JP2005177720A - Inorganic flocculant - Google Patents

Inorganic flocculant Download PDF

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JP2005177720A
JP2005177720A JP2003426518A JP2003426518A JP2005177720A JP 2005177720 A JP2005177720 A JP 2005177720A JP 2003426518 A JP2003426518 A JP 2003426518A JP 2003426518 A JP2003426518 A JP 2003426518A JP 2005177720 A JP2005177720 A JP 2005177720A
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inorganic flocculant
raw material
flocculant
aqueous solution
shell
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Katsuyoshi Suzuki
勝義 鈴木
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic flocculant which can be safely and economically produced because dangerous high heat is not caused, harmful sulfur dioxide is not produced and the damage of a production vessel due to acid is not caused during the manufacture process and enables a further enhancement of flocculation function. <P>SOLUTION: The inorganic flocculant promotes a flocculation action for associating particulates dispersed in liquid to form a larger associated body. The inorganic flocculant is obtained by using shells of oyster and the like as raw material, and the flocculation function components included in the raw material is eluted by acting an aqueous solution of aluminium sulfate, polyaluminium chloride or chemicals having the same function with them to the raw material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、貝殻を原料として得られる高性能で安価な無機凝集剤に関する。   The present invention relates to a high-performance and inexpensive inorganic flocculant obtained from shells as a raw material.

牡蠣等の貝殻を原料として、この原料に酸性液を作用させ、原料が含有する凝集成分を溶出させた無機凝集剤は、本発明者の先発明に係るものであり、煩雑な操作も技術の熟練も要せず安定した効果が得られて、しかも、従来の凝集剤では不可能な繰り返し使用ができ、製品のコストは最も安価な有機高分子凝集剤の数10分の1以下であるという理想的な特性を有するものである。(例えば、特許文献1参照)
特願2002−157928号明細書(第2頁)
An inorganic flocculant obtained by using an oyster shell or the like as a raw material and causing an acidic liquid to act on the raw material and eluting the aggregating components contained in the raw material is related to the inventor's prior invention, and the complicated operation is also technical. Stable effects are obtained without requiring skill, and it can be used repeatedly, which is impossible with conventional flocculants, and the cost of the product is less than a few tenths of the cheapest organic polymer flocculants. It has ideal characteristics. (For example, see Patent Document 1)
Japanese Patent Application No. 2002-157828 (second page)

しかしながら、貝殻から酸性液を用いて凝集成分を抽出する無機凝集剤は、製造過程において危険な高熱と、有害な亜硫酸ガスを発生するという安全上の問題点と、製造容器が強酸により損壊されて短期間で更新を要するという経済的な問題点とを有する。   However, an inorganic flocculant that extracts an agglomerated component from seashells using an acidic liquid has a safety problem of generating dangerously high heat and harmful sulfurous acid gas in the production process, and the production container is damaged by strong acid. It has the economical problem of requiring renewal in a short period of time.

本発明は、前記課題を解決して、製造過程において危険な高熱や、有害な亜硫酸ガスの発生や、製造容器の酸による損壊を生じないため、安全且つ経済的に凝集剤を製造できて、凝集機能の一層の向上も望める無機凝集剤を提供することをその課題とする。   The present invention solves the above-mentioned problems, does not cause dangerous high heat in the production process, generation of harmful sulfurous acid gas, or damage due to acid in the production container, so that the flocculant can be produced safely and economically, It is an object of the present invention to provide an inorganic flocculant that can further improve the aggregation function.

前記課題を解決するため、本発明に係る無機凝集剤は、下記の構成を採用することを特徴とする。
液体中に分散する微粒物質が会合して、より大きな会合体を造る凝集作用を助長させる無機凝集剤であって、
この無機凝集剤は、牡蠣等の貝殻を原料として、この原料に硫酸アルミニウム、ポリ塩化アルミニウムか、これらと同効質剤の水溶液を作用させて、原料が含有する凝集機能成分を溶出させたものであること。
In order to solve the above problems, the inorganic flocculant according to the present invention employs the following constitution.
An inorganic flocculant that promotes the agglomeration action by which fine substances dispersed in a liquid associate to form a larger aggregate,
This inorganic flocculant is made from shells such as oysters, and the raw material is made of aluminum sulfate, polyaluminum chloride, or an aqueous solution of the same effect agent, and the aggregating functional components contained in the raw material are eluted. Be.

(1)貝殻に硫酸アルミニウム、ポリ塩化アルミニウムか、これらと同効質剤の水溶液を作用させて、凝集成分を抽出する場合は、製造過程における高熱や、有害ガスの発生及び酸による製造容器の損壊が防止されるため、無機凝集剤を安全且つ経済的に製造することができる。
(2)貝殻から抽出された凝集機能成分は、凝集性・吸着性・沈降速度等において有機高分子凝集剤と同等の機能を発揮する。
(3)凝集剤を処理液に混合するだけで、前段において処理液のPH調整をしたり、助剤による効果の向上を図る等の煩雑な操作や技術の熟練等は必要とせずに、最良の効果を安定して上げることができる。
(4)従来の凝集剤では不可能であった繰り返し使用が可能である。
(5)有機高分子凝集剤では取り残し易かった溶解性物質を分離除去することができる。
(6)廃物の貝殻を有用な資源として活用できて、製品のコストが有機高分子凝集剤の安価なものに比べても数10分の1以下と極めて安い。
(7)貝殻からの凝集機能成分の抽出に硫酸アルミニウム、ポリ塩化アルミニウムか、これらと同効質剤の水溶液を用いると、アルミニウム成分により溶解性物質(コロイド)の吸着が行なわれるので凝集の効果が大きく増進される。
(1) When extracting agglomerated components by causing aluminum sulfate, polyaluminum chloride, or an aqueous solution of these same agents to act on shells, the heat generated during the production process, generation of harmful gases, and acid Since damage is prevented, the inorganic flocculant can be produced safely and economically.
(2) The coagulation functional component extracted from the shell exhibits a function equivalent to that of the organic polymer coagulant in cohesion, adsorbability, sedimentation speed, and the like.
(3) Just by mixing the flocculant with the treatment liquid, it is best to adjust the pH of the treatment liquid in the previous stage, without requiring complicated operations such as improving the effect of the auxiliary agent, technical skill, etc. The effect of can be raised stably.
(4) It can be used repeatedly, which was impossible with conventional flocculants.
(5) Soluble substances that are easily left behind by the organic polymer flocculant can be separated and removed.
(6) The waste shell can be used as a useful resource, and the cost of the product is extremely low, such as a few tenths or less, compared to the inexpensive organic polymer flocculant.
(7) Use of aluminum sulfate, polyaluminum chloride, or an aqueous solution of the same effect agent for extraction of the functional component for aggregation from the shell will cause the soluble component (colloid) to be adsorbed by the aluminum component. Is greatly improved.

以下に、本発明に係る無機凝集剤の実施形態を説明する。   Hereinafter, embodiments of the inorganic flocculant according to the present invention will be described.

本発明において主原料とする貝殻は、公知の通り石灰を主成分として、多種の微量元素(ミネラル)を含有するものであり、これら微量元素中に硫酸アルミニウム、ポリ塩化アルミニウムか、これらと同効質剤の水溶液によって溶出させると、凝集、吸着、沈降等の機能を発揮する成分を有しているものが存在する総てが適用される。しかし、大量を容易に入手できることが好ましいので、現在は蠣殻を使用している。   The shell as the main raw material in the present invention contains lime as a main component and contains various trace elements (minerals) as known in the art. In these trace elements, aluminum sulfate, polyaluminum chloride, or the same effect as these. When elution is performed with an aqueous solution of a material, all those having components that exhibit functions such as aggregation, adsorption, and sedimentation are applied. However, rice husks are currently used because it is preferable to be able to obtain large quantities easily.

前記貝殻は、洗浄等により汚れを除去して、原形のままか、成分抽出液との接触面積を大きくするため適当な大きさに粉砕するか、あるいは、粉状に粉砕したもの等をそのままか、凝集機能等を助長するための剤等を加えて、結合剤により粒状、塊状に成形したものを用いてもよい。   The shell shall be cleaned to remove the dirt and remain in its original form, crushed to an appropriate size to increase the contact area with the component extract, or the powdered crushed shell as it is. In addition, an agent for promoting the aggregation function or the like may be added, and a product formed into a granular or lump shape with a binder may be used.

前記貝殻から凝集機能成分を溶出させる水溶液は、硫酸バンドと称される硫酸アルミニウム、PACと称されるポリ塩化アルミニウムか、これらと同効質剤であって、凝集剤の製造に際して、高熱や有害ガスを発生せず、強酸による製造容器の損壊も生じないが、貝殻から凝集機能成分を溶出する特性に優れた材料を水により適当な濃度に希釈して用いるものであり、この水溶液は以後においては硫酸アルミニウム水溶液を代表として述べる。   The aqueous solution for eluting the coagulation functional component from the shell is aluminum sulfate called a sulfate band, polyaluminum chloride called PAC, or the same effect agent as these. It does not generate gas and does not cause damage to the production container due to strong acid, but is used by diluting a material excellent in the property of eluting the coagulation functional component from the shell to an appropriate concentration with water. Describes aluminum sulfate aqueous solution as a representative.

硫酸アルミニウム水溶液を原料の貝殻に作用させるには、浸漬・接触・その他の適当な手段を用いる。このうち、浸漬式は原料貝殻の適量を製造容器に入れて、この容器に適当濃度の硫酸アルミニウム水溶液を貝殻が漬かるように注入して、静置するか、必要に応じて攪拌を行なうことにより、貝殻に硫酸アルミニウム水溶液を作用させて、貝殻に含有される微量元素(ミネラル)を凝集機能成分として溶出させて凝集剤の原液を調製する。   In order for the aluminum sulfate aqueous solution to act on the shell of the raw material, immersion, contact, or other suitable means is used. Among these, the immersion method is to put an appropriate amount of raw material shells in a production container, inject an appropriate concentration of aluminum sulfate aqueous solution into the container so that the shells are soaked, and let stand, or stir as necessary Then, an aluminum sulfate aqueous solution is allowed to act on the shell, and the trace element (mineral) contained in the shell is eluted as an aggregating functional component to prepare a stock solution of the flocculant.

又、接触式は、通水底を有する容器に貝殻を必要とする接触時間が得られる層厚をなすように収容して置き、容器の上から適当濃度に希釈した硫酸アルミニウム水溶液をシャワー状に流下させるか、反対に下から流入させて上へ流出させるか、あるいは、水溶液の流路中に原料貝殻の充填部を設けて、この充填部に貝殻層を充填し、硫酸アルミニウム水溶液が貝殻層を横に貫流するようにする。こうすと、原理的には硫酸アルミニウム水溶液が一定時間で貝殻層を通過して貝殻に作用し、貝殻が含有する凝集剤機能成分の微量元素(ミネラル)を溶出させるのであって、この方式では通過時間の設定により適当な濃度の凝集剤を連続して調製することができる。   In the contact type, a container having a water passage bottom is placed in a container having a layer thickness that can provide a contact time that requires a shell, and an aluminum sulfate aqueous solution diluted to an appropriate concentration flows down from the container in a shower-like manner. Or, on the contrary, it flows from the bottom and flows upward, or a filling portion of the raw material shell is provided in the flow path of the aqueous solution, and this filling portion is filled with the shell layer, and the aqueous aluminum sulfate solution forms the shell layer. Try to flow sideways. In this way, in principle, the aqueous solution of aluminum sulfate passes through the shell layer in a certain period of time and acts on the shell to elute the trace elements (minerals) of the flocculant functional component contained in the shell. Depending on the setting of the passage time, an appropriate concentration of the flocculant can be continuously prepared.

前記の通り貝殻に硫酸アルミニウム水溶液を作用させて溶出させた成分が何であるか、これら成分中の何が凝集機能を発揮するものであるかは、分析設備を持たないため確認することはできない。しかしながら、硫酸アルミニウム水溶液に浸漬して貝殻成分から溶出させた凝集剤の原液を1000倍程度に希釈して、この希釈液を試験容器に取った500ccの豚尿排水に加え、緩やかに攪拌した後に静止させて凝集試験を行って見ると、豚尿排水中の懸濁物質は20秒で凝集し始めてフロックを形成し、フロックの成長に伴ない、逐次沈降して2分後にはフロックが製造容器の底部に沈降層を造り、通常はこの沈降層より上は無色透明の状態となった。しかし、1回で無色透明の状態にならない場合は、上澄液のみを取り出して、更に、上記作業を繰り返し行なうと無色透明の状態とすることができる。   As described above, it is not possible to confirm what the components eluted by the action of the aluminum sulfate aqueous solution on the shell are, and what are the components that exhibit the coagulation function, because they do not have an analysis facility. However, after diluting the stock solution of the flocculant soaked in the aluminum sulfate aqueous solution and eluting from the shell component to about 1000 times, and adding this diluted solution to the 500 cc swine urine drainage taken in the test container, When the flocculation test is performed after standing still, the suspended matter in the swine urine drainage begins to aggregate in 20 seconds to form a floc. A sedimentation layer was formed at the bottom of the material, and the sedimentation layer was usually colorless and transparent. However, if it does not become colorless and transparent at a time, it can be made colorless and transparent by taking out only the supernatant and further repeating the above operation.

前述の通り無色透明の状態となった上澄水のBOD値と、凝集処理を行なう前の処理液とのBOD値を比較検査すると、95%以上が除去されていて溶解性物質の除去も極めて効果的に行なわれることが実証された。しかも、本発明の無機凝集剤は、これを単に処理液に混合して攪拌するだけで、事前に処理液のPH調整をしたり、無機凝集剤等の助剤添加による機能増進を図ったりする煩雑な操作や、技術の熟練などは一切不要であって、充分な効果を安定して上げることができる。   As described above, when the BOD value of the supernatant water in a colorless and transparent state is compared with the BOD value of the treatment liquid before the coagulation treatment, 95% or more is removed, and the removal of soluble substances is extremely effective. It has been demonstrated that Moreover, the inorganic flocculant of the present invention simply adjusts the pH of the treatment liquid in advance by simply mixing it with the treatment liquid and stirring it, or promotes the function by adding an auxiliary agent such as an inorganic flocculant. No complicated operation or technical skill is required, and sufficient effects can be stably achieved.

また、本発明の無機凝集剤は、一回目の使用により凝集沈降した物質を除去すれば、この無機凝集剤液を次の処理液に加えて、処理液中に分散する微粒物質(コロイド溶液)の凝集・沈降等を助成する2回目の作用を行わせ、この際に凝集・沈降した物質を除去した後に、凝集剤液を更に新たな処理液に加えて、液中に分散する物質の凝集・沈降を助成させる3回目の作用を行うという実験を多数回繰り返しても、凝集剤液の濃度保障に留意すれば、凝集・沈降等の助成機能には変化が認められず、このことから、本発明の無機凝集剤は繰り返し使用できるものであることが実証された。
(実験例1)
In addition, the inorganic flocculant of the present invention is a finely divided substance (colloidal solution) that is dispersed in a treatment liquid by adding the inorganic flocculant liquid to the next treatment liquid if the substance that has been aggregated and settled by the first use is removed. After aggregating / sedimenting, etc., the second action is performed, and the agglomerated / precipitated material is removed, the aggregating agent liquid is further added to the new treatment liquid, and the substance dispersed in the liquid is agglomerated.・ Even if the experiment of performing the third action to support sedimentation is repeated many times, if attention is paid to the concentration guarantee of the flocculant liquid, there is no change in the subsidizing functions such as aggregation and sedimentation. It has been demonstrated that the inorganic flocculant of the present invention can be used repeatedly.
(Experimental example 1)

蠣殻500gを減速攪拌機を備えた200lの製造容器に入れて、この容器へ濃度8%の硫酸アルミニウムの水溶液200lを加えて、蠣殻が上記水溶液に漬かる状態で24時間攪拌した。その結果、容器には蠣殻から凝集機能成分となる微量元素(ミネラル)が溶出した200lの凝集剤原液が得られた。そこで、水180lに凝集剤原液の20lを加えて凝集剤液を調製した。
(実験例2)
500 g of rice husk was placed in a 200 l production vessel equipped with a speed reducer, 200 l of an aqueous solution of aluminum sulfate having a concentration of 8% was added to this vessel, and the rice hulls were stirred for 24 hours in a state of being immersed in the aqueous solution. As a result, 200 l of a flocculant stock solution in which trace elements (minerals) serving as aggregating functional components were eluted from the rice husk was obtained in the container. Therefore, 20 l of the flocculant stock solution was added to 180 l of water to prepare a flocculant solution.
(Experimental example 2)

実験例1において得た凝集剤液の10倍液20lを、10mのタンクに取った8mの豚尿排水に加えて、15分間攪拌してその後静止させた。その結果、豚尿排水中の微粒物質は、60秒で凝集を始めてフロックを形成し、フロックの成長に伴い沈降して、60分後にはフロックがタンクの底に沈降層を形成し、その上には透明な水が存在する状態となった。そして、この上澄水のBOD値を計測すると、1回目は150ppm以下であり、原排水のBODは6000ppmであるから、本発明の凝集剤液による処理ではBODの除去率が97.5%以上に達することが実証された。また、2回目の処理では、150ppmのBOD排水に対して上記処理を繰り返し行なった。その結果、BOD値は15ppmとなり、除去率は90%になることが確認された。
(実験例3)
20 l of the 10-fold solution of the flocculant solution obtained in Experimental Example 1 was added to 8 m 3 swine urine drainage taken in a 10 m 3 tank, stirred for 15 minutes, and then allowed to stand still. As a result, the fine particulate matter in the swine urine drainage begins to agglomerate in 60 seconds to form a floc, settles as the floc grows, and after 60 minutes, the floc forms a sedimentation layer at the bottom of the tank. There was clear water in the state. And when the BOD value of this supernatant water is measured, the first time is 150 ppm or less, and the BOD of the raw waste water is 6000 ppm. Therefore, in the treatment with the flocculant liquid of the present invention, the removal rate of BOD is 97.5% or more. Proved to reach. In the second treatment, the above treatment was repeated for 150 ppm BOD wastewater. As a result, it was confirmed that the BOD value was 15 ppm and the removal rate was 90%.
(Experimental example 3)

実験例2において、豚尿排水に凝集剤を加え、緩やかに攪拌した後に、攪拌を停止するとき、廃水のPHを検査して酸性状態にあれば、アルカリ剤を注入して廃水が中性となるように加減した。こうすると、酸性状態のときに比べて凝集沈降が著しく増進されて、30分で実験例2と同様の結果が得られた。
(実験例4)
In Experimental Example 2, after adding flocculant to swine urine drainage and stirring gently, when stirring is stopped, the pH of the wastewater is inspected and if it is in an acidic state, the alkaline agent is injected to make the wastewater neutral. Adjusted to be. As a result, the coagulation sedimentation was remarkably enhanced as compared with the acidic state, and the same result as in Experimental Example 2 was obtained in 30 minutes.
(Experimental example 4)

豚尿排水500ccをビーカーに取って、希釈凝集剤の5cc加え、5.6秒間攪拌してその後静止させた。その結果、豚尿排水中の微粒物質は、20秒で凝集を始めてフロックを形成し、フロックの成長に伴い沈降して、2分後にはフロックが容器の底に沈降層を形成して、その上には透明な水が存在する状態となった。この試料についてBOD値は未計測である。
(実験例5)
500 cc of swine urine drainage was taken in a beaker, 5 cc of diluted flocculant was added, and the mixture was stirred for 5.6 seconds and then allowed to stand still. As a result, the fine substance in the swine urine drainage begins to aggregate in 20 seconds to form a floc, settles as the floc grows, and after 2 minutes the floc forms a sedimentation layer at the bottom of the container. There was clear water on the top. The BOD value is not measured for this sample.
(Experimental example 5)

曝気によりエマルジョン化している油脂類を含有する製菓工場の排水500ccを容器に取って、希釈凝集剤5ccを加え、5.6秒間攪拌してその後静止させた。その結果、排水中の微粒物質は20秒で凝集し始めてフロックを形成し、フロックの成長に伴い沈降して、2〜3分後にはフロックが容器の底に沈降層を形成して、その上には透明な水が存在する状態となった。この資料ついてもBOD値は未計測である。
(実験例6)
500 cc of waste water from a confectionery factory containing fats and oils emulsified by aeration was placed in a container, 5 cc of diluted flocculant was added, and the mixture was stirred for 5.6 seconds and then allowed to stand still. As a result, the fine particles in the wastewater start to aggregate in 20 seconds to form flocs, settle as the flocs grow, and after a few minutes, the flocs form a sedimentation layer at the bottom of the container. There was clear water in the state. The BOD value has not been measured for this material.
(Experimental example 6)

曝気によりエマルジョン化している油脂類を含有する弁当工場の排水500ccを容器に取って、希釈凝集剤5ccを加え、5.6秒間攪拌してその後静止させた。その結果、排水中の微粒物質は、20秒で凝集し始めてフロックを形成し、フロックの成長に伴な沈降して、2、3分後にはフロックが容器の底に沈降層を形成して、その上には透明な水が存在する状態となった。この試料についてもBOD値は未計測である。
(実験例7)
500 cc of wastewater from a bento factory containing fats and oils emulsified by aeration was placed in a container, 5 cc of diluted flocculant was added, and the mixture was stirred for 5.6 seconds and then allowed to stand still. As a result, the particulate matter in the wastewater begins to aggregate in 20 seconds to form flocs, settles as the flocs grow, and after a few minutes the flocs form a sedimentation layer at the bottom of the container, On top of that, transparent water was present. The BOD value is not measured for this sample as well.
(Experimental example 7)

生活排水500ccを容器に取って、希釈凝集剤5ccを加え、5.6秒間攪拌してその後静止させた。その結果、排水中の懸濁物質は、20秒で凝集し始めてフロックを形成し、フロックの成長に伴い沈降して、2,3分後にはフロックが容器の底に沈降層を形成して、その上には透明な水が存在する状態となった。この試料についてもBOD値は未計測である。   500 cc of domestic wastewater was taken in a container, 5 cc of diluted flocculant was added, and the mixture was stirred for 5.6 seconds and then allowed to stand still. As a result, suspended substances in the wastewater start to aggregate in 20 seconds to form flocs, settle as the flocs grow, and after a few minutes the flocs form a sedimentation layer at the bottom of the container, On top of that, transparent water was present. The BOD value is not measured for this sample as well.

本発明に係る無機凝集剤は、これが最も反応し易い状況で使用することが重要であり、処理の対象となる排水の濃度に応じて凝集剤の濃度を800ppm以下の範囲内で適正な値に設定する。但し、畜産や水産関連の排水の連続処理において一定した濃度が保てるように希釈処理を行なうこととし、凝集沈降の処理は1回で終了するよりも、1回目の上澄液に対して同じ処理を2回以上繰り返す方が効率的であり、安全性が確保される。   It is important to use the inorganic flocculant according to the present invention in a state where it reacts most easily, and the concentration of the flocculant becomes an appropriate value within a range of 800 ppm or less depending on the concentration of wastewater to be treated. Set. However, dilution treatment is performed so that a constant concentration can be maintained in continuous processing of livestock and fishery-related wastewater, and the same treatment is performed on the first supernatant rather than completing the coagulation sedimentation treatment once. It is more efficient to repeat the process twice or more, and safety is ensured.

排水処理において微粒物質を極めて経済的に効率よく除去するのに適用できる。

It can be applied to the removal of fine substances in wastewater treatment very economically and efficiently.

Claims (1)

液体中に分散する微粒物質が会合して、より大きな会合体を造る凝集作用を助長させる無機凝集剤であって、
この無機凝集剤は、牡蠣等の貝殻を原料として、この原料に硫酸アルミニウム、ポリ塩化アルミニウムか、これらと同効質剤の水溶液を作用させて、原料が含有する凝集機能成分を溶出させたものである
ことを特徴とする無機凝集剤。
An inorganic flocculant that promotes the agglomeration action by which fine substances dispersed in a liquid associate to form a larger aggregate,
This inorganic flocculant is made from shells such as oysters, and the raw material is made of aluminum sulfate, polyaluminum chloride, or an aqueous solution of the same effect agent, and the aggregating functional components contained in the raw material are eluted. An inorganic flocculant characterized by
JP2003426518A 2003-12-24 2003-12-24 Inorganic flocculant Pending JP2005177720A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009050752A (en) * 2007-08-23 2009-03-12 Shoichi Yoshizumi Flocculant
JP5492335B1 (en) * 2013-08-08 2014-05-14 株式会社ケイ・アール・ジー Method for producing flocculant and flocculant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009050752A (en) * 2007-08-23 2009-03-12 Shoichi Yoshizumi Flocculant
JP5492335B1 (en) * 2013-08-08 2014-05-14 株式会社ケイ・アール・ジー Method for producing flocculant and flocculant

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