CN103664126A - Sludge curing treatment agent and method for treating sludge by use of curing treatment agent - Google Patents
Sludge curing treatment agent and method for treating sludge by use of curing treatment agent Download PDFInfo
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- CN103664126A CN103664126A CN201210352174.5A CN201210352174A CN103664126A CN 103664126 A CN103664126 A CN 103664126A CN 201210352174 A CN201210352174 A CN 201210352174A CN 103664126 A CN103664126 A CN 103664126A
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Abstract
The invention provides a novel sludge curing treatment agent. The curing treatment agent comprises a curing agent A and a curing conditioner B, wherein the curing agent A comprises the following components in percentage by weight: 40-60% of MgO, 5-20% of magnesium chloride salt, 10-20% of SiO2, 10-30% of CaO, 0.1-4% of dehydrating agent and 0-20% of fly ash; the curing conditioner B comprises the following components in percentage by weight: 20-40% of H3PO4, 30-50% of NH4H2PO4 and 20-40% of oxalic acid; the curing agent A accounts for 0.5-10% of the total amount of sludge in treatment by mass; and the curing conditioner B accounts for 0-5% of the total amount of sludge in treatment by mass. By adopting the sludge curing treatment agent provided by the invention to treat the sludge with relatively high water content and particularly water content over 80%, the sludge can be cured generally in 1-2 days, the curing time is short, and the water content is reduced to about 30% 7 days later; after the curing, the water content of the sludge is low; and the sludge after the curing treatment can be subjected to landfill on site or applied to roadbed, greening, earthing, ecological restoration and the like, thereby avoiding secondary pollution to environment.
Description
[technical field]
The present invention relates to field of environment protection, relate in particular to a kind of solidification treatment agent and adopt the method for this solidification treatment agent lignin-sludge.
[background technology]
The mud that sewage work produces in sewage treatment process, water ratio, up to 60～99%, wherein contains the objectionable impuritiess such as a large amount of microorganisms, pathogenic agent and heavy metal, if dealt with improperly, can cause serious secondary pollution.
At present sludge disposal mainly be take and is transferred agricultural, landfill and burning to as main, but because the water ratio of mud is high, mechanical property is poor, pollutant load is high, these processing modes exist that environmental pollution is large, processing cost is too high or easily cause the problems such as landfill yard engineering project disaster.Sludge curing stabilization is a kind of the most common method of industrial lignin-sludge in recent years, sludge curing is stable is that inertia base material is joined in mud as solidification treatment agent such as common silicate cement, lime, by the physical-chemical reaction of series of complex, cementing, the poisonous and hazardous material of mud granule is fixed in the network chain solidifying to form, make it change into similar soil or the very large solid of consolidation strength, on the spot landfill or as material of construction.
Existing solidification treatment agent lignin-sludge, generally need to be cured for 10～20 days, moisture percentage in sewage sludge after processing is generally 50～60%, adopts as seen solidification treatment agent lignin-sludge of the prior art to exist set time longer, and the higher shortcoming still of the moisture percentage in sewage sludge after processing.
[summary of the invention]
When solving existing solidification treatment agent lignin-sludge, set time is long, and the high problem of moisture percentage in sewage sludge after processing, the invention provides a kind of novel solidification treatment agent.
This solidification treatment agent comprises: solidifying agent A and curing amendment B, in described solidifying agent A, each component and weight percent thereof are: MgO40%～60%, chlorination magnesium salts 5%～20%, SiO
210%～20%, CaO10%～30%, dewatering agent 0.1%～4%, flyash 0%～20%; In described curing amendment B, each component and weight percent thereof are: H
3pO
420%～40%, NH
4h
2pO
430%～50%, oxalic acid 20%～40%; The mass percent that described solidifying agent A accounts for sludge treatment total amount is 0.5%～10%, and the mass percent that described solidification treatment agent B accounts for sludge treatment total amount is 0%～5%.
As a kind of embodiment of the present invention, described dewatering agent is a kind of or its combination of powdery aqueous high molecular dispersion agent, powdery polycarboxylic acid water reducer, powdery melamine water reducing agent, powdery naphthalene water reducer.
As a preferred embodiment of the present invention, described solidifying agent A also comprises: a kind of or its combination of the sulphate of iron of 0.5～1% weight percent or ferrous sulfate.
As a preferred embodiment of the present invention, described solidifying agent A also comprises: the magnesium sulfate salt of 3%～10% weight percent.
As a preferred embodiment of the present invention, described solidifying agent A also comprises: heavy metal stabilizer 0.01～2%, described heavy metal stabilizer is a kind of or its combination in calcium-base bentonite, hydroxyapatite, chitosan, Weibull, Na2S9H2O, edta and its sodium salt, ethylene diaminetetraacetic acid and sodium salt thereof, diethylenediamine pentaacetic acid and sodium salt thereof.
As a kind of embodiment of the present invention, described solidifying agent A also comprises: the properties-correcting agent of 1.5%～6% weight percent, described properties-correcting agent is Al
2o
3, Na
2siO
3or NaAlO
2a kind of or its combination.
The present invention also provides a kind of method that adopts environmentally-friendly sludge solidification treatment agent lignin-sludge, it is characterized in that: comprise the following steps: (1) joins each component of solidifying agent A in powder mixier by preset proportion, after mixing, make solidifying agent A finished product; (2) in agitator, solidifying agent A finished product is added in pending mud, be stirred to and mix; (3) material mixing in step (2) is at room temperature carried out to maintenance.
As a preferred embodiment of the present invention, a kind of method of environmentally-friendly sludge solidification treatment agent lignin-sludge that adopts comprises the following steps: (1) joins each component of solidifying agent A in powder mixier by preset proportion, after mixing, make solidifying agent A finished product; By preset proportion, each component of solidifying amendment B is joined in powder mixier, after mixing, make and solidify amendment B finished product; (2) in agitator, solidifying agent A finished product is added in pending mud, be stirred to and mix; Add again and solidify amendment B finished product, be stirred to and mix; (3) material mixing in step (2) is at room temperature carried out to maintenance.
As a preferred embodiment of the present invention, in step (2), add and solidify after amendment B, regulating PH is 7 left and right.
As a preferred embodiment of the present invention, in step (3), curing time is 7 days.
Compared with prior art, adopt solidification treatment agent of the present invention to process water content higher, especially the mud of 80% above water ratio, general 1～2 day curable, set time is short, and after 7 days, water ratio is reduced to 30% left and right, and after solidifying, sludge moisture content is low, mud after solidification treatment is landfill or be applied to roadbed, greening, earthing, restoration of the ecosystem etc. on the spot, environment is not caused to secondary pollution.
[embodiment]
Sludge treating agent provided by the invention, comprises solidifying agent A and curing amendment B, and wherein, in solidifying agent A, each component and weight percent thereof are: MgO40%～60%, chlorination magnesium salts 5%～20%, SiO
210%～20%, CaO10%～30%, dewatering agent 0.1%～4%, flyash 0%～20%; In curing amendment B, each component and weight percent thereof are: H
3pO
420%～40%, NH
4h
2pO
430%～50%, oxalic acid 20%～40%.
Adopt the step of solidification treatment agent lignin-sludge of the present invention as follows: (1) joins each component of solidifying agent A in powder mixier by preset proportion, mixes, make solidifying agent A finished product; By preset proportion, each component of solidifying amendment B is joined in powder mixier, mix, make and solidify amendment B finished product; (2), in agitator, the solidifying agent A finished product that is 0.5%～10% by the mass percent that accounts for sludge treatment total amount adds in pending mud, is stirred to and mixes; Add again and account for the curing amendment B finished product that the mass percent of sludge treatment total amount is 0%～5%, be stirred to and mix, now preferably the PH of mud is adjusted to 7 left and right; (3) material mixing in step (2) is at room temperature carried out to maintenance.
In solidification treatment agent of the present invention, MgO in solidifying agent A is for participating in the active MgO of hydration reaction, there is distortion and exist defect can aggravate the nonsaturation of key in the nonsaturation of active oxidation magnesium surface valence link, lattice, improve the activity with sludge reaction, described MgO contains active MgO composition >=50%, preferably active MgO composition >=60%.
Chlorination magnesium salts is mainly MgCl
2or MgCl
26H
2o, chlorination magnesium salts is blender, with MgO and H
2there is hydration reaction and generate gelling material in O.
MgO and MgCl
2react the equation that generates gel can be expressed as with free-water in mud:
mMgO+MgCl
2+nH
2O→mMg(OH)
2·MgCl
2·nH
2O
General m: n equals 3: 8 or 5: 8, the free-water that this reaction can consume in mud slurry in a large number makes the free-water in mud lose flowability and form gel, and separate out gradually fibrous crystals, the interlaced adhesion ramp of fibrous crystals is filled between other particles, finally formed the closely knit body structure of piling up, make the sclerosis of mud slurry, intensity constantly increases simultaneously.
CaO easily absorbs water and generates Ca (OH)
2, Ca (OH)
2with CO in air
2reaction generates CaCO
3precipitation, the pH value of the adjustable mud slurry of this process, supplies with mud with vesicular graticule mesh skeleton, changes sludge structure, improves solidification effect, and the final calcium carbonate generating can increase the intensity of mud.
Under the alkaline condition mixing at many kinds of substance, SiO
2with MgCl
2the Mg of middle surplus
2+reaction generates MgSiO
3floss, also can with Ca (OH)
2generate CaSiO
3precipitation, can reduce soluble M g
2+and Ca
2+concentration, stop up the capillary channel in hardenite, change pore structure, reduce porosity, on the other hand SiO
2as ultra-fine filling material, also can increase the density of gelling material, improve the impermeability of cement.
Dewatering agent is mainly a kind of or its combinations such as powdery aqueous high molecular dispersion agent, powdery polycarboxylic acid water reducer, powdery melamine water reducing agent, powdery naphthalene water reducer.In mud, the existence form of water comprises the free-water being present in mud granule gap, accounts for sludge water content 70%, is present in capillary water in the kapillary between mud granule, accounts for 20%; Attach to the attached water on mud granule surface and be present in its inner internal water (comprising the water in biomass cells), accounting for sludge water content 10%.Above-mentioned dewatering agent is anion surfactant, can be adsorbed on mud granule or its hydrated product, has changed the physico-chemical property of solid-liquid interface and the reactive force between particle, thereby improves the dispersiveness between particle.After adding polymkeric substance dewatering agent, free-water and the internal water of parcel are freed, play strong dehydration and stabilization, greatly reduce the water ratio of mud.
In flyash, contain active SiO
2, Al
2o
3deng, rise on the one hand and SiO
2identical effect, can make the later strength strengthen continuously of gelling material on the other hand.
As a kind of embodiment of the present invention, can in the compound of mud and solidifying agent A, continue to sneak into curing amendment B, wherein H
3pO
4the phosphate anion that dissociation goes out and Mg
2+coordination, has reduced hydrate and has formed Mg
2+concentration, makes m: n=5: hydrolysis reaction does not occur the gel of 8 o'clock in water, can improve the stability of chlorine oxygen magnesium hydrate in water, meanwhile, and due to H
3pO
4be acid, also work the sludge pH value effect of adjusting.
It is acid that oxalic acid is, and adjustable mixture pH value works to suppress sludge bulking.
NH
4h
2pO
4can promote activity when oxalic acid reacts in goods, thus can play a role to deformation of products, the nitrogen element that can provide in addition plant-growth to use.
As a kind of embodiment of the present invention, solidifying agent A also comprises the sulphate of iron of 0.5～1% weight percent or a kind of or its combination in ferrous sulfate, and described sulphate of iron is Fe
2(SO
4)
3, described ferrous sulfate is FeSO
4or FeSO
47H
2o, sulphate of iron or ferrous sulfate salt pair MgO and MgCl
2play a driving role with reacting between free-water in mud, can shorten the sludge curing time, in addition, Fe belongs to transition element, can form Fe (OH) under alkaline condition
3gluey throw out, stops up capillary channel, has improved the water permeability resistance of gelling material and has reduced its water absorbability, improves the intensity of mud after processing.
As a kind of embodiment of the present invention, solidifying agent A also comprises the magnesium sulfate salt of 3%～10% weight percent, and described magnesium sulfate salt is MgSO
4, MgSO
4h
2o, MgSO
44H
2o, magnesium sulfate salt makes to generate a certain amount of crystalline compounds that is insoluble in water after gelling material aquation, to supplement the chlorine oxygen magnesium hydrate strength decreased that phase change causes in water.
As a kind of embodiment of the present invention, solidifying agent A also comprises the Al of 1.5%～6% weight percent
2o
3, Na
2siO
3or NaAlO
2a kind of or its combination, this three, as properties-correcting agent, can improve the water tolerance of magnesia oxychloride cement, as NaAlO
2be spiked in chlorine oxygen magnesium hydrate and can produce cholesteric-nematic transition, work as MgO/MgCl
2during > 5, the main hydrate forming after hardening of cement is easy in air and CO
2in conjunction with generating the good chlorine magnesiumcarbonate phase of water stability.
As a kind of embodiment of the present invention, solidifying agent A also comprises heavy metal stabilizer 0.01%～2%, described heavy metal stabilizer is a kind of or its combination in calcium-base bentonite, edta and its sodium salt, ethylene diaminetetraacetic acid and sodium salt thereof, diethylenediamine pentaacetic acid and sodium salt thereof, they can be combined by the heavy metal in mud, make heavy metal be transformed into the steady state of low-solubility and low migration and be difficult for being leached, with this, reaching the object of eliminating heavy metal contamination.
Sludge curing amendment of the present invention can be processed water ratio at more than 60% mud, especially be applicable to processing the mud of 80% above water ratio, mud maintenance after processing can realize curing after 1～2 day, physical strength is strengthened, and the water ratio after 7 days is significantly reduced to 30～40% left and right.Part active ion in solidification treatment agent of the present invention can be combined by the heavy metal in mud, transforming heavy metal contaminants is harmless form, after solidifying, in mud soak solution, concentration of heavy metal ion meets GB5085.3-2007 < < Hazardous wastes judging standard leaching characteristic identification > > requirement, mud is not caused to secondary pollution.Activeconstituents in solidification treatment agent can react with chemical composition in bacterium and moisture, has germicidal action, can reduce the burst size of the foul gass such as NH3.Mg, Ca, Fe, P, N plasma have been added in solidification treatment agent of the present invention, and soil is had to good improving effect, make that mud after solidifying is stable, fertilizer efficiency is high.Solidification treatment agent main raw material of the present invention is cheap and easy to get, and operating procedure is simple, and processing costs is cheap, has higher economic benefit concurrently.
Below in conjunction with embodiment, the present invention will be further described.In following examples, the hardness of the mud after solidifying with unconfined compression strength (Kpa) expression, this numerical value is higher, illustrates that the mud hardness after solidifying is higher, and solidification effect is better; Water content (%) represents the dehydrating effect of sludge treating agent, and this numerical value is lower, illustrates that the dehydrating effect of sludge treating agent is better; Heavy metal content (mg/L) represents the content of the Heavy Metals in Sludge after processing, and this numerical value is less, and the more difficult leaching of heavy metal is described.
Embodiment 1
In powder mixier, according to the formula of solidifying agent A in table 1 and curing amendment B, add successively various starting material respectively, mix and blend is 5～6 minutes respectively, makes respectively solidifying agent A and curing amendment B finished product.
In agitator, adding the solidifying agent A of mud weight 5% to water ratio is in 90% mud, and mix and blend is after 5～6 minutes, then will solidify amendment B and add rear mix and blend 10～15 minutes, conditioning of mud pH is 8, carries out maintenance after stirring under room temperature.Within 2 days, test afterwards the unconfined compression strength of mud; within 7 days, test afterwards the water ratio of mud; after 7 days, according to the solid waste toxicity of Environmental Protection Agency, leach (TCLP) method, with atomic absorption spectrophotometer, measure leach liquor heavy metal content, in table 1, listed test result.
Embodiment 2
According to the formula of solidifying agent A in table 1 and curing amendment B, repeat embodiment 1, the pH that wherein reconciles mud is 8.5, has listed test result in table 1.
Embodiment 3
According to the formula of solidifying agent A in table 1 and curing amendment B, repeat embodiment 1, the pH that wherein reconciles mud is 7, has listed test result in table 1.
Embodiment 4
According to the formula of solidifying agent A in table 1 and curing amendment B, repeat embodiment 1, the pH that wherein reconciles mud is 9, has listed test result in table 1.
Embodiment 5
According to the formula of solidifying agent A in table 1 and curing amendment B, repeat embodiment 1, the pH that wherein reconciles mud is 7, has listed test result in table 1.
Embodiment 6
According to the formula of solidifying agent A in table 1 and curing amendment B, repeat embodiment 1, the pH that wherein reconciles mud is 7, has listed test result in table 1.
Embodiment 7
According to the formula of solidifying agent A in table 1 and curing amendment B, repeat embodiment 1, the pH that wherein reconciles mud is 8, has listed test result in table 1.
Embodiment 8
In powder device, the formula according to solidifying agent A in table 1, adds various starting material successively, and mix and blend 5～6 minutes makes solidifying agent A finished product.
In agitator, adding the solidifying agent A of mud weight 9% to water ratio is that in 90% mud, mix and blend, after 5～6 minutes, carries out maintenance under room temperature after stirring.Within 2 days, test afterwards the unconfined compression strength of mud; within 7 days, test afterwards the water ratio of mud; after 7 days, according to the solid waste toxicity of Environmental Protection Agency, leach (TCLP) method, with atomic absorption spectrophotometer, measure leach liquor heavy metal content, in table 1, listed test result.
Table 1
From the test result of table 1, the mud that adopts method of the present invention to process, no matter in set time, solidification effect, effect preferably all on dehydrating amount and fixedly heavy metal content.
Although the present invention has been explained in detail and has quoted as proof embodiment, for those of ordinary skill in the art, various schemes, modification and the change that obviously can make according to above-mentioned explanation, within all should being included in the scope of claim.
Claims (10)
1. an environmentally-friendly sludge solidification treatment agent, is characterized in that: described solidification treatment agent comprises solidifying agent A and curing amendment B,
Wherein, in described solidifying agent A, each component and weight percent thereof are:
MgO 40％～60％；
Chlorination magnesium salts 5%～20%;
SiO
2 10％～20％；
CaO 10％～30％；
Dewatering agent 0.1%～4%;
Flyash 0%～20%;
In described curing amendment B, each component and weight percent thereof are:
H
3PO
4 20％～40％；
NH
4H
2PO
4 30％～50％；
Oxalic acid 20%～40%;
The mass percent that described solidifying agent A accounts for sludge treatment total amount is 0.5%～10%, and the mass percent that described solidification treatment agent B accounts for sludge treatment total amount is 0%～5%.
2. solidification treatment agent as claimed in claim 1, is characterized in that: described dewatering agent is a kind of or its combination of powdery aqueous high molecular, powdery polycarboxylic acid water reducer, powdery melamine water reducing agent, powdery naphthalene water reducer.
3. solidification treatment agent as claimed in claim 1, is characterized in that: described solidifying agent A also comprises a kind of or its combination of sulphate of iron or the ferrous sulfate of 0.5～1% weight percent.
4. solidification treatment agent as claimed in claim 1, is characterized in that: described solidifying agent A also comprises the magnesium sulfate salt of 3%～10% weight percent.
5. solidification treatment agent as claimed in claim 1, it is characterized in that: described solidifying agent A also comprises heavy metal stabilizer 0.01～2%, described heavy metal stabilizer is a kind of or its combination in calcium-base bentonite, hydroxyapatite, chitosan, Weibull, Na2S9H2O, edta and its sodium salt, ethylene diaminetetraacetic acid and sodium salt thereof, diethylenediamine pentaacetic acid and sodium salt thereof.
6. solidification treatment agent as claimed in claim 1, is characterized in that: described solidifying agent A also comprises the properties-correcting agent of 1.5%～6% weight percent, described properties-correcting agent is Al
2o
3, Na
2siO
3or NaAlO
2a kind of or its combination.
7. a method that adopts environmentally-friendly sludge solidification treatment agent lignin-sludge, is characterized in that: comprise the following steps:
(1) by preset proportion, each component of solidifying agent A is joined in powder mixier, after mixing, make solidifying agent A finished product;
(2) in agitator, solidifying agent A finished product is added in pending mud, be stirred to and mix;
(3) material mixing in step (2) is at room temperature carried out to maintenance.
8. a method that adopts environmentally-friendly sludge solidification treatment agent lignin-sludge, is characterized in that: comprise the following steps:
(1) by preset proportion, each component of solidifying agent A is joined in powder mixier, after mixing, make solidifying agent A finished product; By preset proportion, each component of solidifying amendment B is joined in powder mixier, after mixing, make and solidify amendment B finished product;
(2) in agitator, solidifying agent A finished product is added in pending mud, be stirred to and mix; Add again and solidify amendment B finished product, be stirred to and mix;
(3) material mixing in step (2) is at room temperature carried out to maintenance.
9. method as claimed in claim 8, is characterized in that: in step (2), add and solidify after amendment B, regulating PH is 7 left and right.
10. method as claimed in claim 9, is characterized in that: in described step (3), the time of maintenance is 1～7 day.
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