CN104310884B - Curing agent for attapulgite reinforced printing and dyeing sludge treatment and curing method thereof - Google Patents

Curing agent for attapulgite reinforced printing and dyeing sludge treatment and curing method thereof Download PDF

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CN104310884B
CN104310884B CN201410526438.3A CN201410526438A CN104310884B CN 104310884 B CN104310884 B CN 104310884B CN 201410526438 A CN201410526438 A CN 201410526438A CN 104310884 B CN104310884 B CN 104310884B
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attapulgite
printing
sludge
dyeing sludge
cement
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CN104310884A (en
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任洪强
张瑞
丁丽丽
耿金菊
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Nanjing University
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Nanjing University
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Abstract

The invention discloses curing agent for attapulgite reinforced printing and dyeing sludge treatment and a curing method thereof and belongs to the technical field of printing and dyeing sludge treatment. The mass ratio of attapulgite and a composite additive in the curing agent is (0.05-0.3): (0.3-1.2). The mass ratio of cement, coal ash and calcium chloride in the composite additive is (1-6): (0-5): (0-0.18). The curing method comprises the following steps: (1) determining the adding proportion of the composite additive and attapulgite; (2) crushing and grinding the composite additive and attapulgite and sieving by a 35-mesh sieve; (3) uniformly mixing the printing and dyeing sludge, attapulgite and the composite additive; and (4) packing the stirring product in a die in layers, demoulding in one day and maintaining for 1-28 days at room temperature. The curing agent disclosed by the invention is used for improving the geotechnical property of factory sludge in a printing and dyeing plant, so that the mechanical strength of cured sludge is improved and the leaching ability of pollutants is reduced. Sanitary landfill and resource utilization of sludge are facilitated.

Description

A kind of attapulgite strengthening printing and dyeing sludge processes disposal curing agent and its curing
Technical field
The present invention relates to environment pollution control end, solid waste safe disposal technical field, more particularly, it relates to print Curing agent component in dye Treatment of Sludge disposal process, and the method using this curing agent final disposal printing and dyeing sludge.
Background technology
Dyeing waste water is one of typical difficult industrial wastewater, and its processing procedure generally adopts materialization and biochemical treatment work Skill, can produce substantial amounts of mud in processing procedure.Due to containing substantial amounts of dyestuff, auxiliary agent, slurry, heavy metal in dyeing waste water Deng complicated hard-degraded substance, thus, printing and dyeing sludge has complicated component, special and intractable characteristic.
Mud generally has the processing means such as burning, compost, landfill, recycling.Due to burning high cost, easily produce Secondary pollution, the problems such as compost may bring heavy metallic poison to crops again, thus landfill and recycling are current dirts The mode that mud disposal more commonly accepts relatively.But, usual printing and dyeing mill dispatches from the factory moisture percentage in sewage sludge height, complicated component, foul smelling, soil Work poor performance, is not suitable for being directly entered sanitary filling field, nor meet safe reuse will to the control of pollutant leaching concentration Ask.So that printing and dyeing sludge is carried out solidifying with stable process, improve the mechanical strength of mud, reduce the leaching energy of polluter Power.Select suitable curing agent for shortening the sludge treatment time, improve process performance, reduce processing cost and there is great meaning Justice.
Attapulgite, also known as palygorskite, are a kind of clay minerals containing magnesium silicon components, and chemical molecular formula is Mg5Si8O20 (OH)2(OH2)4·4H2O.Russia scholar finds early in Ural mining area and is named as palygorskite within 1862.Nineteen thirty-five is French Scholar finds new clay in concavo-convex fort, and is named as attapulgite, proves identical with palygorskite structure afterwards, China is to attapulgite Research is started late and is still had certain gap with the world.But attapulgite is huge in China's reserves, account for the world more than half it is easy to Obtain.The unique layer chain crystal structure of attapulgite and larger specific surface area, greatly extend its application, rationally Can metal ingredient effectively in solidification sludge and organic component using its stronger absorption property.
Through retrieval, Chinese Patent Application No. 200810036184.1, the applying date is on April 17th, 2008, innovation and creation name Referred to as:A kind of sludge solidifying agent and application, this application case discloses one kind and is used for municipal sewage plant drain sludge and river The curing agent of road mud and application, curing agent is mixed according to a certain percentage by sulphate aluminium cement, gypsum, lime and coagulant Close, then with sludge agitation so that mud can reach the soil mechanics performance of landfill or other construction material requirements.Mud is solid The mass ratio that agent includes each component raw material is:Sulphate aluminium cement 30%-60%, gypsum 20%-40%, lime 8%- 20%, coagulant 1%-5%.After mud adds curing agent stirring solidification, the maintenance time of 1-6 days, you can reach landfill and require Intensity and water content.After this application case sludge curing, toxic heavy metal ion is wrapped so that the pollution of mud reduces, quilt The mud of solidification does not have the stench of primary sludge, decreases the harm to operating personnel during operation.But this application case is directed to solid Change municipal treatment mud and river sludge, in its process object component, tenor and degree of danger are below industry printing and dyeing Mud, simultaneously this application case compression strength numerical value just beyond 50kPa, there is no certain allowance, also do not quantify to illustrate various The concrete solidification effect of pollutant, actual directive significance has been short of.
China Patent No. ZL201110342103.2, authorized announcement date is on July 24th, 2013, and invention and created name is: Heavy metal pollution bottle sediment curing agent, the curing agent of this application case includes the cement that mass fraction is 20%~50%, mass fraction Flyash for 40%~70%, mass fraction is 5%~15% bentonite and additive that mass fraction is 3%~6%; Additive includes calcium nitrate, natrium nitrosum, sodium metaaluminate, sodium sulphate, sodium lignin sulfonate, lauryl sodium sulfate and three ethanol Amine, the curing agent of this application case processes bed mud solidify afterwards body intensity height, and leachate pH and Leaching of Heavy Metals concentration obtain very great Cheng Degree reduces.But the curing agent component of this application case is various, complex operation, solidification purpose is indefinite, if being used for filling, outward simultaneously Plus agent addition is excessive, high cost;If being used for building materials, with reference to external building standard, metal leaching concentration is too high.
Content of the invention
1. invent technical problem to be solved
Present invention aims to existing printing and dyeing sludge solidification stable treatment technique sludge treatment time length, mud are solid Change the problems such as body mechanical strength is low, pollutant leaching concentration is high, there is provided a kind of attapulgite strengthening printing and dyeing sludge is processed to be disposed With curing agent and its curing, present invention improves printing and dyeing mill dispatches from the factory, the geotechnological performance of mud, improves the machine of solidification sludge Tool intensity, reduces the leaching ability of pollutant, is easy to sanitary landfills and the recycling of mud.
2. technical scheme
For reaching above-mentioned purpose, the technical scheme that the present invention provides is:
A kind of attapulgite strengthening printing and dyeing sludge of the present invention processes disposal curing agent, including compound additive and concavo-convex Rod soil, described compound additive includes cement, flyash and calcium chloride, and the mass ratio of cement, flyash and calcium chloride is (1 ~6):(0~5):(0~0.18);The mass ratio of described attapulgite and compound additive is (0.05~0.3):(0.3~ 1.2).
Further, the mass ratio (0.1~1) of printing and dyeing sludge, attapulgite and compound additive:(0.05~0.3): (0.3~1.2).
Further, in described compound additive, the mass ratio of cement, flyash and calcium chloride is 2:5:0.06, institute The mass ratio of printing and dyeing sludge, attapulgite and the compound additive stated is 1:0.2:0.706;Printing and dyeing sludge firming body under this proportioning Meet sanitary landfills standard.
Further, in described compound additive, the mass ratio of cement, flyash and calcium chloride is 1:0:0, described Printing and dyeing sludge, attapulgite and compound additive mass ratio be 0.433:0.133:0.433;Under this proportioning, printing and dyeing sludge is solid Change body and meet European Union's building materials and pave the way relevant criterion.
A kind of attapulgite strengthening printing and dyeing sludge of the present invention processes disposal curing agent curing, and its step is:
(1) according to sludge characteristics and firming body whereabouts, determine the ratio of each component contained by compound additive and compound add Plus the adding proportion of agent, attapulgite;
(2) by compound additive and attapulgite crushing grinding, 35 mesh sieves are crossed;
(3) determine ratio in step (1), printing and dyeing sludge, attapulgite, compound additive mixing are stirred evenly;
(4) stirring product layering is filled in mould, the demoulding after a day, room temperature maintenance 1~28 day.
Further, first is 2 according to cement, flyash and calcium chloride mass ratio:5:0.06 ratio is mixed to prepare multiple Close additive, then printing and dyeing sludge, attapulgite and compound additive are 1 in mass ratio:0.2:0.706 ratio mixing, room Warm maintenance 1 day, the printing and dyeing sludge firming body preparing meets sanitary landfills standard.
Further, first is 1 according to cement, flyash and calcium chloride mass ratio:0:0 ratio is mixed to prepare compound adding Plus agent, then printing and dyeing sludge, attapulgite and compound additive are 0.433 in mass ratio:0.133:0.433 ratio mixing, Room temperature maintenance 28 days, the printing and dyeing sludge firming body preparing meets European Union's building materials and paves the way relevant criterion.
Further, step (3) adopts JJ-5 cement plaster blender, and stirring intensity is first stirring at low speed 10 minutes, High-speed stirred 5 minutes afterwards.
3. beneficial effect
The technical scheme being provided using the present invention, compared with existing known technology, has following remarkable result:
(1) a kind of attapulgite strengthening printing and dyeing sludge of the present invention processes disposal curing agent, by adding attapulgite Produce series of chemical with the water in the conventional additive cement of compound proportioning, flyash and calcium chloride, with printing and dyeing sludge, Improve the geotechnological performance of mud, shorten hardening time, sludge characteristics can be improved by the different collocation of each component of curing agent, meet Enter garbage loading embeading factory, repair the roads or as the different actual demand such as greening construction material;
(2) a kind of attapulgite strengthening printing and dyeing sludge of the present invention processes disposal curing agent curing, curing operation Simply, component is cheap and easy to get, and solidification intensity is suitable for multiple situations, pollutant good fixing effect, has good replicability And practicality.
Brief description
Fig. 1 is the XRD of the printing and dyeing sludge firming body being obtained using the curing agent that the present invention provides.
Specific embodiment
For further appreciating that present disclosure, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1
A kind of attapulgite strengthening printing and dyeing sludge of the present embodiment processes disposal curing agent, including compound additive and recessed Convex rod soil, described compound additive includes cement, flyash and calcium chloride.According to moisture percentage in sewage sludge, content of organics and weight Tenor and sludge curing application purpose, in conjunction with design software design expert8.0.6, after newly-built task Select Optimal type in mixture tab, set component number and each component maximin.Response to selection index Determine the ratio of each component and the adding proportion of compound additive, attapulgite contained by compound additive afterwards.In view of this enforcement The printing and dyeing sludge firming body that example solidification obtains is mainly used in sanitary landfills.Cement, flyash and calcium chloride in compound additive Mass ratio is 2:5:0.06, the mass ratio of printing and dyeing sludge, attapulgite and compound additive is 1:0.2:0.706.
According to aforementioned proportion, 168.4g cement, 421.1g flyash and 5.05g calcium chloride are mixed to get compound additive, Then by compound additive and attapulgite crushing grinding, 35 mesh sieves are crossed, so that subsequently mixing is more uniform.Aqueous in 842.1g Rate be 86% printing and dyeing sludge in add 168.4g attapulgite and above-mentioned compound additive, be placed in JJ-5 cement plaster blender Middle mixing stirs evenly.The rotating speed of JJ-5 cement plaster blender is:Low speed rotation 140 ± 5r/min, revolve round the sun 62 ± 5r/min;At a high speed Rotation 285 ± 10r/min, revolve round the sun 125 ± 10r/min.Will be first low for the mixture of printing and dyeing sludge, attapulgite, compound additive Speed stirring 10 minutes, rear high-speed stirred 5 minutes, mix.By stirring product room temperature lower leaf be filled in 70.7mm × Compacting in 70.7mm × 70.7mm mould, adopts compressed-air ejection after shaping 24h, and compressed air pressure is 6Bar, and room temperature is supported Shield 1 day.
After maintenance 1 day, the unconfined compressive strength of printing and dyeing sludge firming body reaches 335.75kPa.XRD analysis are done to sample, As shown in figure 1, firming body majority crystallographic structure is shown as quartz, calcite and tricalcium silicate, also confirm CSH gel from side Presence.Leaching test, wherein Cu and Pb in leachate are done using sulfonitric method (HJ/T299-2007) to firming body Concentration be 0.455mg/L and 0.1827mg/L, meet sanitary landfills and building banketed related request.
Inventor points out, although the present embodiment adopts conventional additive cement, flyash and the compound interpolation of calcium chloride composition Agent, but the present embodiment, by carrying out ratio allotment to attapulgite, cement, flyash, calcium chloride and printing and dyeing sludge, makes concave convex rod It is anti-that water in soil, the conventional additive cement of compound proportioning, flyash and calcium chloride, with printing and dyeing sludge produces a series of chemistry Should.Wherein, to carry out aquation anti-for the compound such as the tricalcium silicate in cement component, dicalcium silicate, tricalcium aluminate, calcium aluminoferrite and water Should, form the needle-like such as entringite and CSH gel or club shaped structure.Flyash and printing and dyeing sludge composition carry out pozzolanic reaction, show Write the mechanical compression strength strengthening mud.Attapulgite has good characterization of adsorption, can reduce oozing out of metal in sludge, Compared with similar clays bentonite, attapulgite structure is chain, its surface more stable with respect to bentonitic layer structure Long-pending and adsorption capacity is above bentonite.The addition of calcium chloride can improve the concentration of calcium in hydrated reaction of cement, promotes aquation mistake Journey is carried out to the process producing entringite and CSH, shortens the hydration reaction time of cement.Attapulgite, cement, flyash and chlorine Each performs its own functions and mutually promotes to change calcium, and the sludge characteristics such as the geotechnological performance of solidification printing and dyeing sludge, mechanical strength significantly improve, The leaching ability of pollutant is significantly reduced, and reaches the standard of Liao Jin garbage loading embeading factory sanitary landfills.By to curing agent each group Divide and carry out different collocation, also can meet and repair the roads or as the different actual demand such as greening construction material.Additionally, above-mentioned biography System additive cement, flyash and calcium chloride are cheap and easy to get, and attapulgite is in the reserves also very abundant of China, curing agent component Simply, preparation cost is low, has good replicability and practicality.
Embodiment 2
First according to cement in the present embodiment:Flyash:Calcium chloride=1:0:0 is mixed to prepare compound additive, then according to Printing and dyeing sludge:Attapulgite:Compound additive=0.433:0.133:0.433 will be mixing cured for each component.According to said ratio Add 133g attapulgite and 433g cement in 433g printing and dyeing sludge, mix.70.7mm × 70.7mm is loaded under room temperature 24h shaping in × 70.7mm mould, after the demoulding, the unconfined compressive strength of 28 days cured blocks of maintenance reaches 3.0MPa.Meet Patel delivered document Evaluation of physical stability and leachability of Portland Pozzolona Cement(PPC)solidified chemical sludge generated from textile wastewater treatment plants,Journal of Hazardous Materials 207:To soil in 56-64 Base, the compression strength of fragment of brick of repairing the roads require.XRD result display quartz and calcite are main component, similar with Fig. 1.Using sulphur Acid+nitric acid method (HJ/T299-2007) does Leaching test to cured block, and wherein in leachate, the concentration of Cu and Pb is The concentration of 0.2741mg/L and 0.0775mg/L, COD is 573.32mg/L, and pollutant is solidified further.
Embodiment 3
A kind of attapulgite strengthening printing and dyeing sludge of the present embodiment processes disposal curing agent and its curing, substantially same Embodiment 1, its difference is:Cement in the present embodiment:Flyash:Calcium chloride=6:0:0.18, printing and dyeing sludge:Concave convex rod Soil:Compound additive=0.1:0.05:0.3.
Embodiment 4
A kind of attapulgite strengthening printing and dyeing sludge of the present embodiment processes disposal curing agent and its curing, substantially same Embodiment 1, its difference is:The present embodiment is first according to cement:Flyash:Calcium chloride=4:1:0.16 be mixed to prepare compound Additive, then according to printing and dyeing sludge:Attapulgite:Compound additive=0.24:0.11:0.7 will be mixing cured for each component, room Temperature is lower to load 24h shaping in 70.7mm × 70.7mm × 70.7mm mould, and maintenance after the demoulding obtains printing and dyeing sludge firming body in 12 days.
A kind of attapulgite strengthening printing and dyeing sludge described in embodiment 1~4 processes disposal curing agent and its curing, Improve printing and dyeing mill to dispatch from the factory the geotechnological performance of mud, improve the mechanical strength of solidification sludge, reduce the leaching energy of pollutant Power, is easy to sanitary landfills and the recycling of mud, and curing operation is simple, and component is cheap and easy to get, and solidification intensity is suitable for Multiple situations, pollutant good fixing effect, there is good replicability and practicality.
Below schematically the present invention and embodiments thereof are described, this description does not have restricted, institute in accompanying drawing Show is also one of embodiments of the present invention, and actual structure is not limited thereto.So, if the common skill of this area Art personnel enlightened by it, in the case of without departing from the invention objective, designs and this technical scheme without creative Similar frame mode and embodiment, all should belong to protection scope of the present invention.

Claims (2)

1. a kind of attapulgite strengthening printing and dyeing sludge process disposal curing agent it is characterised in that:Including compound additive and recessed Convex rod soil, described compound additive includes cement, flyash and calcium chloride, and the mass ratio of cement, flyash and calcium chloride is 2:5:0.06;The mass ratio of described printing and dyeing sludge, attapulgite and compound additive is 1:0.2:0.706;Print under this proportioning Stain mud firming body and meet sanitary landfills standard.
2. attapulgite described in a kind of claim 1 strengthens the curing that printing and dyeing sludge processes disposal curing agent, its step For:
(1) determine the adding proportion of the ratio of each component and compound additive, attapulgite contained by compound additive, specially In compound additive, the mass ratio of cement, flyash and calcium chloride is 2:5:0.06;Printing and dyeing sludge, attapulgite and compound interpolation The mass ratio of agent is 1:0.2:0.706;
(2) by compound additive and attapulgite crushing grinding, 35 mesh sieves are crossed;
(3) determine ratio in step (1), using JJ-5 cement plaster blender, by printing and dyeing sludge, attapulgite, compound interpolation Agent mixing stirs evenly, and the rotating speed of JJ-5 cement plaster blender is:Low speed rotation 140 ± 5r/min, revolve round the sun 62 ± 5r/min;At a high speed Rotation 285 ± 10r/min, revolve round the sun 125 ± 10r/min;Stirring intensity is first stirring at low speed 10 minutes, rear high-speed stirred 5 minutes;
(4) stirring product layering is filled in mould, the demoulding after a day, room temperature maintenance 1 day.
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