JP2006320836A - Instant flocculant for treating polluted water and method for treating polluted water using the same - Google Patents

Instant flocculant for treating polluted water and method for treating polluted water using the same Download PDF

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JP2006320836A
JP2006320836A JP2005146197A JP2005146197A JP2006320836A JP 2006320836 A JP2006320836 A JP 2006320836A JP 2005146197 A JP2005146197 A JP 2005146197A JP 2005146197 A JP2005146197 A JP 2005146197A JP 2006320836 A JP2006320836 A JP 2006320836A
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flocculant
cement
water
alkaline
polluted water
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JP2005146197A
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Japanese (ja)
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Etsuro Sakagami
越朗 坂上
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Teramura Tokuzo
寺村 徳三
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an instant flocculant for treating polluted water being effective as a means for increasing the added-value for conventional alkaline cements, environment-friendly and safe, having strong cohesion and stability, providing a short reaction time and rapid settling of sludge, and being inexpensive from a viewpoint of running cost without being affected by water temperature, pH and the like, and a method for treating polluted water using the flocculant. <P>SOLUTION: The instant flocculant for treating polluted water is obtained by adding artificial zeolite containing silicon oxide and aluminum oxide as ingredients or a flocculation accelerator such as non-aluminum based cinderellite (R)S to a base resin comprising an alkaline cement containing at least one of a calcareous substance comprising limestone and calcium carbonate, and an alkaline viscous substance comprising soft viscosity loam of a main component of silica, wherein the alkaline cement is any of a portland cement, a portland cement-based cement mixture and a special cement. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention can recover sludge generated by civil engineering work or waste water such as waste liquid discharged by industrial waste treatment in a state of instantaneous solid-liquid separation into neutral floc and water, and recycle these. The present invention relates to an instantaneous flocculant for treating polluted water that can be used in the present invention and a method for treating polluted water using the same.
  Conventionally used soil improvement stabilizers are mainly cement-based solidifying agents, lime-based solidifying agents, and high-molecular-weight solidifying agents, and generally adjust the high moisture content generated at civil engineering sites. It is used to For example, when coal ash is used as a soil conditioner, it is difficult to handle because its particles are too fine, and the elution of hexavalent chromium often exceeds the soil environmental standards. There is a limit to the use of fly ash in the state.
Also, tens of thousands of tons of cement are used in reclamation projects. This cement-based solidifying agent (for example, Patent Document 1) is obliged to conduct a hexavalent chromium elution test according to national environmental standards. In other words, the solidification agent cannot be used unless a hexavalent chromium elution test is conducted and the result is below the soil environmental standard. As described above, the soil improvement material as a conventional solidifying agent has a large adverse effect on the natural environment, and it is necessary to pay sufficient attention to the use of these solidifying agents.
JP 2004-292568 A
  However, in the past, for example, sludge produced by civil engineering work or waste water such as waste liquid discharged by industrial waste treatment is separated into neutral floc and water in a short period of time and made harmless. The fact is that an instant flocculant for treating contaminated water that can be easily recovered has not been developed yet. Moreover, conventionally, the utility value of alkaline cement is limited only as a cement-based solidifying agent, and other added values cannot be increased.
  Therefore, the present invention was created in view of the existing circumstances as described above, and is effective as a means for increasing the added value with respect to the existing alkaline cement, and is environmentally friendly, safe, and has a strong cohesive force. And instant flocculant for the treatment of contaminated water, which is stable and has a short reaction time and fast sludge sedimentation, is not affected by water temperature, pH, etc., and is low in running cost. The purpose is to provide a contaminated water treatment method.
In order to solve the above-mentioned problems, the instant flocculant for treating contaminated water according to claim 1 according to the present invention is at least one of a calcareous substance composed of limestone and calcium carbonate, and an alkaline viscosity substance composed of a soft viscosity loam composed mainly of silica. It is characterized in that it is made by adding an artificial zeolite containing silicon oxide and aluminum oxide as a main component, or a non-aluminum-based agglomeration accelerator, to an alkaline cement containing
The instant flocculant for treating contaminated water according to claim 2 is the invention according to claim 1, wherein the alkaline cement is any one of Portland cement, Portland cement-based mixed cement, and special cement.
The instant flocculant for treating polluted water according to claim 3 may include pulp sludge (PS ash) that can be artificially converted into zeolite in the main agent and the flocculant accelerator in the invention according to claim 1 or 2.
The instant flocculant for treating polluted water according to claim 4 is the structure according to any one of claims 1 to 3, wherein the alkaline cement is mixed with 8 to 9 and the aggregation accelerator is mixed in a ratio of 2 to 1. And
The instant flocculant for treating polluted water according to claim 5 is the invention according to claim 1, wherein the non-aluminum-based flocculant accelerator is Cinderellite (registered trademark) S.
The method for treating polluted water according to claim 6 is characterized in that an instantaneous flocculating agent comprising an alkaline cement as a main ingredient and an artificial zeolite or a non-aluminum flocculating accelerator added thereto is added to a sewage water treating tank provided with a stirring means. Introduced, the contaminated water is stirred to neutralize floc and water, and the floc and water are collected individually.
  The instant flocculant for treating polluted water according to the present invention configured as described above and the method for treating polluted water using the same, and an artificial zeolite containing silicon oxide and aluminum oxide as a constituent relative to the main component of alkaline cement In addition, the instantaneous flocculant formed by adding a flocculant accelerator such as non-aluminum Cinderellaite S makes the fouled water neutral and makes it possible to collect these floc and water individually. .
  In other words, the surface of most suspended fine particles that cause water pollution in nature is negatively charged. The suspended fine particles are dispersed and suspended in the water by Brownian motion due to electrostatic repulsion. By adding an instantaneous flocculant that is a positively charged substance (cation) to the surface of these negatively charged fine particles (anions), the repulsive negative charge on the surface of the pollutant is neutralized and the repulsive force is reduced. The particles attract each other by van der Waals attractive force acting between the particles to form an aggregate. The resulting fine aggregates are further cross-linked to coarsen the aggregates for precipitation separation or flotation separation.
  According to the present invention, it is effective as a means for increasing the added value to the existing alkaline cement, is environmentally friendly and safe, has strong cohesive force and stability, and has a short reaction time and fast sludge precipitation. In addition, it is possible to provide an instant coagulant for treating contaminated water that is not affected by the water temperature, pH, etc., and is low in running cost, and a method for treating contaminated water using the same.
  That is, since the cement itself as the main agent is alkaline, it is easy to neutralize or weakly acidize the acidic polluted water so that it is within the standard value that can be discharged into the soil or the like. In addition, when the sediment is harmless, when it is dehydrated and returned to the ground, it is also used as a soil solidifying agent or a soil improvement stabilizer by mixing other waste such as PS ash. be able to.
  Specifically, the cement price is currently stagnant at around 6000 to 10000 yen per ton (6 to 10 yen per kg). Since the instantaneous flocculant according to the present invention has a production cost set at around 100 to 120 yen per kg, the general wholesale price is provided as 350 to 450 yen per kg. This is effective as a means for increasing the added value of cement. In addition, it is very useful and convenient to be able to return the sediment to the ground in a harmless state while the ground is exhausted and acidified due to the influence of acid rain and the like.
  Hereinafter, the best mode for carrying out the present invention will be described. The instant flocculant of the present invention is an alkaline cement having a porous structure containing at least one of a calcareous material composed of limestone and calcium carbonate, and an alkaline viscosity material composed of a silica-based soft viscosity loam, such as Portland cement and Portland cement. High cation exchange consisting mainly of various cements such as mixed cements and special cements, and agglomeration accelerators, for example, silicon oxide and aluminum oxide mixed at a specified caivan ratio and heated with an alkaline aqueous medium. An artificial zeolite-based instantaneous flocculant is obtained by adding an artificial zeolite having a capacity and an adsorptivity.
  This alkaline cement has a function of neutralizing acidified soil. The specific surface area of cement is generally said to be about 3300 square m / g. It can be said that this has 3-6 times the adsorption capacity compared with adsorbents, such as activated carbon. That is, since these fine particles have a large specific surface area, the contact area with negative ions in the polluted water also increases, and the agglomeration effect can be remarkably increased.
  Artificial zeolite, which is coal ash that has been subjected to alkali treatment, has excellent functions such as adsorption performance, ion exchange capacity, and catalyst capacity. Artificial zeolite itself is a porous structure and has micropores such as acropores and micropores, and contributes to adsorption of toxic substances in water. The artificial zeolite to be added contains a large amount of silicon dioxide (silica) and dialuminum trioxide (alumina), and also contains iron oxide, calcium oxide, titanium oxide and the like. In particular, composite alumina has ion exchange properties.
  In addition, aluminum oxide becomes aluminum hydroxide and polycondensed aluminum, and has the function of forming aggregates by accelerating the potential drop between the suspended suspended particles, causing the particles to collapse and atomize. . Therefore, the pollutant can be encapsulated in the gap between the OH groups in water by this reaction.
  Further, composite alumina contains mineral trace elements and has a function of adsorbing, precipitating and separating metals dissolved in water by elution into water and playing a catalytic role. At this time, in order to link the process of coarsening between fine pollutants by cross-linking, the rate of formation of condensed ions or solid aluminum oxide generated when aluminum ions are hydrolyzed in water increases the size of the aggregates. It plays a big role in affecting the precipitation rate.
  Specifically, this mineral trace element acts as an oxidation catalyst, and converts water-soluble organic substances into insoluble organic substances and aggregates them as a precipitated solid. In other words, mineral trace elements need to have a formulation that works with an organic oxidation catalyst by dissolved oxygen in water or dissociated ions in water, part of which becomes a salt and turns into an insoluble substance, forming sludge. .
  In other words, the surface of most suspended fine particles that cause water pollution in nature is negatively charged. The suspended fine particles are dispersed and suspended in the water by Brownian motion due to electrostatic repulsion. By adding a positively charged substance to the surface of these negatively charged fine particles, the repulsive negative charge on the surface of the pollutant is neutralized, the repulsive force is reduced, and the van der Waals attractive force acting between the particles. The particles attract each other to form an aggregate. The resulting fine aggregates can be further crosslinked to coarsen the aggregates for precipitation separation or flotation separation.
  The basic agglomeration theory is that the basic natural mineral powder produces hydrolysis products and polymers (polynuclear complexes) that are produced in the process of ion hydrolysis to form agglomeration nuclei, which are adsorbed and crosslinked between particles. As a result, secondary coupling occurs and flocs are formed. At this time, the hydrolysis product of the inorganic composite aluminum is said to be a polynuclear hydroxo metal complex salt and a polycation having a high charge. The hydrolysis reaction of metal ions is a reaction in which protons dissociate from an aco-complex, and further involves dehydration and oscillation.
  On the other hand, the process from coagulation to coagulation and precipitation is based on the process from the hydrolysis reaction of trivalent aluminum ions to polymerization, and from aging to the formation of water-insoluble colloidal, hydroxo and polymer, followed by coagulation and precipitation. ing.
Based on this agglomeration theory, it is necessary to use a composite aluminum silicate in a natural mineral as a polymer, and to add a polymerized ion having a charge larger than that of the monomer, thereby to neutralize the surface charge of the suspended substance. Therefore, a small amount of [Al 2 (OH) nCl 6 -n] m, [Al 2 (SO 4 ) 3 ] or the like is added to accelerate the aggregation.
  Further, as another example of the present embodiment, non-aluminum-based Cinderellite S that does not use any sulfate or aluminum sulfate as an agglomeration accelerator is added to the above-mentioned main components that are various cements. It can also be a system instantaneous flocculant.
  That is, for the purpose of improving the agglomeration rate and generating strong flocs, Cinderella S as an auxiliary agent by forcibly applying a charge to a substance as a special base material at a high pressure is mixed with, for example, Portland cement or Portland cement Add a small amount to various types of cement such as cement and special cement.
  The Cinderellite S has, for example, pH 6.7, high specific gravity and water insolubility, and its components and contents are 41.4% sulfur trioxide, 29% calcium oxide, and 15.1 silicon dioxide. %, Dialuminium trioxide 9.2%, Ferric trioxide 2.1%, Sodium oxide 1.3%, Potassium oxide 0.9%, Magnesium oxide 0.5%, Titanium dioxide 0.2% is used.
  As a specific blending example of the agglomeration accelerator with respect to the main agent, the agglomeration accelerator is mixed at a ratio of 2 to 8 for the alkaline cement at a normal water content. Further, in the case of low humidity with a water content of 15% or less, the coagulation promoter is mixed at a ratio of 1 to 9 for the alkaline cement. Specifically, for example, alkaline cement contains 150 to 200 g of an aggregation accelerator per ton.
  As still another example of the present embodiment, pulp sludge (PS ash) that contains a large amount of unburned carbon and can be artificially converted into zeolite can be included in the main agent and the aggregation accelerator. This artificial zeolitic pulp sludge (PS ash) has a remarkable deodorizing function and a high fusion property with existing soil, and is excellent in water permeability and water retention, and can be produced at a very low cost.
  Next, a specific method for treating contaminated water for the best mode configured as described above will be described. That is, the method for treating polluted water according to the present invention includes an instantaneous flocculant obtained by adding an agglomeration accelerator such as artificial zeolite or Cinderellaite S to alkaline cement as a main agent in a polluted water treatment apparatus equipped with a stirring means. It introduces, stirs the polluted water in the apparatus, separates it into neutral floc and water, and collects these floc and water individually via a suction hose.
  Specifically, as shown in the polluted water treatment flow of FIG. 1, the stirring tank 2 provided with stirring means such as a badge-type V mixer, corn mixer, resin tumbler, Henschel mixer, etc. A sedimentation tank 3 is installed on each side, and an agglomeration accelerator tank 4 for supplying an agglomeration accelerator is provided on the upper side of the agitation tank 2 to constitute the polluted water treatment apparatus 1. In this apparatus 1, the polluted water is lifted from the polluted water tank 6 through the suction hose 5 attached to the pump, and supplied into the stirring tank 2. At the same time, the coagulation promoter is added from the coagulation promoter tank 4 into the agitation tank 2, and the contaminated water is agitated here to be instantaneously solid-liquid separated into neutral floc and water into the precipitation tank 3. There is something to store.
  Then, the water in the settling tank 3 is discharged through the suction hose 5, while the floc precipitated at the bottom of the settling tank 3 is introduced into the sludge knock tank 7 through the suction hose 5 as sludge. The sludge introduced into the sludge knock tank 7 is sent, for example, to the dewatering means side by natural dewatering through the suction hose 5 and dehydrated and dried there. At this time, the water dehydrated on the dehydrator 8 side is returned to the sludge knock tank 7 and then discharged through the suction hose 5.
  The dewatering means 8 uses ton bag natural dewatering when the amount of sludge is about 20 tons or less. In addition, when the amount of sludge is about 100 tons or more, for example, dewatering by a filter press, dewatering by centrifugation, etc. Is adopted.
  It should be noted that the above-described contaminated water treatment flow is merely an example of an embodiment of the present invention, and does not limit the present invention in any way, and it goes without saying that other contaminated water treatment flows can be employed.
  Next, the analysis test result of the treated water when using the instantaneous flocculant for the best mode configured as described above will be described. That is, raw polluted water having a hydrogen ion concentration (hydrogen index) of 7.3 (25 ° C.), a biochemical oxygen demand of 19 mg / L, a chemical oxygen demand of 160 mg / L, and a suspended solid content of 4100 mg / L As a result of the water quality analysis test of the treated water, the hydrogen ion concentration (hydrogen index) is 7.4 (25 ° C.), the biochemical oxygen demand is less than 1 mg / L, the chemical oxygen The required amount was 2 mg / L and the suspended solid amount was 11 mg / L.
  In addition, raw pollution with a hydrogen ion concentration (hydrogen index) of 7.6 (25 ° C.), a biochemical oxygen demand of less than 1 mg / L, a chemical oxygen demand of 15 mg / L, and a suspended solid content of 16000 mg / L When water was treated with an instantaneous flocculant, the results of a water quality analysis test of the treated water showed that the hydrogen ion concentration (hydrogen index) was 7.7 (25 ° C.), the biochemical oxygen demand was less than 1 mg / L, chemical The oxygen demand was 1 mg / L and the suspended solids amount was 12 mg / L.
As an analytical test method adopted, the hydrogen ion concentration (hydrogen index) is JIS K
0102 12.1, biochemical oxygen demand is JIS K 0102 21 and JIS K 0102 32.3, chemical oxygen demand is JIS K 0102 17, and suspended solids is S46. The analysis was made based on Appendix 8 of Circular 59.
  In addition, as a result of an acute toxicity test on the number of organisms of 10 using the medaka of the aggregation promoter using Cinderellite S, both the control group and 1000 mg / L were exposed and exposed to the sun. The cumulative mortality rate of medaka was 0% even after time, and no abnormal breathing, abnormal swimming, non-swimming, or other special cases were observed with respect to toxic symptoms, and all were normal.
  At this time, the water quality of the test solution is pH 8.1 at 0 hours, pH 8.0 at 48 hours, pH 7.7 at 96 hours, and 0 when the set concentration is 1000 mg / L. The pH becomes 8.0 at time, pH 7.8 at 48 hours, pH 7.6 at 96 hours, and both approach pH 7.
  Demand oxygenogen DO dissolved in water is 7.9 mg / L at 0 hours, 6.6 mg / L at 48 hours, and 6.4 mg at 96 hours when the set concentration is the control group. When the set concentration is 1000 mg / L, it is 7.9 mg / L at 0 hour, 6.5 mg / L at 48 hours, and 6.3 mg / L at 96 hours.
  Furthermore, the water temperature of the test solution was 25.0 ° C. in 0 hours, 24.6 ° C. in 48 hours, 25.0 ° C. in 96 hours, and when the set concentration was 1000 mg / L, 25.0 ° C. in 0 hours, It was 24.6 ° C. in 48 hours and 25.0 ° C. in 96 hours, showing almost no change.
  Further, the LC50 value shows a value of 1000 mg / L or more even after 96 hours have passed, the NOEC value shows a value of 1000 mg / L, and the LOEC value shows a value of 1000 mg / L or more.
  Instead of using the above-mentioned alkaline cement as the main agent, for example, bagasse containing cellulose which is a water-insoluble plant fiber, pineapple containing guar gum which is a water-soluble plant fiber, sugarcane, etc. After carbonizing into porous carbides, an organic instantaneous flocculant can be formed by adding an aggregation promoter such as artificial zeolite or non-aluminum Cinderellite S to these.
  Moreover, the main agent can also be manufactured with iron oxide-based red clay. In any case, other main agents may be used as long as the main agent itself has a porous structure. For example, a pulverized product of a porous concrete block can be reused.
It is explanatory drawing which shows the polluted water processing flow in the best form for implementing this invention.
Explanation of symbols
DESCRIPTION OF SYMBOLS 1 Polluted water processing apparatus 2 Agitation tank 3 Precipitation tank 4 Aggregation promoter tank 5 Suction hose 6 Polluted water tank 7 Sludge knock tank 8 Dehydration apparatus

Claims (6)

  1.   Artificial zeolite composed mainly of alkaline cement containing at least one of calcareous material composed of limestone and calcium carbonate, alkaline viscosity material composed of silica-based soft viscosity loam, and silicon oxide and aluminum oxide as a main component, or non An instant flocculant for treating polluted water, comprising an aluminum-based flocculant accelerator.
  2.   The instant flocculant for treating contaminated water according to claim 1, wherein the alkaline cement is any one of Portland cement, Portland cement-based mixed cement, and special cement.
  3.   The instant flocculant for contaminated water treatment according to claim 1 or 2, comprising pulp sludge (PS ash) that can be artificially converted into zeolite in the main agent and the flocculant accelerator.
  4.   The instantaneous flocculant for contaminated water treatment according to any one of claims 1 to 3, wherein the coagulation promoter is mixed in a ratio of 2 to 1 to 8 to 9 in the alkaline cement.
  5.   The non-aluminum aggregation promoter is Cinderellite (registered trademark) S. The instant flocculant for dirty water treatment according to claim 1.
  6.   Instant flocculant composed mainly of alkaline cement and artificial zeolite or non-aluminum flocculant accelerator is introduced into the polluted water treatment tank equipped with stirring means, and the polluted water is stirred to floc A method for treating polluted water, characterized in that it is neutrally separated into water and water, and these floc and water are individually collected.
JP2005146197A 2005-05-19 2005-05-19 Instant flocculant for treating polluted water and method for treating polluted water using the same Pending JP2006320836A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885575A (en) * 2010-07-02 2010-11-17 广东工业大学 Solidification/stabilization treatment method for papermaking sludge
CN102161562A (en) * 2011-03-10 2011-08-24 北京科技大学 Process for treating excess sludge by utilizing fly ash
CN103641285A (en) * 2013-11-30 2014-03-19 河南华天环保科技有限公司 Conditioning agent for sludge treatment and method for sludge treatment by using same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885575A (en) * 2010-07-02 2010-11-17 广东工业大学 Solidification/stabilization treatment method for papermaking sludge
CN102161562A (en) * 2011-03-10 2011-08-24 北京科技大学 Process for treating excess sludge by utilizing fly ash
CN103641285A (en) * 2013-11-30 2014-03-19 河南华天环保科技有限公司 Conditioning agent for sludge treatment and method for sludge treatment by using same

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