CN103880122B - A kind of method preparing the anti-granular unburned iron-carbon micro-electrolysis filler that hardens - Google Patents
A kind of method preparing the anti-granular unburned iron-carbon micro-electrolysis filler that hardens Download PDFInfo
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Abstract
The present invention relates to a kind of method preparing the anti-granular unburned iron-carbon micro-electrolysis filler that hardens.The method comprises, and using iron filings, charcoal, flyash, cement, unslaked lime, clay as raw material, mixes respectively according to the massfraction of 32-36%, 8-10%, 32-35%, 9-12%, 5-7%, 5-7%, granulation, obtained after maintenance.The obtained anti-granular unburned iron-carbon micro-electrolysis filler particle diameter that hardens is 5-7mm.Product of the present invention is used for sewage disposal, can reduce the COD of waste water within the shorter time
crand colourity, and reduce the toxicity of waste water, improve biodegradability.In the process used, be less likely to occur to harden, maintenance cost is cheap, and life cycle is long.Preparation process takes full advantage of waste resource, and adopts unburned technique, reaches the object of the energy-saving and emission-reduction treatment of wastes with processes of wastes against one another.
Description
Technical field
The present invention relates to a kind of method preparing the anti-granular unburned iron-carbon micro-electrolysis filler that hardens, belong to technical field of sewage, the especially especially preprocessing technical field of high-concentration hardly-degradable waste water.
Technical background
After the sixties in 20th century, due to the fast development of modern chemical industry, the macromole organic materialss such as synthetic plastics, synthon, synthetic rubber, nylon, by suitability for industrialized production.In the process that these organic materialss are produced, the organic waste water of a large amount of high densitys can be produced.According to the display of " national Environmental statistics publication " statistics, in China's waste water total release in 2008, industrial organic waste water amount proportion reaches 44.3%.Its concentration is high, complicated component, and wherein often containing many hardly degraded organic substances, especially the material such as polycyclic aromatic hydrocarbons, alkyl benzene sulphonate (ABS), chlorophenol, polychlorobiphenyl, there is the effects such as carcinogenic, teratogenesis, mutagenesis, biodegradability is low, be difficult to be degraded by biochemical treatment, remain in water body simultaneously and can have huge harm to human health and physical environment.And traditional process and pretreatment process, or processing cost is comparatively large, or technique means imperfection, be difficult to extensive implementation.
A kind of solid waste that waste iron filing is mainly produced by machinery manufacturing industry, its generation is very large, not only occupies valuable land resources, and can cause the pollution of environment.Innoxious and the recycling of waste iron filing is studied widely.Flyash receives to catch the thin ash got off from the flue gas after coal combustion, is the primary solids refuse that coal-burning power plant discharges, one of industrial residue that the current discharge capacity of Ye Shishi China is larger.Nineteen ninety-five, flyash quantity discharged reached 1.25 hundred million tons, and within 2000, be about 1.5 hundred million tons, will reach 300,000,000 tons by 2010, a large amount of flyash does not add process, will produce airborne dust, atmosphere pollution; River can be caused to silt up if enter water system, and toxic chemical substance wherein also can work the mischief to human body and biology.On the other hand, China is again the limited country of a per capita resource reserve, and the recycling of flyash, turns waste into wealth, turning bane into boon causes the extensive concern of people.
Micro electrolysis tech is on the basis of electrochemical process, a kind of new technique that development is formed, and be otherwise known as internal electrolysis, is to be widely studied and a kind of method for pre-treating high-concentration organic waste water applied.This technique, in the eighties in 20th century, is introduced into China.Be widely used in the wastewater treatment of the industries such as printing and dyeing, pharmacy, petrochemical complex in recent years.The ultimate principle of weak electrolysis mechanism is that the potential difference utilizing the micro-electrolysis material be filled in waste water to produce processes waste water.Be characterized in low cost, use range is wide, technique is simple, treatment effect is good, especially for high salinity, high toxicity, high COD
crand the process of the higher trade effluent of colourity comparatively other techniques there is more significantly advantage.But at traditional weak electrolysis mechanism in the process run, can harden between filler, sewage produces channel in filler, make water outlet water degradation, the efficiency of impact process, make micro-electrolysis reactor want frequent back flushing and replacement, this is also the principal element limiting this technique widespread use.Therefore, the research and development of the novel anti-micro-electrolysis stuffing hardened, seem necessity very.And utilize the unburned iron-carbon micro-electrolysis filler that flyash is prepared for major auxiliary burden, in anti-hardening, there is larger advantage compared with conventional filler.
Traditional micro-electrolysis stuffing, as the micro-electrolysis stuffing of a kind of sewage disposal that CN201010184817.0 announces, mostly uses sintering process, in the process of high-temperature firing, wastes a large amount of energy, add preparation cost.Unburned technique is combined with micro electrolysis tech, can energy consumption be reduced, reduce production cost, but research is in this respect also less.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, unburned technique is combined with micro electrolysis tech, and take full advantage of trade waste flyash, waste iron filing, provide a kind of method preparing the anti-granular unburned iron-carbon micro-electrolysis filler that hardens.
Technical scheme of the present invention is as follows:
Prepare a method for the anti-granular unburned iron-carbon micro-electrolysis filler that hardens, comprise the following steps:
(1) iron filings, charcoal, flyash, cement, unslaked lime, clay are carried out drying and processing 1-2 hour at 105-110 DEG C respectively, then pulverize, cross 100 mesh sieves;
In above-mentioned raw materials, iron content>=95% in iron filings; SiO in flyash
2content 47-52%, Al
2o
3content 27-30%, CaO, MgO, Na
2o and K
2the total content 5-7% of O; Be mass percentage;
(2) by step (1) through pretreated starting material, according to iron filings 32-36%, charcoal 8-10%, flyash 32-35%, cement 9-12%, unslaked lime 5-7%, the massfraction of clay 5-7% mixes, granulation; Cross 5-6 mesh sieve, the particle diameter filtered out is that the raw material ball of 5-7mm is placed in dry ventilation drying at room temperature 20-24 hour, obtains raw material ball;
(3) raw material ball of drying step (2) obtained, at the Water Under steam curing 30-60 minute of 100-110 DEG C; After this once, described natural curing is naturally place after described raw material ball uniform sprinkling, and after natural curing 5-7 days, must resist the granular unburned iron-carbon micro-electrolysis filler that hardens, sealing is preserved in natural curing in every 24 hours.
For preventing the iron in filler oxidized, in step (3) after each maintenance, filler semitight being preserved, filler so both can have been made dry as early as possible, iron and water, air generation oxidizing reaction can be prevented again to greatest extent.
Preferred according to the present invention, in step (2), the massfraction of each raw material is respectively iron filings 36%, charcoal 9%, flyash 33%, cement 10%, unslaked lime 6%, clay 6%.
Preferred according to the present invention, the granulation in step (2) pours raw material into tablets press to make raw meal particulate, constantly sprays the spraying of binding agent diluent in the process to help raw material balling-up.Granulation is by prior art.Described binding agent is by prior art, and preferred binding agent is the water glass solution of modulus 2.5-2.8.Described binding agent diluent, doubly formulated by described binding agent thin up 2-3.
Preferred according to the present invention, in step (3), raw material ball is the Water Under steam curing 45 minutes of 105 DEG C, and once, obtained anti-granular unburned iron-carbon micro-electrolysis filler sealing of hardening, after 6 days, is preserved by continuous maintenance in natural curing in after this every 24 hours.
The anti-granular unburned iron-carbon micro-electrolysis filler that hardens prepared by aforesaid method, profile is round shaped grain shape, particle diameter 5-7mm, tap density 900-950kg/m
3, water-intake rate 9%-12%.
Main raw material waste iron filing of the present invention, flyash are trade waste or byproduct, and all the other raw material cement, charcoal, clay, unslaked lime are cheap industrial raw material, and wherein cement is ordinary Portland cement.Above-mentioned raw materials is all bought by market.
The anti-pre-treatment of granular unburned iron-carbon micro-electrolysis filler for high-concentration hardly-degradable waste water of hardening prepared by the present invention.
The present invention is a kind of based on iron carbon galvanic interaction, with the reaction such as high-concentration hardly-degradable organic pollutant generation redox, coagulation-flocculation in waste water, be small-molecule substance by macromolecular organic pollutant degradation, in the short period of time, the COD reducing waste water can be reached
crand toxicity, improve the effect of wastewater biodegradability.The present invention is that the process of high-concentration hardly-degradable organic industrial sewage and pre-treatment provide a feasible program.Unburned technique and iron-carbon micro-electrolysis combine with technique are got up by the present invention, utilize unslaked lime, the agent of cement equal excitation, excite flyash activity, make packing hardening, not only achieve the recycling of solid waste, also reach the effect of the treatment of wastes with processes of wastes against one another and energy-saving and emission-reduction simultaneously.
Beneficial effect of the present invention is as follows:
1. the unburned micro-electrolysis stuffing in the present invention, in its main raw material prepared, waste iron filing, flyash are industrial solid castoff, long-term exposure, in the middle of environment, not only occupies valuable land resources, also can cause human health and natural ecological environment and have a strong impact on.The present invention using waste iron filing, flyash, charcoal as main raw material, and be equipped with appropriate cement, clay, unslaked lime, the unburned micro-electrolysis stuffing be prepared from, not only achieve waste iron filing, flyash recycling simultaneously, be applied to the process of high-concentration hardly-degradable trade effluent, achieve the treatment of wastes with processes of wastes against one another especially.
2. the present invention is in the process of the unburned micro-electrolysis stuffing of preparation, in conjunction with unburned technique, not only makes the intensity of haydite reach the service requirements of water treatment, and decreases the consumption of the energy in preparation process, achieve energy-saving and emission-reduction.
3. the unburned micro-electrolysis stuffing that prepared by the present invention is round shaped grain shape, particle and intergranular contact area less, thus in wastewater treatment process, decrease the passivation of hardening between filler, provide good hydraulics.And along with the carrying out of galvanic etching reaction, the surface of filler can constantly come off, and makes filling surface be upgraded, and extends the life cycle of filler, improves the utilising efficiency of environmental protection filtrate.
4. the unburned micro-electrolysis stuffing prepared of the present invention, achieves cathode anode integration, adds the quantity of microcosmic galvanic cell, thus improve electrochemical reaction speed, improve processing efficiency.
5. preparation cost of the present invention is lower, and working service is simple, and technological operation is simple, can be widely used in process and the pre-treatment of high-concentration hardly-degradable organic industrial sewage, have good application prospect.
Accompanying drawing explanation
Fig. 1 is the cylindricality micro-electrolysis reactor loading hardening resistant micro-electrolysis filler of the present invention, and wherein: 1 is into water peristaltic pump, and 2 is aeration pumps, and 3 is water tank inlets, 4 is distribute water and air plates, and 5 is thief holes, and 6 is water outlets, and 7 is hardening resistant micro-electrolysis fillers.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.But be not limited thereto.
Flyash SiO in embodiment
2content about 48%, Al
2o
3content about 27%, CaO, MgO, Na
2o, K
2it is on sale that O total content is about 7%(Shandong Zibo power plant); Waste iron filing iron level>=95%(Jinan machine works is on sale); Charcoal is purchased from Linyi charcoal factory; Cement is ordinary Portland cement (cement mill, Jinan is produced and sold); Clay (Zibo City of Shandong Province brick field is on sale); Unslaked lime CaO content>=95%(Zibo Lime Factory produces and sells).Be mass percentage.
Binding agent diluent in embodiment, by the water glass solution of modulus 2.5-2.8, thin up 2-3 doubly obtains.
Embodiment 1
Prepare a method for the anti-granular unburned iron-carbon micro-electrolysis filler that hardens, comprise the following steps:
(1) iron filings, charcoal, flyash, cement, unslaked lime, clay are carried out drying and processing 2 hours at 105 DEG C respectively, then pulverize, cross 100 mesh sieves;
(2) by step (1) through pretreated starting material, according to iron filings 36%, charcoal 9%, flyash 33%, cement 10%, unslaked lime 6%, the massfraction of clay 6% mixes, be placed in dribbling balling machine rolling, and in rolling process, spray the auxiliary balling-up granulation of binding agent diluent (the water glass solution thin up 2 times again of modulus 2.5-2.8); Cross 5-6 mesh sieve, the particle diameter filtered out is that the raw material ball of 5-7mm is placed in dry ventilation drying at room temperature 20 hours, obtains raw material ball;
(3) raw material ball of drying step (2) obtained, the Water Under steam curing 45 minutes of 105 DEG C; After this once, described natural curing is naturally place after described raw material ball uniform sprinkling, and natural curing, after 6 days, must resist the granular unburned iron-carbon micro-electrolysis filler that hardens, and sealing is preserved in natural curing in every 24 hours.
The performance perameter of the filler obtained is as follows: particle diameter: 5-6mm; Tap density: 923kg/m
3; Water-intake rate: 10%.
Embodiment 2
Prepare a method for the anti-granular unburned iron-carbon micro-electrolysis filler that hardens, comprise the following steps:
(1) iron filings, charcoal, flyash, cement, unslaked lime, clay are carried out drying and processing 1 hour at 110 DEG C respectively, then pulverize, cross 100 mesh sieves;
(2) by step (1) through pretreated starting material, according to iron filings 32%, charcoal 8%, flyash 35%, cement 11%, unslaked lime 7%, the massfraction of clay 7% mixes, be placed in dribbling balling machine rolling, and in rolling process, spray the auxiliary balling-up granulation of binding agent diluent (the water glass solution thin up 3 times again of modulus 2.5-2.8); Cross 5-6 mesh sieve, the particle diameter filtered out is that the raw material ball of 5-7mm is placed in dry ventilation drying at room temperature 24 hours, obtains raw material ball;
(3) raw material ball of drying step (2) obtained, the Water Under steam curing 30 minutes of 110 DEG C; After this once, described natural curing is naturally place after described raw material ball uniform sprinkling, and natural curing, after 7 days, must resist the granular unburned iron-carbon micro-electrolysis filler that hardens, and sealing is preserved in natural curing in every 24 hours.
The performance perameter of the filler obtained is as follows: particle diameter: 6-7mm; Tap density: 914kg/m
3; Water-intake rate: 11%.
Application test is illustrated
Respectively the iron carbon filler prepared according to embodiment 1, embodiment 2 is loaded in the cylindricality micro-electrolysis reactor shown in Fig. 1, carry out the application test for this anti-novel unburned iron carbon filler that hardens.
1. COD handled by the unburned filler of iron carbon of embodiment 1 is the oil of mirbane trade effluent of 1300-1800mg/L, inlet flow-patterm be 4, air water throughput ratio A/L=2.0, HRT(hydraulic detention time) 4h condition under, COD
crclearance can reach 50%-60%, and chroma removal rate can reach more than 50%.
Reactor runs 4 weeks continuously, does not find significantly to harden phenomenon, and waste water treatment efficiency is stablized.Median size after described filler process waste water is 5-5.5mm.
2. the iron carbon filler process industry coking chemical waste water of embodiment 2, its COD is 13000-16000mg/L, and colourity is about 11000-12000.Wastewater pH is adjusted to about 3, at HRT(hydraulic detention time) under the condition of 6h, the COD of 60-70% can be removed
cr, colourity is all removed.
Reactor runs 3 weeks continuously, and outlet effect is more stable, does not occur situation about hardening.Median size after described filler process waste water is 5.5-6.5mm.
Claims (7)
1. prepare a method for the anti-granular unburned iron-carbon micro-electrolysis filler that hardens, comprise the following steps:
(1) iron filings, charcoal, flyash, cement, unslaked lime, clay are carried out drying and processing 1-2 hour at 105-110 DEG C respectively, then pulverize, cross 100 mesh sieves;
In above-mentioned raw materials, iron content>=95% in iron filings; SiO in flyash
2content 47-52%, Al
2o
3content 27-30%, CaO, MgO, Na
2o and K
2the total content 5-7% of O; Be mass percentage;
(2) by step (1) through pretreated starting material, according to iron filings 32-36%, charcoal 8-10%, flyash 32-35%, cement 9-12%, unslaked lime 5-7%, the massfraction of clay 5-7% mixes, granulation; Cross 5-6 mesh sieve, the particle diameter filtered out is that the raw material ball of 5-7mm is placed in dry ventilation drying at room temperature 20-24 hour, obtains raw material ball;
(3) raw material ball of drying step (2) obtained, at the Water Under steam curing 30-60 minute of 100-110 DEG C; After this once, described natural curing is naturally place after described raw material ball uniform sprinkling, and after natural curing 5-7 days, must resist the granular unburned iron-carbon micro-electrolysis filler that hardens, sealing is preserved in natural curing in every 24 hours.
2. preparation according to claim 1 resists the method for the granular unburned iron-carbon micro-electrolysis filler that hardens, and it is characterized in that the massfraction of each raw material in step (2) is respectively iron filings 36%, charcoal 9%, flyash 33%, cement 10%, unslaked lime 6%, clay 6%.
3. preparation according to claim 1 resists the method for the granular unburned iron-carbon micro-electrolysis filler that hardens; it is characterized in that the granulation in step (2) pours raw material into tablets press to make raw meal particulate, constantly spray the spraying of binding agent diluent in the process to help raw material balling-up.
4. preparation according to claim 3 resists the method for the granular unburned iron-carbon micro-electrolysis filler that hardens, and it is characterized in that described binding agent is the water glass solution of modulus 2.5-2.8.
5. preparation according to claim 3 resists the method for the granular unburned iron-carbon micro-electrolysis filler that hardens, and it is characterized in that described binding agent diluent is doubly formulated by described binding agent thin up 2-3.
6. preparation according to claim 1 resists the method for the granular unburned iron-carbon micro-electrolysis filler that hardens, it is characterized in that in step (3), raw material ball is the Water Under steam curing 45 minutes of 105 DEG C, after this natural curing in every 24 hours once, obtained anti-granular unburned iron-carbon micro-electrolysis filler sealing of hardening, after 6 days, is preserved by continuous maintenance.
7. preparation according to claim 1 resists the method for the granular unburned iron-carbon micro-electrolysis filler that hardens, and it is characterized in that the described anti-granular unburned iron-carbon micro-electrolysis filler that hardens, profile is round shaped grain shape, particle diameter 5-7mm, tap density 900-950kg/m
3, water-intake rate 9%-12%.
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