CN102515551B - Multi-hole foam glass carrier for fast mass transfer biological fluidized bed and preparation method and application thereof - Google Patents
Multi-hole foam glass carrier for fast mass transfer biological fluidized bed and preparation method and application thereof Download PDFInfo
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- CN102515551B CN102515551B CN201110392155.0A CN201110392155A CN102515551B CN 102515551 B CN102515551 B CN 102515551B CN 201110392155 A CN201110392155 A CN 201110392155A CN 102515551 B CN102515551 B CN 102515551B
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- 238000012546 transfer Methods 0.000 title claims abstract description 58
- 239000011494 foam glass Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 244000005700 microbiome Species 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000003245 coal Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
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- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000010865 sewage Substances 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000006260 foam Substances 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
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- 239000002893 slag Substances 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 17
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- 239000006063 cullet Substances 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
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- 229910021532 Calcite Inorganic materials 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- Y02W10/12—
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- Biological Treatment Of Waste Water (AREA)
Abstract
The invention relates to a multi-hole foam glass carrier for a fast mass transfer biological fluidized bed and a preparation method and application thereof, which belong to sewage disposal technology. The multi-hole foam glass carrier is prepared by using waste glass as a raw material to be composited with volcanic rocks, coal ash, coal gangue, furnace clinker, iron powder, aluminum powder, binding agents, foaming agents, foam stabilizer and fluxing agents by weight, and multi-hole foam glass is obtained by stages of preheating, fast sintering, foaming, fast cooling and annealing. The preparation process of the multi-hole foam glass carrier is simple in route, easy to control and low in cost, and the prepared carrier is stable in performance, high in porosity, large in specific surface area, resisting in impact, good in mechanical performance, high in biocompatibility, favorable to efficient fixing of the microorganism, and suitable to the fast mass transfer biological fluidized bed. The multi-hole foam glass carrier solves the problem that biological immobilization carriers in the prior art are easy to abrade, small in bio-film formation amount, low in mass transfer effects and the like in the fast mass transfer biological fluidized bed. The preparation method opens up new approaches for preparing the biological carriers, and fills blank spaces in using of foam glass materials in sewage disposal.
Description
Technical field
The present invention relates to a kind of porous foam glass carrier for quick mass transfer biological fluidized bed and preparation method thereof, application, belong to sewage disposal technology.The suitable porous foam glass carrier GM-2 of density, take cullet, volcanics, slag the like waste as raw material, makes by simple technique, and with low cost, stable performance, is applicable to quick mass transfer biological fluidized bed.
Background technology
Biological fluidized bed (FBR) wastewater processing technology is the efficient biological process of wastewater treatment of one growing up nineteen seventies, it is by being coupled biological fixnig and chemical industry fluidization technology to increase the alternate relative velocity contrast that flows of gas-liquid-solid three-phase, accelerate the succession of the old by the new of interphase mass transfer and microorganism, thereby greatly improve biological wastewater treatment efficiency.Compared with other bio-reactor, little (the 5%) ﹑ sludge yield that is about conventional activated sludge process is few, microorganism active advantages of higher and be day by day subject to investigator's attention with its removal efficiency Gao ﹑ hydraulic detention time Duan ﹑ resistance to overload shock Neng Li Qiang ﹑ floor space for biological fluidized bed.
Microbial immobilized be biological fluidized bed research, application, gordian technique in promoting.General microbial fixed carrier exists a lot of deficiencies at aspects such as stability, biological activity, mass transfers, causes that biological fluidized-bed reactor power consumption is large, start time long, operation inconvenience.Therefore, developing suitable carrier, is very necessary for fast, effectively, stably realizing microbial immobilization, improving biochemical degradation efficiency.
In fluidized-bed reactor, conventional carrier can be divided into porous inorganic carrier, and organic porous carrier and composite porous carrier, mainly contain sand, haydite, zeolite, vermiculite, volcanics, polypropylene, polyvinyl chloride, engineering plastics, modified polyurethane etc.It is generally acknowledged that support shapes is take spherical or almost spherical as best; The particle diameter of carrier is between 0.2～0.8 mm; Density is suitable, and pore size distribution is reasonable, and voidage is high, and specific surface area is large; Have good wetting ability, biological affinity is strong; Chemical stability, good mechanical property, low price etc.Inorganic porous property material refers to natural minerals directly or after modification, is used as the carrier of biological fluidized bed, this class carrier surface rough porous, and biological affinity is good, wide material sources, price is relatively cheap, but ubiquity carrier is than great, the features such as fluidization energy consumption is high, and porosity is low.Organic porous carrier is generally the excellent propertys such as synthetic polymer support, carrier specific surface area and density, and outer carrier aperture distributes reasonable and porosity is high, and wear resistance is good.But the wetting ability of organic porous carrier and biological affinity are poor, at aspect Shortcomings such as microorganism colonization speed, biofilm amount and microorganism activies, such support density is less simultaneously, easy up-flow in quick mass transfer biological fluidized bed, difficult sedimentation, and it is poor to be difficult to form larger alternate relative velocity, thereby greatly reduces interphase mass transfer efficiency and final biochemical degradation efficiency.Composite porous carrier generally refers to porous inorganic carrier and organic porous carrier or a kind of novel carriers organically combining with other materials wherein.This carrier has organically combined the advantage of compound carrier, in physical and chemical performance and performance characteristic, all has greatly improved.
Application number is that 02129972.2 patent of invention discloses a kind of functional ceramsite carrier and fixed microorganism treating sewage technology thereof.Described carrier, take potter's clay as main raw material, through batching, grinding, granulation, moulding, sintering process, and makes after processing by 10% silicone couplet toluene solution hole surface.Its light weight, resistance to flushing, load of microorganisms amount are high, stable chemical nature, but this ceramsite carrier will be through repeatedly washing and acetone displacement in preparation process, complex steps, simultaneously in the time that hole surface is processed, the medicament of use not only can cause secondary pollution as hydrogen peroxide, γ-aminopropyl triethoxysilane etc., add larger vector preparation cost simultaneously, be not suitable for large-scale production.
Application number is the fluidized bed processor that 200910155860.1 patent of invention discloses a kind of dyeing waste water, and wherein the become reconciled microbial fixed carrier of oxygen flow fluidized bed reactor of anaerobic fluidized bed reactor is shell preparing active carbon particle.Although this device has improved the phenomenon that carrier runs off to a certain extent, and there is the rapidly and efficiently characteristic of degrade azo dyestuff, colourity and COD clearance are high, the advantages such as effluent quality is good, but its fluidized-bed is especially anaerobic fluidized bed because anerobe propagation is slow, meanwhile, the outer polymer of born of the same parents of anaerobic bacterium secretion is few, be difficult for and carrier adhesion, and the active fruit shell carbon porosity using is low, bioaffinity is poor, microorganism is easy to be filmed not, and bad mechanical strength, grade easy to wear is more unfavorable for microorganism cohesion biofilm, cause anaerobic reactor long start time, limit the application of this device.
Application number is that 99804643.4 patent of invention discloses a kind of method of wastewater treatment of removing organism and nitrogen and this method carrier used and preparation method thereof, wherein relates to two kinds of organic porous carriers.The carrier using in the first aeration tank is by foamed polymer (having urethane, polystyrene or the polyethylene of spongy foam structure or non-woven fibrous structure), is attached to powder-type gac on foamed polymer and powder-type gac is adhered to binding agent (mixture of acrylic resin and phenylethylene/butadiene latex) on foamed polymer synthetic, is mainly used to load aerobic microbiological; The carrier using in the second aeration tank is polyvinyl alcohol foam carrier or cellulosic fibre carrier, and this carrier is to make as follows: 1) cellulosic fibre is molded into laminar; 2) with the foaming composition impregnated sheets shape cellulosic fibre that comprises polyvinyl alcohol, linking agent and whipping agent; 3) make step 2 by dehydration) foaming of the product that obtains; 4) soak into step 3 by the enhancing composition that comprises polyvinyl alcohol and linking agent) product that obtains; 5) product step 4) being obtained takes out and is dried from composition, is mainly used to load nitrobacteria.Although above two kinds of carrier specific surface areas are large, good endurance, be beneficial to load of microorganisms.But, because belonging to organic polymer, preparation process synthesizes, and technique is loaded down with trivial details, and reaction requires strict, and cost is higher, and polymer is easily biodegradable simultaneously, and these have all limited its widespread use.Meanwhile, high molecular polymer support density is close to water, little with the alternate relative velocity contrast that flows of liquid phase at fluidized-bed up-flow district carrier, a little less than the friction of solid-liquid contact face, make the dynamic turbulent flow of carrier and liquid phase poor, easily cause carrier organism theca cell mass transfer concentration boundary layer trend to stablize and restriction mass-transfer efficiency.This kind of situation is more outstanding in quick mass transfer biological fluidized bed Jiang Liu district, under unpowered suitable gravity field, the alternate relative speed difference of carrier granule and liquid phase is very little, interphase mass transfer efficiency is lower, in the time of fluidisation, easily cause skewness simultaneously, affect microorganism mass transfer, thereby reduce the processing efficiency of fluidized-bed.Therefore the porous support of developing a kind of high porosity, high bioaffinity and higher density has very important realistic meaning.
Summary of the invention
The object of the invention is for above-mentioned weak point, a kind of porous foam glass carrier for quick mass transfer biological fluidized bed and preparation method thereof, application are provided, take cullet, volcanics, slag the like waste as raw material, by simple technique, prepare the porous foam glass carrier GM-2 of high porosity, high bioaffinity and higher density, thereby it is relative violent that carrier is rubbed between the up-flow district of quick mass transfer biological fluidized bed and liquid phase contact surface, has certain alternate current difference; Jiang Liu district, because support density overweights waste water density, is easy to sedimentation, has greatly improved the convective mass transfer performance of system.
The present invention is used for porous foam glass carrier of quick mass transfer biological fluidized bed and preparation method thereof, application is to take following technical scheme to realize:
For the porous foam glass carrier of quick mass transfer biological fluidized bed, it is characterized in that take cullet as raw material, formulated by mass percentage with volcanics, flyash, coal gangue, slag, iron powder, aluminium powder, binding agent, whipping agent, suds-stabilizing agent, fusing assistant, obtain porous foam glass by preheating, Fast Sintering, foaming, fast cooling and annealing stage.Wherein quality of material per-cent is:
Cullet 30 ~ 50%
Volcanics 10 ~ 20%
Flyash 5 ~ 20%
Iron powder 10 ~ 20%
Binding agent 0.5 ~ 2%
Whipping agent 1 ~ 5%
Suds-stabilizing agent 0.5 ~ 1.2%
Fusing assistant 0.5 ~ 1%.
The preparation method who is used for the porous foam glass carrier of quick mass transfer biological fluidized bed comprises the following steps:
1) cullet is cleaned up, after drying, ball milling becomes the glass powder below 200 orders;
2) 30 ~ 50% cullet powder, 10 ~ 20% volcanics, 5 ~ 20% flyash, 2 ~ 10% coal gangue, 5 ~ 10% slag, 10 ~ 20% iron powder, 5 ~ 10% aluminium powder, 0.5 ~ 2% binding agent, 1 ~ 5% whipping agent, 0.5 ~ 1.2% suds-stabilizing agent and 0.5 ~ 1% fusing assistant mixture are put into ball grinder, be milled to 200 orders and add below mould to foam;
3) pre-heating stage, rises to 300 ~ 320 ℃ and be incubated 20 ~ 30min with the temperature rise rate of 5 ~ 8 ℃/min from room temperature; In the Fast Sintering stage, rise to 730 ~ 750 ℃ and be incubated 10 ~ 20min with the temperature rise rate of 15 ~ 18 ℃/min from 300 ~ 320 ℃; Foaming stages, rises to 850 ~ 880 ℃ and be incubated 20 ~ 30min with the temperature rise rate of 9 ~ 12 ℃/min from 730 ~ 750 ℃; In the fast cooling stage, rate of temperature fall is 12 ~ 18 ℃/min, is cooled to 600 ~ 650 ℃ of insulation 30 ~ 40min; Annealing stage, rate of temperature fall is 1 ~ 2 ℃/min, be annealed to 400 ~ 450 ℃ after fast cooling, rate of temperature fall is 12 ~ 18 ℃/min, makes for the quick porous foam glass carrier of mass transfer biological fluidized bed.
The addition of above material is mass percent.
Described cullet is one or more in container glass, sheet glass, laboratory abandoned laboratory glass wares.
Described binding agent is one or more in PEG-4000, polyvinyl alcohol, phosphoric acid.
Described whipping agent is one or more in silicon carbide, carbide of calcium, calcium sulfate, sodium sulfate, Manganse Dioxide, calcium carbonate, antimonous oxide, SODIUMNITRATE, carbon black, water glass.
Described suds-stabilizing agent is one or more in zinc oxide, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, trimagnesium phosphate.
Described fusing assistant is one or more of Sodium Silicofluoride, lithionite, triphane, mullite, borax, boric acid, feldspar, calcite, Bai Shizhong.
The average pore diameter of described porous foam glass carrier is between 0.5 ~ 1mm.
The density of described porous foam glass carrier is 1.2 ~ 1.6g/cm
3.
Described porous foam glass carrier is mainly used in the quick mass transfer biological fluidized bed in field of waste water treatment, as the carrier of microorganism colonization.
Described a kind of porous foam glass carrier for mass transfer biological fluidized bed is fast for the biochemical treatment field of various wastewater, as for sanitary sewage, petrochemical wastewater, paper waste, coking chemical waste water biochemical treatment.
Compare with the carrier of existing document and patent report, a kind of porous foam glass carrier GM-2 for quick mass transfer biological fluidized bed of the present invention has following positively effect:
(1) porous foam glass carrier average pore diameter of the present invention is between 0.5 ~ 1mm, and porosity reaches more than 80%, and hole distribution evenly and interconnect.High porosity carrier, greatly promoted waste water and the microorganism that adheres between alternate touch opportunity, thereby improved the mass transfer effect of system; And flow resistance is less, energy consumption is also relatively low.Under quick mass transfer condition, microorganism is more easily held back in above-mentioned duct, is beneficial to microorganic adhesion, breeding simultaneously, improves sewage treating efficiency.But the existence of a large amount of holes has reduced the unit weight of carrier, in quick mass transfer biological fluidized bed, easily be gathered in fluidized-bed reactor top, cause metabolic degradation mainly to occur in bed upper end, and bottom carrier is less, cause carrier skewness in whole reactor, thereby greatly reduce the effective volume utilization ratio of biological fluidized bed.In order to overcome above-mentioned shortcoming, we add density greatly and aboundresources in carrier preparation process, cheap slag and volcanics, and not only specific surface area is large, porosity is high, connectivity is good to make carrier, and density is suitable simultaneously, is easy to fluidisation.
(2) in porous foam glass carrier of the present invention, introduce ferro element, after foaming is processed, iron changes Z 250 into.Z 250 is a kind of magnetic particle, can produce Weak magentic-field.It makes carrier granule be equal to a miniature magnetic field reactor, utilizes microorganism magnetic effect and metabolism or common metabolism, inducible enzyme synthetic, improve enzyme and live, stimulate microorganism growth, shorten its growth cycle, accelerate biomembranous the old and new and upgrade, make waste water treatment efficiency be able to obvious raising.Meanwhile, magnetic effect has the water of promotion mineral dissolves and makes partial organic substances be decomposed into the ability of the element such as C, N, thereby for microbial growth provides necessary nutrition, is conducive to the breeding of adhering to of microorganism, improves biological degradation efficiency.
(3) the reaction bonded moulding process (RBAO) of porous ceramics in firing used for reference in the preparation of porous foam glass carrier of the present invention, adds in proportion aluminium powder in carrier.So-called RBAO technology, refers in starting raw material, add metallic aluminium powder, and after moulding, green compact heat in air, and aluminium powder generation oxidizing reaction generates aluminum oxide.This reaction is accompanied by Volumetric expansion, can make up the volumetric shrinkage in sintering process, reduces base substrate shrinking percentage.Newborn alumina particle is tiny, has high activity, can reduce sintering temperature.In addition,, due to newborn fine structure, make its intensity obtain obvious improvement.Meanwhile, aluminum oxide has the ability of improving chemical durability of glass, reducing devitrification of glass tendency, raising glass machinery intensity and wear resistance.
(4) porous foam glass carrier of the present invention is take cullet, flyash, coal gangue, slag the like waste as main raw material, it not only has sufficiently high physical strength, can resist the effect of frictional force mutually between flow shear and carrier, and raw material is easy to get, cost is lower, whole preparation process does not have waste discharge, belongs to environment friendly technology.
Preparation were established of the present invention is simple, be easy to control, production cost is low, and the carrier property of preparation is stable, porosity is high, specific surface area is large, shock-resistant, good mechanical property, bioaffinity are high, be beneficial to the efficient fixing of microorganism, is applicable to quick mass transfer biological fluidized bed.It has solved the problems such as biological fixing carrier was easy to wear in quick mass transfer biological fluidized bed in the past, biofilm amount is few, mass transfer effect is low.Meanwhile, the method had both been opened up new way for the preparation of bio-carrier, had also filled up the blank that uses multicellular glass material in sewage disposal.
Accompanying drawing explanation
Fig. 1 is the schematic diagram for the quick mass transfer biological fluidized-bed reactor of anaerobic type.
Describe the present invention below in conjunction with embodiment.Scope of the present invention is not limited with embodiment, but is limited by the scope of claim.
Embodiment
Porous foam glass carrier GM-2 of the present invention is applicable to the quick mass transfer biological fluidized bed of all kinds of internal recycle.The quick mass transfer biological fluidized-bed reactor of anaerobic type comprises waste water tank 1, liquid feeding pump 2, mixing tank 3, reflux pump 4, three-phase fluidized bed 5.
Below in conjunction with specific embodiment, the present invention is further described:
Embodiment 1:
Container glass is cleaned up, and after drying, ball milling becomes the glass powder below 200 orders; The mullite mixture of the sodium phosphate of the silicon carbide of the PEG-4000 of the aluminium powder of the iron powder of the slag of the coal gangue of the flyash of the volcanics of the container glass powder of 5Kg, 1.68Kg, 0.8Kg, 0.2Kg, 0.5Kg, 1Kg, 0.5Kg, 0.1Kg, 0.1Kg, 0.06Kg and 0.06Kg is put into ball grinder, being milled to 200 orders adds mould to foam below: pre-heating stage, rises to 300 ℃ and be incubated 20min with the temperature rise rate of 5 ℃/min from room temperature; In the Fast Sintering stage, rise to 730 ℃ and be incubated 10min with the temperature rise rate of 15 ℃/min from 300 ℃; Foaming stages, rises to 850 ℃ and be incubated 20min with the temperature rise rate of 9 ℃/min from 730 ℃; In the fast cooling stage, rate of temperature fall is 12 ℃/min, is cooled to 600 ℃ of insulation 30min; Annealing stage, rate of temperature fall is 1 ℃/min, be annealed to 400 ℃ after fast cooling, rate of temperature fall is 12 ℃/min, makes for the quick porous foam glass carrier of mass transfer biological fluidized bed.
More than the amount of adding materials weight percent is: container glass 50%, volcanics 16.8%, flyash 8%, coal gangue 2%, slag 5%, iron powder 10%, aluminium powder 5%, PEG-4000 1%, silicon carbide 1%, sodium phosphate 0.6%, mullite 0.6%.
In the quick mass transfer biological fluidized bed of anaerobism, add porous foam glass carrier GM-2 in order to process certain petrochemical wastewater, and compare wherein loadings 30%(V/V with diatomite treatment effect), residence time 3h, flow velocity is 2.15L/h, 31 ℃ of water temperatures.Former water COD 6002mg/L, TA 1790 mg/L.Experimental result is as follows:
Embodiment 2:
Sheet glass is cleaned up, and after drying, ball milling becomes the glass powder below 200 orders; The borax mixture of the SODIUM PHOSPHATE, MONOBASIC of the carbon black of the polyvinyl alcohol of the aluminium powder of the iron powder of the slag of the coal gangue of the flyash of the volcanics of the sheet glass powder of 5Kg, 1.2Kg, 0.87Kg, 0.2Kg, 0.7Kg, 1.07Kg, 0.55Kg, 0.12Kg, 0.14Kg, 0.07Kg and 0.08Kg is put into ball grinder, being milled to 200 orders adds mould to foam below: pre-heating stage, rises to 300 ℃ and be incubated 25min with the temperature rise rate of 6 ℃/min from room temperature; In the Fast Sintering stage, rise to 730 ℃ and be incubated 15min with the temperature rise rate of 15 ℃/min from 300 ℃; Foaming stages, rises to 860 ℃ and be incubated 25min with the temperature rise rate of 10 ℃/min from 730 ℃; In the fast cooling stage, rate of temperature fall is 14 ℃/min, is cooled to 615 ℃ of insulation 35min; Annealing stage, rate of temperature fall is 1 ℃/min, is annealed to after 410 ℃, fast cooling, rate of temperature fall is 18 ℃/min, makes the porous foam glass carrier for quick mass transfer biological fluidized bed.
More than the amount of adding materials weight percent is: sheet glass 50%, volcanics 12%, flyash 8.7%, coal gangue 2%, slag 7%, iron powder 10.7%, aluminium powder 5.5%, polyvinyl alcohol 1.2%, carbon black 1.4%, SODIUM PHOSPHATE, MONOBASIC 0.7%, borax 0.8%.
In aerobic quick mass transfer biological fluidized bed, add porous foam glass carrier GM-2 in order to process certain municipal sewage plant's waste water, loadings 35%(V/V), residence time 1.5h, flow velocity 4.3L/h, DO value 3.4mg/L, 28 ℃ of water temperatures.Former water COD is 480 mg/L, NH
3-N is 57mg/L.Experimental result is as follows:
| Former water COD (mg/L) | Water outlet COD (mg/L) | COD clearance | Former water NH 3-N（mg/L） | Water outlet NH 3-N（mg/L） | NH 3-N clearance |
| 480 | 12 | 97.5% | 57 | 1.1 | 98.1% |
Embodiment 3:
Laboratory abandoned laboratory glass wares are cleaned up, and after drying, ball milling becomes the glass powder below 200 orders; The carbon black of the polyvinyl alcohol of the aluminium powder of the iron powder of the slag of the coal gangue of the flyash of the volcanics of the laboratory abandoned laboratory glass wares glass powder of 3Kg, 1.5Kg, 1.6Kg, 0.8Kg, 0.65Kg, 1.45Kg, 0.65Kg, 0.1Kg, 0.1Kg, the SODIUM PHOSPHATE, MONOBASIC of 0.08Kg and the borax mixture of 0.07Kg are put into ball grinder, being milled to 200 orders adds mould to foam below: pre-heating stage, rises to 310 ℃ and be incubated 25min with the temperature rise rate of 7 ℃/min from room temperature; In the Fast Sintering stage, rise to 740 ℃ and be incubated 15min with the temperature rise rate of 16 ℃/min from 310 ℃; Foaming stages, rises to 870 ℃ and be incubated 23min with the temperature rise rate of 11 ℃/min from 740 ℃; In the fast cooling stage, rate of temperature fall is 15 ℃/min, is cooled to 620 ℃ of insulation 37min; Annealing stage, rate of temperature fall is 2 ℃/min, is annealed to after 420 ℃, and rate of temperature fall is 16 ℃/min, and fast cooling makes the porous foam glass carrier for quick mass transfer biological fluidized bed.
More than the amount of adding materials weight percent is: laboratory abandoned laboratory glass wares 30%, volcanics 15%, flyash 16%, coal gangue 8%, slag 6.5%, iron powder 14.5%, aluminium powder 6.5%, phosphatase 11 %, calcium carbonate 1%, trimagnesium phosphate 0.8%, boric acid 0.7%.
In the quick mass transfer biological fluidized bed of anoxic, add porous foam glass carrier GM-2 in order to process certain printing and dyeing mill's waste water, loadings 30%(V/V), the residence time is 2.2h, and flow velocity is 2.93 L/h, and water temperature is 32 ℃.Former water COD is 1537 mg/L, and colourity is 300 times.Experimental result is as follows:
| Former water COD (mg/L) | Water outlet COD (mg/L) | COD clearance | Former colority of water | Effluent color dilution |
| 1537 | 351 | 77.2% | 300 | 36 |
Embodiment 4:
Sheet glass is cleaned up, and after drying, ball milling becomes the glass powder below 200 orders; The feldspar mixture of the zinc oxide of the antimonous oxide of the phosphoric acid of the aluminium powder of the iron powder of the slag of the coal gangue of the flyash of the volcanics of the sheet glass powder of 3.8Kg, 1.4Kg, 1.36Kg, 0.75Kg, 0.7Kg, 0.8Kg, 0.6Kg, 0.05Kg, 0.4Kg, 0.05Kg and 0.09Kg is put into ball grinder, being milled to 200 orders adds mould to foam below: pre-heating stage, rises to 320 ℃ and be incubated 30min with the temperature rise rate of 8 ℃/min from room temperature; In the Fast Sintering stage, rise to 750 ℃ and be incubated 20min with the temperature rise rate of 18 ℃/min from 320 ℃; Foaming stages, rises to 880 ℃ and be incubated 30min with the temperature rise rate of 12 ℃/min from 750 ℃; In the fast cooling stage, rate of temperature fall is 18 ℃/min, is cooled to 650 ℃ of insulation 40min; Annealing stage, rate of temperature fall is 2 ℃/min, be annealed to 450 ℃ after fast cooling, rate of temperature fall is 18 ℃/min, makes for the quick porous foam glass carrier of mass transfer biological fluidized bed.
More than the amount of adding materials weight percent is: sheet glass 38%, volcanics 14%, flyash 13.6%, coal gangue 7.5%, slag 7%, iron powder 8%, aluminium powder 6%, phosphoric acid 0.5%, antimonous oxide 4%, zinc oxide 0.5%, feldspar 0.9%.
In the quick mass transfer biological fluidized bed of A/O internal recycle, add porous foam glass carrier GM-2 in order to process certain coking chemical waste water, loadings 35%(V/V), residence time 2.7h, flow velocity 2.39 L/h.25 ℃ of water temperatures.Former water COD is 2706 mg/L, NH
3-N is 342mg/L.Experimental result is as follows:
| Former water COD (mg/L) | Water outlet COD (mg/L) | COD clearance | Former water NH 3-N（mg/L） | Water outlet NH 3-N（mg/L） | NH 3-N clearance |
| 2706 | 179 | 93.4% | 342 | 10 | 97.1% |
Compared with prior art, of the present invention for the porous foam glass carrier raw materials for production of mass transfer biological fluidized bed are easy to get fast, technique is succinct, cost is lower.The porous foam glass carrier GM-2 high porosity of gained, high bioaffinity, density is suitable, duct connectivity is good, physical strength is high, in quick mass transfer biological fluidized bed easily fluidisation, easy to be filmed, be evenly distributed, greatly shorten fluidized-bed start time, improve biofilm efficiency, and be applicable to the biochemical treatment field of the various wastewater such as sanitary sewage, petrochemical wastewater, paper waste, coking chemical waste water.
Claims (10)
1. the porous foam glass carrier for quick mass transfer biological fluidized bed, it is characterized in that take cullet as raw material, formulated by mass percentage with volcanics, flyash, coal gangue, slag, iron powder, aluminium powder, binding agent, whipping agent, suds-stabilizing agent, fusing assistant, obtain porous foam glass by preheating, Fast Sintering, foaming, fast cooling and annealing stage;
Wherein quality of material per-cent is:
Cullet 30 ~ 50%
Volcanics 10 ~ 20%
Flyash 5 ~ 20%
Coal gangue 2 ~ 10%
Slag 5 ~ 10%
Iron powder 10 ~ 20%
Aluminium powder 5 ~ 10%
Binding agent 0.5 ~ 2%
Whipping agent 1 ~ 5%
Suds-stabilizing agent 0.5 ~ 1.2%
Fusing assistant 0.5 ~ 1%.
2. a kind of porous foam glass carrier for quick mass transfer biological fluidized bed according to claim 1, is characterized in that described cullet is one or more in container glass, sheet glass, laboratory abandoned laboratory glass wares.
3. a kind of porous foam glass carrier for quick mass transfer biological fluidized bed according to claim 1, is characterized in that described binding agent is one or more in PEG-4000, polyvinyl alcohol, phosphoric acid.
4. a kind of porous foam glass carrier for quick mass transfer biological fluidized bed according to claim 1, is characterized in that described whipping agent is one or more in silicon carbide, carbide of calcium, calcium sulfate, sodium sulfate, Manganse Dioxide, calcium carbonate, antimonous oxide, SODIUMNITRATE, carbon black, water glass.
5. a kind of porous foam glass carrier for quick mass transfer biological fluidized bed according to claim 1, is characterized in that described suds-stabilizing agent is one or more in zinc oxide, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, trimagnesium phosphate.
6. according to claim 1 a kind of for the quick porous foam glass carrier of mass transfer biological fluidized bed, it is characterized in that described fusing assistant is one or more of Sodium Silicofluoride, lithionite, triphane, mullite, borax, boric acid, feldspar, calcite, Bai Shizhong.
7. the preparation method of the porous foam glass carrier for quick mass transfer biological fluidized bed claimed in claim 1, is characterized in that concrete preparation method is as follows:
1) cullet is cleaned up, after drying, ball milling becomes the glass powder below 200 orders;
2) 30 ~ 50% cullet powder, 10 ~ 20% volcanics, 5 ~ 20% flyash, 2 ~ 10% coal gangue, 5 ~ 10% slag, 10 ~ 20% iron powder, 5 ~ 10% aluminium powder, 0.5 ~ 2% binding agent, 1 ~ 5% whipping agent, 0.5 ~ 1.2% suds-stabilizing agent and 0.5 ~ 1% fusing assistant mixture are put into ball grinder, be milled to 200 orders and add below mould to foam;
3) pre-heating stage, rises to 300 ~ 320 ℃ and be incubated 20 ~ 30min with the temperature rise rate of 5 ~ 8 ℃/min from room temperature; In the Fast Sintering stage, rise to 730 ~ 750 ℃ and be incubated 10 ~ 20min with the temperature rise rate of 15 ~ 18 ℃/min from 300 ~ 320 ℃; Foaming stages, rises to 850 ~ 880 ℃ and be incubated 20 ~ 30min with the temperature rise rate of 9 ~ 12 ℃/min from 730 ~ 750 ℃; In the fast cooling stage, rate of temperature fall is 12 ~ 18 ℃/min, is cooled to 600 ~ 650 ℃ of insulation 30 ~ 40min; Annealing stage, rate of temperature fall is 1 ~ 2 ℃/min, be annealed to 400 ~ 450 ℃ after fast cooling, rate of temperature fall is 12 ~ 18 ℃/min, makes for the quick porous foam glass carrier of mass transfer biological fluidized bed;
The addition of above material is mass percent.
8. according to claim 7 for the quick preparation method of the porous foam glass carrier of mass transfer biological fluidized bed, the average pore diameter that it is characterized in that porous foam glass carrier is at 0.5 ~ 1mm: the density of described porous foam glass carrier is 1.2 ~ 1.6g/cm
3.
9. the porous foam glass carrier for quick mass transfer biological fluidized bed claimed in claim 1 is for the quick mass transfer biological fluidized bed in field of waste water treatment, as the carrier of microorganism colonization.
10. the porous foam glass carrier for quick mass transfer biological fluidized bed claimed in claim 1 is used in sanitary sewage, petrochemical wastewater, paper waste, coking chemical waste water biochemical treatment.
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| CN101302077B (en) * | 2008-06-06 | 2010-07-21 | 西安交通大学 | Method for directly producing foamed glass by using slag tapping boil slag |
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