CN100341601C - Filtering material used for water-treatment made from waste mud and its prodn. method - Google Patents
Filtering material used for water-treatment made from waste mud and its prodn. method Download PDFInfo
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- CN100341601C CN100341601C CNB2005100105786A CN200510010578A CN100341601C CN 100341601 C CN100341601 C CN 100341601C CN B2005100105786 A CNB2005100105786 A CN B2005100105786A CN 200510010578 A CN200510010578 A CN 200510010578A CN 100341601 C CN100341601 C CN 100341601C
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Abstract
The present invention relates to a filtering material used for water treatment and made from sludge, particularly to a filtering material used in the process of water treatment, and a preparation method of the material. At present, the sludge is not effectively used, and people need invest to the sludge treatment, which increases the workload of people. The filtering material which is used for water treatment and made from the sludge is prepared from the raw materials of the following proportion: clay soil accounts for 300 to 400 wt% of the sludge and adhesive accounts for 10 to 20 wt% of the clay soil. The preparation method comprises: mixing all raw materials according to the proportion and sintering the mixed materials at a temperature of 900 to 1200 DEG C for 15 to 35 min. The filtering material of the present invention has enough intensity and difficult breakage, and due to the rough surface of the obtained filtering material, biofilm culturing of microbe is easy. The filtering material manufactured by the method and the raw materials of the present invention can consume a large amount of the dewatered sludge, the treating cost is low, and secondary pollution of the sludge is avoided, so the present invention is convenient to popularize and use.
Description
Technical field
The present invention relates to filtering material that uses in a kind of water treatment procedure and preparation method thereof.
Background technology
BAF is applied in the wastewater treatment, and the selection of particulate filter is very big for obtaining the effect that greater activity biomass and bio-diversity play.At present, Chang Yong filtrate has quartz sand, active carbon, zeolite, haydite and plastic products (synthetic fibers, polyethylene bead, corrugated plating etc.).BAF to the general requirement of filtrate is: (1) rough surface.Shaggy filtrate has been for microorganism provides desirable growth, breeding spot, shows as that easy extension is touched, the biomass height.(2) density is moderate.Density is unfavorable for the carrying out of backwash too greatly, shows as that required backwashing strength is big, the recoil required time is long; Density is too little, runs material, wayward backwashing strength when recoil easily.(3) certain intensity is arranged, rub resistance.(4) nontoxic, chemical property is stablized.(5) moderate cost.At present, domesticly in biological process of wastewater treatment, developed multiple new packing, set up a collection of manufacturer, product category is various, and class is comparatively complete, but existing filtrate respectively has its weakness at aspects such as physics characteristic and biomembrane adhesion properties, they or smooth surface, microorganism are difficult to biofilm, or insufficient strength, badly broken, or the difficulty that costs an arm and a leg, regenerates, and present employed filtrate does not nearly all possess the characteristic that promotes microbial activity.Therefore researching and developing a kind of good contact filtrate is to be related to BAF to be applied to one of water treatment key of success.
Mud is that what to form in the water treatment procedure is the gunk of main component with the organic matter, and on apparent, mud is black, indefinite form, and hand touches sticking sensation.Its content of organics height is degenerated smellyly easily, and particle is thinner, and density is less, and moisture content is high and be difficult for dehydration, is the hydroaropic substance that is colloid form structure.Present mud is not effectively used as the surplus products of conventional sewage disposal, and on the contrary, people also need to invest extra-pay it is disposed, thereby have increased the people's work burden.
Summary of the invention
At the problem that existing mud is not used effectively, the invention provides and a kind ofly not only can effectively utilize mud, can also make product have fabulous performance simultaneously and possess filtering material that promotes the microbial activity characteristic and preparation method thereof.The water treatment filtering material of making by mud, it is that feedstock production by following composition forms: mud, clay, binding agent, the addition of described each raw material is respectively: clay comprises dewatered sludge quality 300～400%, binding agent accounts for 10～20% of clay quality; Its preparation method after each raw material is mixed in described ratio, fires 15～35min under 900～1200 ℃ of conditions, said dewatered sludge is for carrying out the raw material after drying, fragmentation and the screening to mud, and specifically preparation process is as follows successively:
A. mud is carried out drying, fragmentation and screening;
B. add the clay that accounts for dewatered sludge quality 300～400%, the binding agent that accounts for clay quality 10～20%, mix the back extrusion modling with dewatered sludge;
C. sintering: earlier the moulding filtrate is carried out drying and preheating, its moisture is fully got rid of; Under 900～1200 ℃ of conditions, carry out roasting 15～35min then;
D. naturally cool to room temperature,
The extrusion modling process of described b step is: each raw material is fully mixed in the dry grinding container back well in described ratio weighing; mix after the end; raw material is poured in the mixer; add an amount of water; fully stir; the moisture content of compound is controlled between 10～20%, and extrusion modling on granulator then makes filtrate after the screening.
The inventor combines the data of relevant BAF filtering material both domestic and external, having carried out a large amount of is the test of feedstock production filtering material with mud and clay, technological parameter when once obtaining the clay addition and being no more than 1.5 times of sludge qualities, test finds, if the gained media performance obviously reduces when the clay addition surpasses 1.5 times of sludge qualities.But continue to find in the research the inventor, when the clay addition is 3～4 times of sludge qualities, the gained media performance is significantly improved again, so the inventor tests the influence degree of various conditions to media performance, pass through orthogonal test, mud adds the influence of percentage, binding agent adds the influence of percentage, a large amount of tests such as the influence of firing temperature and the influence of temperature retention time, obtained suitable firing temperature, time and temperature-rise period system, and according to testing result to some physical and chemical performances of filtering material, determine the proportioning and the burning process parameter of sludge filtration material, prepared the complete satisfactory mud filtrate of performance.After tested, gained filtering material of the present invention can reach following performance: the methylene blue adsorbance is 0.158mg/g, and iodine absorption number is 15.6mg/g, yield is 83.3%, and burning the mistake rate is 18.2%, and water absorption rate is 9.3%, voidage is 41.2%, and loose volume weight is 571kg/m
3, apparent particle density is 1021kg/m
3Yield=M among the present invention
Product/ M
Raw material* 100%, burn mistake rate=(1-yield) * 100%.As can be seen, gained filtering material of the present invention has enough intensity, cracky not, and because gained filtering material rough surface, so the easy biofilm of microorganism; This filtering material also possesses the characteristic that intensifies microbial activity simultaneously, and with the filtering material of the inventive method and feedstock production can be a large amount of the consumption dewatered sludge, not only processing cost is significantly less than burning method, and can avoid the mud secondary pollution, especially meet useless admittedly innoxious, minimizing of handling of China and resource principle, vast potential for future development will be arranged.Pass through heavy metal Cr in the filtering material simultaneously
6+Leaching test, through XRD analysis as can be known, the heavy metal Cr in the raw material
6+Through high temperature sintering, mainly the form with crystal is present in the finished product, and the heavy metal that is detected all is to exist with the stable state compound structure.Because ionic bond has higher lattice energy and very strong stability, so heavy metal has ability to cure preferably in the bed mud haydite, thereby eliminated gained filtering material issuable misgivings in application process, is beneficial to and applies.
Description of drawings
Fig. 1 is that the specific embodiment six described biofilms of carrying out are tested employed experimental rig structural representation.
The specific embodiment
The specific embodiment one: the water treatment filtering material of present embodiment for making by mud, it is that feedstock production by following composition forms: mud, clay, binding agent, the addition of described each raw material is respectively: clay comprises dewatered sludge quality 300～400%, binding agent accounts for 10～20% of clay quality; Its preparation method is, after each raw material is mixed in described ratio, fires 15～35min under 900～1200 ℃ of conditions, and the described binding agent of present embodiment is a waterglass.
The specific embodiment two: the addition of each raw material is respectively in the present embodiment: clay comprises dewatered sludge quality 320%, binding agent accounts for 12% of clay quality; After each raw material mixed in described ratio, under 1000 ℃ of conditions, fire 30min.
The specific embodiment three: the addition of each raw material is respectively in the present embodiment: clay comprises dewatered sludge quality 380%, binding agent accounts for 18% of clay quality; After each raw material mixed in described ratio, under 1150 ℃ of conditions, fire 20min.
The specific embodiment four: the addition of each raw material is respectively in the present embodiment: clay comprises dewatered sludge quality 350%, binding agent accounts for 15% of clay quality; After each raw material mixed in described ratio, under 950 ℃ of conditions, fire 32min.
The specific embodiment five: present embodiment elaborates the preparation process of filtering material, and detailed process is as follows successively:
A. mud is carried out drying, fragmentation and screening: dry purpose is that the moisture in the mud is removed; Behind the sludge crushing, adopt the unification of the motherland standard screen to sieve.
B. add the clay that accounts for dewatered sludge quality 300～400%, the binding agent that accounts for clay quality 10～20%, mix the back extrusion modling with dewatered sludge: mud can reduce the loose volume weight of product and reduce firing temperature; Aluminium matter composition in the raw clay can increase the plasticity of raw material, increases the intensity of product simultaneously and burn the performance that expands in sintering process, can overcome the shortage of silicon in the mud, aluminium component like this.The waterglass that adding accounts for clay quality 10～20% helps molding bonded as binding agent, and the effect that reduces product unit weight and firing temperature is arranged.Each raw material is mixed the back extrusion modling: with each raw material in described ratio weighing after, mix in the container in dry grinding because the high speed of blade is rotated, raw material is fully mixed.Mix after the end, raw material is poured in the mixer, add an amount of water, fully stir, the moisture content of compound is controlled between 10～20%, and extrusion modling on granulator makes filtering material after the screening.
C. sintering: earlier the moulding filtrate is carried out drying and preheating, its moisture is fully got rid of, avoid that filtering material ftractures because of excess moisture in sintering procedure; Under 900～1200 ℃ of conditions, carry out roasting 15～35min then;
D. naturally cool to room temperature.
The specific embodiment six:
Can a kind of novel filtrate be applied to go in the unit of Sewage Biological Treatment, be used widely, and mainly sees its treatment efficiency in reactor.The contrast experiment that present embodiment selects for use Jiangxi haydite (3-5mm), Guangzhou haydite (3-6mm), ature of coal column-shaped active carbon and four kinds of filtrates of filtrate of the present invention (4-6mm) to do investigates and utilizes dewatered sludge to make the feasibility of novel filtrate as aerating biological filter pool filler.
One. experimental rig and test water
1. experimental rig: carry out the biofilm test, used filter post height is 200cm, and diameter is 5cm, and filtering layer is thick to be 120cm, and supporting layer is 10cm, in order to eliminate the influence of wall effect, carried out the special coarse processing of limit wall to filtering post in test.Adopt the aeration tube aeration, the aeration position is provided with and improves to some extent than conventional method, and at distance supporting layer 40cm place, to stream, experimental rig as shown in Figure 1 under water intake mode adopted.
2. test water: because the test period is longer, the test water amount is big, directly test relatively difficulty in the laboratory with sanitary sewage, so adopt the method for artificial dilution raw sewage to be used as obtaining the experimental rig water, sanitary sewage is taken from Harbin Institute of Technology's second school district effluent sewerage, add before the water tank, the bulky grain pollutant removal, duration of test reactor water quality sees Table 1 to sewage through screen cloth.
Table 1 test sanitary sewage water quality
| Index | Numerical value | Index | Numerical value |
| COD (mg/L) ammonia nitrogen (mg/L) pH | 110-300 10.5-33.7 6.9-8.3 | Turbidity ultraviolet total phosphorus (mg/L) | 30-60 0.215-0.882 1.9-3.0 |
| SCOD(mg/L) | 92-210 | Water temperature (℃) | 20-28 |
Two. the biofilm of four kinds of filtrate reactors starts and the operational effect contrast
The startup of bioreactor operation is one of key technology of biological treatment, adopts suitable startup method, starts rapidly and enters steady-state operation, not only can shorten the debug time of operation, and effective remedial measure can also be provided when the generation interruption of service.
The same with other biomembrance process treatment technology, the startup of BAF also needs to carry out synchronously microorganism at the enrichment process of reactor with in the breeding of adhering to of filling surface, be the biomembranous forming process of filling surface steady-state growth, be also referred to as " biofilm ".
In this experimental study, adopt down and move to the stream mode, the biofilm startup of BAF adopts the pattern that adds kind of a mud-vexed exposing to the sun-Continuous Flow cultivation to carry out, promptly when reactor start-up, add a certain amount of activated sludge as kind of a mud, the vexed 3d that exposes to the sun of elder generation, then at flow of inlet water 2L/h, gas-water ratio 3-5: operation continuously under 1 the condition, continuously behind the operation 14d, find that by microscopic examination a large amount of campanularians is arranged in the biomembrane on the filler, paramecium, amoeba, wheel animalcule, nematode and a large amount of der Pilz, the visible biomembrane of naked eyes is light yellow and transparent, still there is strand shape flco at the edge, and water outlet simultaneously is also more stable.So far biofilm work is finished, and reactor starts smoothly.
It is a progressive continuous process that the biofilm of BAF reactor starts, because the particulate filler specific area is big, high adsorption capacity, microorganism in the sanitary sewage very easily is adsorbed in filter material surface, also increased the degree of roughness of filter material surface simultaneously by the organic granular of filtrate institute detention, further strengthened suction-operated free bacteria.Under the oxygen supply of abundance, suitable temperature and certain density substrate condition, the microorganism that is adsorbed begins a large amount of breedings, and metabolism simultaneously produces various outer polymers not born of the same parents (EPS), and the existence of these materials has also promoted biomembranous quick formation.The sunk surface of filtrate has been offset the expansion that the air water shear action helps microbial film more preferably.The friction of the shear action of current between filtrate is formed with side effect to biomembranous in this process.When being covered with biomembrane, filter material surface forms nascent biomembrane, along with the prolongation biomembrane of incubation time constantly thickens and ripe gradually.As a whole, the BAF ratio is easier to biofilm, has the characteristics such as rapid, easy and simple to handle that start, and this also has certain positive effect in the operation debugging of actual engineering.
In this test, select for use 4 kinds of filtrates to carry out biofilm and operation test as the filtrate of BAF, investigate and utilize dewatered sludge to make the feasibility of novel filtrate as aerating biological filter pool filler.
1. contrast to stream BAF turbidity treatment effect under four kinds of filtrates
In the start-up course of descending 14d before the stream BAF, it is very big to the removal effect fluctuation of turbidity that each filters post, during mainly being biofilm, filter material surface is forming biomembrane gradually, crown_interception to contaminant particle is perfect gradually, and because the particle diameter of filtrate is relatively big, thereby turbidity removal rate fluctuates between 30%-95% during biofilm occurring, and it is bigger to fluctuate.From 15d, filter material surface biomembrane maturation, the filter tank enters the operation phase, Guangzhou haydite post, Jiangxi haydite post, Shanxi activated-charcoal column and filtrate post of the present invention are respectively 96.10%, 94.83%, 97.07% and 96.28% to sewage turbidity average removal rate, and filtrate of the present invention is all better slightly than Guangzhou haydite, Jiangxi haydite from the angle of turbidity removal effect and operation stability.
The removal of suspended particles mainly relies on the physics chemical action between suspended particulate and the filtrate in the water, and these effects comprise diffusion, precipitate, hold back, inertia, hydrodynamic force etc.The filter material surface of BAF is with biomembrane, so the removal of turbidity is also had the effect of microorganism aspect: (1) biomembranous agglomeration; (2) the interior bacterium of filter bed is flocculated and helps the effect of coagulating; (3) effect of microfauna.Filtrate concerns very big to the crown_interception of suspended particulate and the surface nature of filtrate, the filtrate of unlike material has been adopted in this test, and all there is biomembrane to cover above the filtrate, influent quality is identical, effluent quality much at one, this illustrates that these several filtrates all are fit to do the filtrate of BAF, no matter filtrate of the present invention is that the character or the physical and chemical stability of the surface of solids is all very good, as seen utilizing mud is a recycling sludge and an innoxious feasible approach for the novel filtrate of feedstock production.
2. contrast to stream BAF COD treatment effect under four kinds of filtrates
Bioreactor for sewage treatment is one of main index of assessing reactor performance to organic place to go ability, four kinds of filler in aerated biologic filter pool of duration of test are in the start-up course of preceding 14d, 4 filter posts are bigger to the removal effect fluctuation of COD, average removal rate is below 40%, during mainly being biofilm, filter material surface is forming biomembrane gradually, what biological agent was not also well brought into play in the filter post comes out, also might test water quality instability exactly, thereby cause the fluctuation of COD removal effect with sanitary sewage; From 15d, filter material surface biomembrane maturation, the filter tank enters the operation phase, the COD clearance is also in continuous rising, Guangzhou haydite post, Jiangxi haydite post, Shanxi activated-charcoal column and filtrate post of the present invention are 73.72%, 73.81%, 77.64% and 74.48% to the COD average removal rate, filtrate of the present invention is compared 3 kinds of filtrates of COD removal effect and other, a poor processing effect than Shanxi active carbon.
3. contrast to stream BAF SCOD treatment effect under four kinds of filtrates
Bioreactor for sewage treatment is one of main index of assessing reactor performance to organic place to go ability, four kinds of filler in aerated biologic filter pool of duration of test are during to the processing of SCOD, no matter be during biofilm, still during the stable operation, 4 filter posts all have fluctuation to the removal effect of sewage SCOD, more relatively stable to the removal effect of SCOD at operation phase 4 filter posts, Guangzhou haydite post, Jiangxi haydite post, Shanxi activated-charcoal column and filtrate post of the present invention are 57.92%, 56.67%, 60.51% and 58.38% to the SCOD average removal rate.
Analyze the reason of 4 filter posts to the removal effect fluctuation of sewage SCOD, may be in process of the test, because the graininess impurity in the continuous trap water of filter bed meeting, microorganism in the filter bed also can make by metabolic activity and self obtain propagation simultaneously, microorganism major part after the propagation also can be trapped within the filter bed as graininess impurity, increase along with filtration time, the impurity of holding back in the filter bed can get more and more, correspondingly the filter bed loss of flood peak increases, when the loss of flood peak is increased to a certain degree, just must carry out the periodicity backwash.Air-water backwashing is adopted in experiment, and back washing strength is: gas intensity 10L/ (m
2S), water intensity 10L/ (m
2S).Backwash: use gas flushing 3min earlier, make filler loosening, aging film comes off, and prevents caking; With about air-water flushing 5min, about last water flushing 5min, backwashing period is 3d again.Because backwash influences biomass and biomembranous activity on the filtrate, thereby cause the fluctuation of water outlet SCOD.
Under four kinds of filtrates to stream BAF NH
3The contrast of-N treatment effect
The nitrated denitrogenation ability of bioreactor for disposing polluted water also is one of leading indicator of estimating its treatment efficiency.BAF has denitrogenation ability preferably because its spatial gradient feature can realize the removal gradually of different pollutants.In the process of the test, when 4 reactor stable operation, can both reach good ammonia nitrogen removal effect, Guangzhou haydite post, Jiangxi haydite post, Shanxi activated-charcoal column and filtrate post of the present invention are respectively 81.48%, 83.52%, 85.05% and 83.63% to the ammonia nitrogen average removal rate, and visible filtrate of the present invention is very good as the BAF filtrate.
Three. brief summary: present embodiment can draw as drawing a conclusion by the application study to filtrate of the present invention:
1, the present invention adopts the Guangzhou haydite respectively, the Jiangxi haydite, Shanxi active carbon and filtrate of the present invention compare test, the filter post of filtrate of the present invention in stable operation stage to turbidity, COD, SCOD and ammonia nitrogen average removal rate are respectively 96.28%, 74.48%, 58.38% and 83.63%, it is feasible by the processing of sanitary sewage is found that filtrate of the present invention is used for BAF as biofilm carrier, and it is under identical service condition, to turbidity, the removal effect of COD and SCOD is better than 96.10% of Guangzhou haydite, 73.72% and 57.92%, 94.83% of Jiangxi haydite, 73.81% and 56.67%, the removal effect of ammonia nitrogen is better than the Guangzhou haydite 81.48% and Jiangxi haydite 83.52%.
2, because filter material surface of the present invention is coarse, voidage is high, loose volume weight and apparent particle density are moderate, can be used for BAF as carrier material, also can be used for the processing of intensive treatment, advanced treating and the micro-polluted water of sewage, and the reuse of sewage etc.
Claims (6)
1. the water treatment filtering material of making by mud, it is characterized in that it is that feedstock production by following composition forms: mud, clay, binding agent, the addition of described each raw material is respectively: clay comprises dewatered sludge quality 300～400%, binding agent accounts for 10～20% of clay quality; After each raw material mixed in described ratio, under 900～1200 ℃ of conditions, fire 15～35min, said dewatered sludge for mud is carried out drying, fragmentation and sieve after raw material.
2. the water treatment filtering material of being made by mud according to claim 1 is characterized in that the addition of described each raw material is respectively: clay comprises dewatered sludge quality 320%, binding agent accounts for 12% of clay quality; After each raw material mixed in described ratio, under 1000 ℃ of conditions, fire 30min.
3. the water treatment filtering material of being made by mud according to claim 1 is characterized in that the addition of described each raw material is respectively: clay comprises dewatered sludge quality 380%, binding agent accounts for 18% of clay quality; After each raw material mixed in described ratio, under 1150 ℃ of conditions, fire 20min.
4. according to claim 1, the 2 or 3 described water treatment filtering materials of making by mud, it is characterized in that described binding agent is a waterglass.
5. the preparation method of the water treatment filtering material of being made by mud is characterized in that concrete preparation process is as follows successively:
A. mud is carried out drying, fragmentation and screening;
B. add the clay that accounts for dewatered sludge quality 300～400%, the binding agent that accounts for clay quality 10～20%, mix the back extrusion modling with dewatered sludge;
C. sintering: earlier the moulding filtrate is carried out drying and preheating, its moisture is fully got rid of; Under 900～1200 ℃ of conditions, carry out roasting 15～35min then;
D. naturally cool to room temperature,
The extrusion modling process of described b step is: each raw material is fully mixed in the dry grinding container back well in described ratio weighing; mix after the end; raw material is poured in the mixer; add an amount of water; fully stir; the moisture content of compound is controlled between 10～20%, and extrusion modling on granulator then makes filtrate after the screening.
6. the preparation method of the water treatment filtering material of being made by mud according to claim 5 is characterized in that described binding agent is a waterglass.
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| CN101781014B (en) * | 2009-12-29 | 2011-06-01 | 山东大学 | Mixed type sludge ceramsite aerator and preparation method thereof |
| CN101773751B (en) * | 2009-12-30 | 2012-05-30 | 山东大学 | Lightweight cathode and anode water treatment filter material and preparation method thereof |
| CN103382098B (en) * | 2013-07-16 | 2015-05-27 | 广州市佳境水处理技术工程有限公司 | Light biological carrier for water treatment, and preparation method and application of light biological carrier |
| CN106241942A (en) * | 2016-10-21 | 2016-12-21 | 东华大学 | A kind of efficient renewable ceramic grain filter processes the method for MB waste water from dyestuff |
| CN112844303A (en) * | 2021-02-02 | 2021-05-28 | 苏州科技大学 | Water purification sludge/sodium silicate composite adsorbent, preparation method thereof and application thereof in treating ammonia nitrogen in water body |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0365295A (en) * | 1989-08-03 | 1991-03-20 | Kankyo Kogaku Kenkyusho:Kk | Filter material for treating waste water |
| JPH054012A (en) * | 1991-06-26 | 1993-01-14 | Minoru Igami | Filter medium made of paper sludge as raw material |
| JPH11221588A (en) * | 1998-02-05 | 1999-08-17 | Hokushin Kogyo Kk | Water purifying medium material and water purifying method |
| AU4021199A (en) * | 1998-07-21 | 2000-02-24 | Roy Tudor Brewer | Device and method for treating waste water |
| CN1380137A (en) * | 2002-03-14 | 2002-11-20 | 安徽工业大学华冶自动化工程公司 | Spherical porous light haydite for treating waste water and its production method |
-
2005
- 2005-11-28 CN CNB2005100105786A patent/CN100341601C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0365295A (en) * | 1989-08-03 | 1991-03-20 | Kankyo Kogaku Kenkyusho:Kk | Filter material for treating waste water |
| JPH054012A (en) * | 1991-06-26 | 1993-01-14 | Minoru Igami | Filter medium made of paper sludge as raw material |
| JPH11221588A (en) * | 1998-02-05 | 1999-08-17 | Hokushin Kogyo Kk | Water purifying medium material and water purifying method |
| AU4021199A (en) * | 1998-07-21 | 2000-02-24 | Roy Tudor Brewer | Device and method for treating waste water |
| CN1380137A (en) * | 2002-03-14 | 2002-11-20 | 安徽工业大学华冶自动化工程公司 | Spherical porous light haydite for treating waste water and its production method |
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