比べ非常に優れていることが分かる。
TABLE 3: Look phosphorus adsorption capacity runoff ([mu] g / cm 2) specimen fertilizer Ingredient Example 2 dishes commercial pesticide adsorbent activated carbon PO 4 -P <1 105 295 or more test results However, it can be seen that the phosphorus removing ability of the ceramic-based removing agent of the present invention is extremely superior to that of the commercially available agricultural chemical adsorbent and activated carbon.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 平原 稔 岐阜県大垣市笠木町49 (72)発明者 中村 俊治 愛知県名古屋市中村区名駅3−28−12 (72)発明者 丹羽 功雄 愛知県名古屋市守山区大字瀬古字柴荷102 −1 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minor Hirahara 49 Minami Kasaki, Ogaki City, Gifu Prefecture (72) Inventor Shunji Nakamura Aichi Prefecture 3-28-12 Mei Station, Nakamura-ku, Nagoya City (72) Inventor Isao Niwa Aichi Prefecture 102-1 Shibaari, Seko, Moriyama-ku, Nagoya

Claims (1)

    【特許請求の範囲】[Claims]
  1. 【請求項1】 炭酸カルシウムと粘土を含む石灰石水洗
    ケーキを母材とし、これに海泡石およびシリカ系粉粒体
    を配合し、この配合物を成形後に焼成してなることを特
    徴とするセラミック系吸着除去剤。
    1. A ceramic characterized in that a limestone washed cake containing calcium carbonate and clay is used as a base material, sepiolite and silica-based powder and granules are blended, and the blend is molded and then fired. System adsorption remover.
JP18704793A 1993-06-29 1993-06-29 Ceramic-based adsorption remover Expired - Fee Related JPH084743B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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KR100330255B1 (en) * 2000-02-26 2002-03-25 서현숙 Composition of inorganic coagulant for water treatment
ITVR20080141A1 (en) * 2008-12-23 2010-06-24 Claudio Zanderigo Method for optimizing the quality of waterways
JP5072988B2 (en) * 2010-02-25 2012-11-14 中国電力株式会社 Granules for water purification, water purification method
CN102266752B (en) * 2011-06-24 2013-01-02 东北师范大学 Method for preparing carbonizing absorption grains used for purifying water
JP2014128744A (en) * 2012-12-27 2014-07-10 Mitsuboshi Mining Co Ltd Method for processing water-washed sludge

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