CN102079563A - Regenerative coagulant, and preparation method and using method thereof - Google Patents
Regenerative coagulant, and preparation method and using method thereof Download PDFInfo
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- CN102079563A CN102079563A CN 201010597694 CN201010597694A CN102079563A CN 102079563 A CN102079563 A CN 102079563A CN 201010597694 CN201010597694 CN 201010597694 CN 201010597694 A CN201010597694 A CN 201010597694A CN 102079563 A CN102079563 A CN 102079563A
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- coagulant
- coagulating agent
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Abstract
The invention relates to a regenerative coagulant, and a preparation method and a using method thereof. The regenerative coagulant is characterized in that: the regenerative coagulant is prepared from waste concrete serving as a raw material. The preparation method comprises the following specific steps of: collecting the waste concrete, rejecting sands, crushing and grinding the waste concrete, sieving the ground concrete by using a 150-mesh sieve, calcinating the sieved concrete for 2h, cooling the calcinated concrete and levigating the cooled concrete to obtain the regenerative coagulant in form of powder with the particle sizes of less than 0.03mm and the specific surface area of 3,000 to 4,000 cm<2>/g. The regenerative coagulant and the preparation method ensure a good coagulation effect by fully utilizing the hydration of artificial minerals such as monocalcium aluminate, dicalcium phosphate, tricalcium silicate, tricalcium aluminate, tetracalcium aluminoferrite and the like, the electrical neutralization, absorption and enmeshment effects of hydrolyzate and the synergism of coagulation and precipitation; and in the using method, coagulant regeneration is realized by utilizing the high precipitation performance of coagulation sludge and adopting filtration, drying and calculation flows to recycle the coagulant for many times.
Description
Technical field
The present invention relates to a kind of reproducible coagulating agent and preparation and using method, be used for the processing of refractory dyeing waste water and other waste water, belong to environmental technology field.
Background technology
Dyeing is the discharge of industrial wastes rich and influential family, and China's dyeing waste water total emission volumn reaches 5.5 * 10 at present
8T/a accounts for 13% of whole trade effluent.The difficulty in treatment of textile printing and dyeing wastewater is: (1) COD height, and biodegradability is poor; (2) colourity height, complicated component, decolouring difficulty are big.
Treatment method of printing and dying wastewater is broadly divided into: (1) biological treatment, promptly utilize micro bioenzyme catalysis degradation of organic substances molecule, by vital movements such as a series of oxidations, reduction, hydrolysis, chemical combination, organic matter degradation becomes simple inorganics or is converted into various nutrition and biomass in the waste water the most at last.Because the waste water from dyestuff complicated component contains a large amount of materials to the toxic property of microorganism, direct biochemical effect is bad, and decoloring ability is limited, often need carry out pre-treatment; (2) chemical oxidization method, comprise high-level oxidation technology, promptly utilize oxygenant to make in the dye molecule unsaturated double-bond of chromophoric group oxidized and disconnect, form less organism or the inorganics of molecular weight, wherein the photosensitization semi-conductor is as the catalyst treatment dyeing waste water, be a more branch of Recent study, catalyzer adopts mostly with TiO in this method
2Titanium based semiconductor catalyst or other noble metal catalysts for representative; (3) physicochemical treatment method mainly comprises absorption method, electrochemical process and Coagulation Method.Absorption method promptly utilizes the cellular solid sorption to separate water pollutant; Electrochemical process promptly utilizes effect saboteurs' such as electrolytic oxidation, electrolytic reduction, electrolytic flocculation or electrolysis come-up structure to reach the decolouring purpose; Coagulation Method is widely used, and as the Wastewater Pretreatment operation, obviously alleviates the load of high turbidity, high-concentration printing and dyeing wastewater biological treatment, also can be placed on after the biochemical treatment, improves percent of decolourization, guarantees qualified discharge, or creates conditions for water depth processing reuse.
Along with the development of dyestuffs industries and the progress of back finishing technique, refractory organics such as New-type adjuvant, dyestuff, finishing composition are used in a large number at dyeing, cause that COD in the dyeing waste water increases, BOD/COD is lower, the wastewater treatment difficulty also increases thereupon day by day, adopt the traditional dyeing and finishing waste water treatment process, effluent index is difficult to reach emission standard.The coagulation operation is often indispensable.Select suitable coagulating agent, improve coagulation effect, reducing processing cost is the main contents of research and development.
Coagulating agent commonly used comprises: organic polymer coagulating agent (as polyacrylamide etc.), inorganic coagulant (as polymerize aluminum chloride, polyaluminium sulfate etc.), the compound coagulating agent of organic-inorganic (as iron(ic) chloride-dimethyl diallyl ammonium chloride homopolymer, poly-ferric chloride-dimethyl diallyl ammonium chloride homopolymer etc.).Coagulating agent ubiquity price height commonly used, to shortcomings such as hydrophilic dye poor processing effect, the mud of generation can't be reused, and needs solidification and stabilization to handle before the landfill, cost is higher, and the landfill place is limited.In addition, traditional coagulating agent treatment of dyeing and printing alumen ustum settling velocity is slow, and mud concentrates, filtration difficulty.If sludge treatment is improper, very easily cause secondary pollution.
Summary of the invention
The purpose of this invention is to provide that a kind of cost is low, coagulation efficiency is high, the adaptable coagulating agent of water quality and preparation and using method.
In order to achieve the above object, the invention provides a kind of reproducible coagulating agent, it is characterized in that, is that raw material is made by discarded concrete.
The present invention also provides the preparation method of above-mentioned reproducible coagulating agent, it is characterized in that, concrete steps are: collect the depleted concrete, reject sandstone, fragmentation, grinding, cross 150 mesh sieves, at 550-650 ℃ of temperature lower calcination 1 ~ 2 h, after the cooling, the levigate particle diameter that obtains is that 0.03 mm is following, specific surface area is 3000～4000 cm
2The powder of/g is reproducible coagulating agent.The fineness of powder has certain influence to coagulation effect, improves fineness, can improve coagulation effect, but the corresponding increase of power consumption simultaneously.There is dust raising phenomenon in grinding and the screening process, therefore dust collection device all should be installed, as settling pocket, cyclone, bag filter etc. at equipment import and export, course of conveying and packing place.
During use, above-mentioned reproducible coagulating agent is joined in the pending waste water, the coagulating agent add-on is 1～15 g/L, in certain intensity (as six stirrers, 150 r/min) leave standstill 30～50 min after fully stirring, utilize charge neutrality, absorption, the net of its hydrolysis, hydrated product to catch that volume is swept, bridging action, make the various material coagulant precipitations in the waste water, and utilize the synergy of physical and chemical processes such as precipitation, absorption, obtain mud and clear water.
The present invention also provides the regeneration method of above-mentioned reproducible coagulating agent, it is characterized in that, concrete steps are: with the mud suction filtration of coagulating sedimentation gained, dry, place 550-650 ℃ of temperature lower calcination 1～2 h, cooling back grinding to particle diameter is below 0.03 mm, specific surface area is 3000～4000 cm
2The powder of/g is used for coagulating waste water as coagulating agent once more and handles.Coagulating agent of the present invention continuous reproducible recycle more than 10 times at least.The coagulation effect of this coagulating agent is with the increase of regeneration times, and treatment effect has reduction slightly, and the mud after the inefficacy does not need other curing, stabilization treatment, can dispose by direct landfill.
The cardinal principle that the present invention realizes is as follows:
The present invention is the material that utilizes artificial mineral aquations such as Calucium Silicate powder, calcium aluminate, calcium ferrite, hydrolysis to produce, and makes the various material coagulant precipitations in the waste water, and utilizes the synergy of physical and chemical processes such as precipitation, absorption, and the realization pollutent separates with water.
(1) monocalcium aluminate (CA) is owing to the coordination irregular of calcium, aluminium in the crystalline structure, and aquation is exceedingly fast.Hydrated product difference under differing temps, the main hydration products under the room temperature are CAH
10Or C
2AH
8, all belong to hexagonal system, its crystal in the form of sheets or needle-like, interlaced seeking connections with, overlapping combination can form strong crystallization symphysis body, thereby reaches absorption, net is caught the coagulation effect that volume is swept, built bridge.
With coagulate sludge calcination and regeneration under 600 ℃ of conditions, hydrated product is reduced to C
xA(0＜x＜1) and Al
2O
3, come into operation once more, still have coagulation effect, renewable repeated use.
(2) tricalcium silicate (C
3S), Dicalcium Phosphate (Feed Grade) (C
2S), tricalcium aluminate (C
3A) and tetracalcium aluminoferrite C
4AF is an essential mineral in the silicate cement.C
3S and C
2The S aquation generates hydrated calcium silicate, and (C-S-H) gel and calcium hydroxide (CH), these materials have charge neutrality, absorption, net to catch coagulations such as volume is swept, bridge formation, and can adjust the pH value.In addition, C
3A and C
4The AF aquation generates the calcium ferrite of hexagonal drated calcium aluminate and colloidal, also has coagulation.
Tricalcium silicate C
3S has comparison intensive hydration reaction ability, and hydration reaction at normal temperatures can be represented with following formula:
Or:
C-S in the formula-H represents the unfixed hydrated calcium silicate of component.
With coagulate sludge calcination and regeneration under 600 ℃ of conditions, hydrated product is reduced to C
xS(0＜x＜3), C
zA(0＜z＜3) and CaO, come into operation once more, still have coagulation effect, renewable repeated use.
The present invention compared with prior art has following characteristics, and technical progress is very remarkable, has solved coagulating agent regeneration and sludge treatment disposal concerns preferably, has positive effect for reducing the treatment of dyeing wastewater cost and alleviating sludge treatment disposal pressure.
(1) owing to contain multiple ionizable metal salt in the coagulating agent, hydrolysis rate is fast, for the processing of waste water, than the monometallic salt coagulant, has stronger charge neutrality, absorption, volume and sweeps ability, and coagulation effect is better.
(2) can realize coagulating agent regeneration by low temperature calcination, improve the coagulating agent utilization ratio, reduce cost for wastewater treatment.
(3) repeatedly recycle the mud coagulating agent of (more than 10 times), when discarded at last, do not need other curing, stabilization treatment, directly landfill is saved the sludge treatment disposal costs.
Description of drawings
The reproducible novel coagulating agent that Fig. 1 proposes for the present invention prepares and recycles the synoptic diagram of flow process.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
As shown in Figure 1, the reproducible novel coagulating agent that proposes for the present invention prepares and recycles the synoptic diagram of flow process.Collect the depleted concrete, reject sandstone, being crushed to particle diameter earlier is below 25 mm, adopting autogenous mill grinding to particle diameter again is below 2 mm, cross 150 mesh sieves, at 550 ℃ of temperature lower calcination 2 h, after the cooling, adopting the high-pressure roller mill levigated to obtain particle diameter is that 0.03 mm is following, specific surface area is 3000～4000 cm
2The powder of/g is coagulating agent.
Hydrophobicity disperse scarlet dye configuration concentration is the dye wastewater of 0.15 g/L, and its initial pH value is about 8.0, and absorbancy is 1.41.Use above-mentioned coagulating agent that it is handled, (200 r/min) stirs 30 min fast earlier, and the back transfers jogging speed (100 r/min) to stir 5 h, precipitates 30 min at last, gets supernatant liquor and surveys absorbancy and pH.Increase the dosage of coagulating agent gradually, the dyestuff clearance of coagulation increases, and when coagulant charging quantity reached 11 g/L, it is best that coagulation efficiency reaches, and the dyestuff clearance reaches 99.0%.Sludge settling property is good, records its SV
30Be 25 mL/L.
With coagulating sedimentation gained mud B suction filtration, drying places 550 ℃ of temperature lower calcination 2 h, and cooling back grinding to particle diameter is below 0.03 mm, specific surface area is 3000～4000 cm
2The powder of/g is used for coagulating waste water as coagulating agent once more and handles.Clearance to dyestuff in the waste water still can reach 96.3%.10 times cyclic regeneration uses, though removal effect slightly descends, clearance still can reach 90.5%.
This coagulating agent has good coagulation effect to hydrophobicity disperse scarlet dye simulated wastewater, and sludge settling property is good, and renewable repeated use.
Embodiment 2
Collect the depleted concrete, reject sandstone, being crushed to particle diameter earlier is below 25 mm, adopting autogenous mill grinding to particle diameter again is below 2 mm, cross 150 mesh sieves, at 600 ℃ of temperature lower calcination 2 h, after the cooling, adopting the levigate particle diameter that obtains of high-pressure roller mill is that 0.03 mm is following, specific surface area is 3000～4000 cm
2The powder of/g is coagulating agent.
Hydrophilic active brilliant blue dye configuration concentration is the dye wastewater of 0.14 g/L, and its initial pH value is about 10.4, and absorbancy is 0.76.Use above-mentioned coagulating agent that it is handled, (200 r/min) stirs 30 min fast earlier, and the back transfers jogging speed (100 r/min) to stir 5h, precipitates 30 min at last, gets supernatant liquor and surveys its absorbancy and pH.Increase the dosage of coagulating agent gradually, the dyestuff clearance of coagulation increases, and when coagulant charging quantity reached 5 g/L, it is best that coagulation efficiency reaches, and the dyestuff clearance reaches 98.4%.Sludge settling property is good, records its SV
30Be 45 mL/L.
With coagulating sedimentation gained mud B suction filtration, drying places 600 ℃ of temperature lower calcination 2 h, and cooling back grinding to particle diameter is below 0.03 mm, specific surface area is 3000～4000 cm
2The powder of/g is used for coagulating waste water as coagulating agent once more and handles.Clearance to dyestuff in the waste water still can reach 91.6%.10 times cyclic regeneration uses, and the rate of removing still can reach 88.2%.
This coagulating agent has good coagulation effect to hydrophilic active brilliant blue dye simulated wastewater, and sludge settling property is good, and renewable repeated use.
Embodiment 3
Collect the depleted concrete, reject sandstone, being crushed to particle diameter earlier is below 25 mm, adopting autogenous mill grinding to particle diameter again is below 2 mm, cross 150 mesh sieves, at 650 ℃ of temperature lower calcination 2 h, after the cooling, adopting the high-pressure roller mill levigated to obtain particle diameter is that 0.03mm is following, specific surface area is 3000～4000 cm
2The powder of/g is coagulating agent.
Get the dyeing waste water of certain printing and dyeing mill's discharging, the dark and foul smelling flavor of its color, color takes on a red color.The water quality situation is after measured: the pH value is 9.5, and absorbancy is 0.56, COD
CrBe 860 mg/L, BOD
5Be 450 mg/L, SS is 230 mg/L, and colourity is 500 times.In the beaker of 1000 mL, add 500 mL dyeing waste water water samples, use above-mentioned coagulating agent that it is handled, (200 r/min) stirs 30 min fast earlier, and the back transfers jogging speed (100 r/min) to stir 5 h, precipitate 50 min at last, get supernatant liquor and survey its absorbancy and COD.Increase the dosage of coagulating agent gradually, the dyestuff clearance of coagulation increases, and when coagulant charging quantity reached 3.8 g/L, it is best that coagulation efficiency reaches, COD
CrClearance reaches 95.7%, and chroma removal rate reaches 90%.
With coagulating sedimentation gained mud B suction filtration, drying places 650 ℃ of temperature lower calcination 2 h, and cooling back grinding to particle diameter is below 0.03 mm, specific surface area is 3000～4000 cm
2The powder of/g is used for coagulating waste water as coagulating agent once more and handles, to COD in the waste water
CrClearance still can reach 93.6 %.10 times cyclic regeneration uses, and the rate of removing still can reach 90.1%.
This coagulating agent has coagulating treatment effect preferably to actual dying, and the result of use that repeats to regenerate is good, and sludge settling is rapid, easily filter dehydration.
Claims (4)
1. a reproducible coagulating agent is characterized in that, is that raw material is made by discarded concrete.
2. the preparation method of the described reproducible coagulating agent of claim 1, it is characterized in that, concrete steps are: collect the depleted concrete, reject sandstone, fragmentation, grinding, cross 150 mesh sieves, at 550-650 ℃ of temperature lower calcination 1 ~ 2 h, after the cooling, the levigate particle diameter that obtains is that 0.03 mm is following, specific surface area is 3000～4000 cm
2The powder of/g is reproducible coagulating agent.
3. the using method of the described reproducible coagulating agent of claim 1, it is characterized in that, concrete steps are: the described reproducible coagulating agent of claim 1 is joined in the pending waste water, the coagulating agent add-on is 1～15 g/L, leave standstill 30～50 min after fully stirring, obtain mud and clear water.
4. the using method of reproducible coagulating agent as claimed in claim 3, it is characterized in that, with the mud suction filtration of coagulating sedimentation gained, drying, place 550-650 ℃ of temperature lower calcination 1～2 h, cooling back grinding to particle diameter is below 0.03 mm, specific surface area is 3000～4000 cm
2The powder of/g is used for coagulating waste water as coagulating agent once more and handles.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016436A (en) * | 2014-06-12 | 2014-09-03 | 南昌大学 | Zinc-containing wastewater treatment method |
| CN104108777A (en) * | 2014-08-04 | 2014-10-22 | 罗光臣 | Method for treating acidic wastewater or waste acid with cement |
| RU2534137C1 (en) * | 2013-06-14 | 2014-11-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Петербургский государственный университет путей сообщения" | Method of sewage water purification from metal ions |
| CN106734113A (en) * | 2017-01-20 | 2017-05-31 | 深圳华云环保科技发展有限公司 | Refuse disposal system and method that a kind of iron, aluminium, calcium, magnesium elements are recycled |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101426735A (en) * | 2006-03-27 | 2009-05-06 | 法国威立雅水务集团 | Method of obtaining a coagulant product, product intended for manufacturing the said coagulant, and method of treating wastewater and/or industrial effluent using the said coagulant |
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2010
- 2010-12-21 CN CN2010105976943A patent/CN102079563B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101426735A (en) * | 2006-03-27 | 2009-05-06 | 法国威立雅水务集团 | Method of obtaining a coagulant product, product intended for manufacturing the said coagulant, and method of treating wastewater and/or industrial effluent using the said coagulant |
Non-Patent Citations (1)
| Title |
|---|
| 《净水技术》 20051231 蒋彬等 生态混凝土护坡在水源保护区生态修复工程中的应用 第24卷, 第4期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2534137C1 (en) * | 2013-06-14 | 2014-11-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Петербургский государственный университет путей сообщения" | Method of sewage water purification from metal ions |
| CN104016436A (en) * | 2014-06-12 | 2014-09-03 | 南昌大学 | Zinc-containing wastewater treatment method |
| CN104108777A (en) * | 2014-08-04 | 2014-10-22 | 罗光臣 | Method for treating acidic wastewater or waste acid with cement |
| CN106734113A (en) * | 2017-01-20 | 2017-05-31 | 深圳华云环保科技发展有限公司 | Refuse disposal system and method that a kind of iron, aluminium, calcium, magnesium elements are recycled |
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| CN102079563B (en) | 2012-07-25 |
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