CN109020600A - A kind of ecology pearl and preparation method thereof - Google Patents
A kind of ecology pearl and preparation method thereof Download PDFInfo
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- CN109020600A CN109020600A CN201811020399.4A CN201811020399A CN109020600A CN 109020600 A CN109020600 A CN 109020600A CN 201811020399 A CN201811020399 A CN 201811020399A CN 109020600 A CN109020600 A CN 109020600A
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- clay
- pearl
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- shale
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004927 clay Substances 0.000 claims abstract description 69
- 239000000654 additive Substances 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 9
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 9
- 239000011686 zinc sulphate Substances 0.000 claims abstract description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 244000005700 microbiome Species 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002366 mineral element Substances 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000011049 pearl Substances 0.000 abstract 3
- 239000000919 ceramic Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 210000001161 mammalian embryo Anatomy 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses a kind of ecological pearls and preparation method thereof, a kind of ecology pearl, it is sintered, is matched are as follows: 30-40% clay, 22-45% clay, 10-20% shale, 8-18% mullite, 0.38-0.85% additive by clay, clay, shale, mullite and additive；Additive is by 0.3-0.6%Ca (OH)2, 0.05-0.1%FeSO4, 0.01-0.05%CuSO4, 0.01-0.05%ZnSO4, 0.01-0.05%MnSO4Composition.The characteristic that the present invention utilizes clay high temperature sharply to shrink, so that forming the ecological pearl of skeleton structure after sintering, intensity is high, and form large aperture hole, it is extended through between hole, the adaptability to water impact load can be improved, accelerate the degradation of organic pollutant, mineral element can be provided for microorganism simultaneously, increase the value volume and range of product of microorganism.
Description
Technical field
The invention belongs to biological filtering material for waste water treatment preparation technical fields, and in particular to a kind of ecology pearl and its preparation side
Method.
Background technique
Filler is biofilm carrier, is the key component of biofilm treatment process, and the quality of filler directly affects biology
The effect of processing, biological nutrition haydite are a kind of novel biofilm carrier filtrates, have light, large specific surface area, adsorption energy
The advantages that power is strong.Existing haydite can be divided into calcination type and non-two class of calcination type, and wherein calcination type can be divided into again burns swollen type and sintering
Two kinds of type.In a certain temperature conditions, haydite embryo material, which can soften, generates viscosity appropriate, can produce plasticity under external force
Deformation can generate certain gas inside haydite, promote its dilatancy while embryo material softening.The dilatancy of haydite is
The two is coefficient as a result, if embryo material surface viscosity is excessive, and liquid phase, which escapes bound gas, leads to haydite swelling performance not
It is enough, if the expansive force of gas is excessive, it will lead to gas and break through haydite surface formation connectivity hole to destroy haydite structure.
It is in honeycomb that existing biological ceramic particle is usually internal, and porosity is high, and intensity is low, and aperture is small, does not connect between hole
It is logical, it is poor to the adaptability of water impact load.In addition, existing biological ceramic particle mineral element is deficient, cause biofilm biomass thin easily
It falls off, the problems such as biomass is few, biological species are single.
Summary of the invention
It is an object of the invention to: it is low for above-mentioned existing biological ceramic particle intensity, and because aperture is small, does not connect between hole
When leading to and leading to it as biological filtering material for waste water treatment, to the problem of the adaptability difference of water impact load, the present invention is provided
A kind of ecology pearl and preparation method thereof, which is skeleton structure, and aperture is big, extends through between hole, and can be micro-
Biology provides mineral element and either there is biggish difference in structure or performance compared with existing biological ceramic particle, because
This, applicant is defined as " ecological pearl ", can be used as a kind of new biological filtering material for waste water treatment, to replace biological ceramic particle.
The technical solution adopted by the invention is as follows:
A kind of ecology pearl, is sintered by clay, clay, shale, mullite and additive.
Clay is soil seldom containing the grains of sand, having stickiness, and moisture is not easy to pass therethrough and have preferable plasticity, stick
Soil is mixed by multi mineral, the fusing point that do not fix, but is gradually softened within the scope of certain temperature.Clay exists
During heating and calcining, eutectic substance starts to melt, and liquid phase occurs and gradually increases, and is filled between solid particle,
Due to the effect of liquid phase surface tension, so that no cofusing particle is further drawn close, causing the contraction of volume sharply, the porosity declines,
Density improves, and when temperature continues to increase, contraction will constantly increase to maximum value, and the porosity minimizes value, and density reaches most
Big value, clay are fully sintered.
The present invention is equipped with clay using clay as primary raw material, and additive selection is generated the inorganic salts of gas by thermal decomposition,
In the subsequent sintering process, clay is sharply shunk, and the porosity is reduced to minimum value, the gas that will be generated to additive by thermal decomposition
Obstruction is generated, so that hole tends to be formed in clay, also, since clay is well bonded clay tool, so that
It when clay is shunk, drives clay mobile, forms big hole, in this way in the ecological pearl of sintering formation, clay is as skeleton, hole
Rate is very low, and aperture is small, significantly improves intensity, and clay is then filled between skeleton, and the porosity in clay is high, aperture
Greatly, it is extended through between hole, when being used as biological filtering material for waste water treatment, the adaptability to water impact load can be improved,
And be conducive to sewage, oxygen, come into full contact between biomembrane, accelerate the degradation of organic pollutant.In addition, being also added in formula
Shale and mullite, shale are that the molecule formed is hardened by clay substance, are one kind of claystone, are mainly less than by partial size
The thin particulate matter of 0.0039mm forms and contains the sedimentary rock of a large amount of clay minerals, these thin particulate matters are evenly distributed on pottery
In soil and clay, intensity is further increased, mullite is a kind of good refractory material, temperature tolerance is improved, so as in high temperature
Lower sintering.
A kind of ecology pearl, by mass percentage, the proportion of clay, clay, shale, mullite and additive are as follows: 30-
40% clay, 22-45% clay, 10-20% shale, 8-18% mullite, 0.38-0.85% additive；The additive by
0.3-0.6%Ca (OH)2, 0.05-0.1%FeSO4, 0.01-0.05%CuSO4, 0.01-0.05%ZnSO4, 0.01-0.05%
MnSO4Composition.
The FeSO that the present invention adds4、CuSO4、ZnSO4、MnSO4It can be thermally decomposed in high-temperature calcination, generate gas,
Such as iron oxide, sulfur dioxide and sulfur trioxide are generated after ferrous sulfate decomposition, copper sulphate generates copper oxide and three oxygen after decomposing
Change sulphur, these gases make to form hole in clay in sintering, and FeSO4、CuSO4、ZnSO4、MnSO4Deng shape after being thermally decomposed
At oxide can provide mineral element for microorganism, provide stable environment for the growth of microorganism, increase the number of microorganism
Amount and type, form microbial abundant, constitute microbial ecosystem, are conducive to the pollutant in water body and are decomposed and only
Change.
The oxide that additive of the present invention generates after being thermally decomposed can also reduce fusing point, increase viscosity, above-mentioned by selecting
Proportion, it is ensured that embryo material surface viscosity is moderate, avoids viscosity excessive and bound gas escapes or viscosity is too small, leads to ecology
Bead surface forms connectivity hole and destroys ecological pearl structure.
A kind of preparation method of ecology pearl, comprising the following steps:
(1) it by the drying of clay, clay, shale and mullite, broken, screening, is then mixed together with additive uniformly；
(2) mixture pelleting in step (1) is formed and is dried, moisture control 5-12%；
(3) particle in step (2) is sintered, it is cooling up to the ecological pearl.
Further, in step (2), grain diameter 10-30mm.
Further, in step (3), sintering process are as follows: in 300-500 DEG C of preheating 10-30min, then in 1100-1300
DEG C roasting 10-15min.
Further, in step (3), the ecological pearl is obtained after sintering in a manner of natural cooling.
Further, in step (3), the partial size of ecological pearl is 12-35mm.
Existing clay haydite is mainly sintering-expanded haydite, and big volume expansion can occur after burning is swollen, and porosity is high, and closes not
Connection, clay of the invention is sintered at 1100-1300 DEG C, does not occur big volume expansion, internal only a small amount of stomata, with
After clay cooperation, mainly as skeleton structure, the intensity of ecological pearl is improved.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. the present invention is equipped with clay using clay as primary raw material, the characteristic sharply shunk using clay high temperature, so that sintering
The ecological pearl of skeleton structure is formed afterwards, intensity is high, meanwhile, fine grained shale is evenly distributed in clay and clay, is further mentioned
The intensity of ecological pearl；
2. filling clay between skeleton of the present invention, hindered since clay forms gas, and clay shrinks and clay is driven to move
It is dynamic, thus, the porosity in clay is high, and aperture is big, extends through between hole, can when being used as biological filtering material for waste water treatment
It improves to the adaptability of water impact load, and is conducive to sewage, oxygen, comes into full contact between biomembrane, accelerate organic dirt
Contaminate the degradation of object；
3. FeSO of the present invention4、CuSO4、ZnSO4、MnSO4It can be provided Deng the oxide formed after being thermally decomposed for microorganism
Mineral element provides stable environment for the growth of microorganism, increases the value volume and range of product of microorganism, form microorganism abundant
Phase constitutes microbial ecosystem, is conducive to the pollutant in water body and is decomposed and purifies；
4. the oxide after additive of the present invention is thermally decomposed can also reduce fusing point, increase viscosity, guarantees that embryo material surface is viscous
It spends moderate, avoids viscosity excessive and bound gas escapes or viscosity is too small, ecological bead surface is caused to form connectivity hole and break
Bad ecology pearl structure.
Detailed description of the invention
Fig. 1 is ecological pearl SEM figure prepared by the embodiment of the present invention 3；
Fig. 2 is biological ceramic particle SEM figure.
Specific embodiment
All features disclosed in this specification can be with any other than mutually exclusive feature and/or step
Mode combines.
Embodiment 1
A kind of ecology pearl, by mass percentage, the proportion of clay, clay, shale, mullite and additive are as follows: 40%
Clay, 26% clay, 15.3% shale, 18% mullite, 0.7% additive；The additive is by 0.5%Ca (OH)2、
0.1%FeSO4, 0.03%CuSO4, 0.05%ZnSO4, 0.02%MnSO4Composition.
A kind of preparation method of ecology pearl, comprising the following steps:
(1) it by the drying of clay, clay, shale and mullite, broken, screening, is then mixed together with additive uniformly；
(2) mixture pelleting in step (1) is formed and is dried, grain diameter 10-30mm, moisture control 5-
12%；
(3) particle in step (2) is in 450 DEG C of preheating 15min, and then in 1150 DEG C of roasting 15min, natural cooling to obtain the final product
The ecology pearl, partial size 12-35mm.
Embodiment 2
A kind of ecology pearl, by mass percentage, the proportion of clay, clay, shale, mullite and additive are as follows:
32.5% clay, 45% clay, 12% shale, 10% mullite, 0.5% additive；Additive is by 0.3%Ca (OH)2、
0.05%FeSO4, 0.05%CuSO4, 0.05%ZnSO4, 0.05%MnSO4Composition.
A kind of preparation method of ecology pearl, comprising the following steps:
(1) it by the drying of clay, clay, shale and mullite, broken, screening, is then mixed together with additive uniformly；
(2) mixture pelleting in step (1) is formed and is dried, grain diameter 10-30mm, moisture control 5-
12%；
(3) particle in step (2) is in 350 DEG C of preheating 20min, and then in 1200 DEG C of roasting 13min, natural cooling to obtain the final product
The ecology pearl, partial size 12-35mm.
Embodiment 3
A kind of ecology pearl, by mass percentage, the proportion of clay, clay, shale, mullite and additive are as follows:
35.6% clay, 32% clay, 18% shale, 14% mullite, 0.4% additive；Additive is by 0.3%Ca (OH)2、
0.05%FeSO4, 0.02%CuSO4, 0.02%ZnSO4, 0.01%MnSO4Composition.
A kind of preparation method of ecology pearl, comprising the following steps:
(1) it by the drying of clay, clay, shale and mullite, broken, screening, is then mixed together with additive uniformly；
(2) mixture pelleting in step (1) is formed and is dried, grain diameter 10-30mm, moisture control 5-
12%；
(3) particle in step (2) is in 300 DEG C of preheating 30min, and then in 1250 DEG C of roasting 10min, natural cooling to obtain the final product
The ecology pearl, partial size 12-35mm.
Experimental example
The ecological pearl for taking biological ceramic particle and embodiment 3 to prepare carries out Mechanics Performance Testing, ecological pearl and biological ceramic particle respectively
Respectively take three samples, number is respectively 1#, 2#, 3#, the results are shown in Table 1, it can be seen that the mean compressive strength of ecological pearl is
6.9Mpa, the mean compressive strength of biological ceramic particle are 3.57Mpa, 90% or more performance boost.Specific surface is carried out to said sample
Product measurement, the results are shown in Table 2, it can be seen that the specific surface area of ecological pearl is obviously improved.
It takes 1# biological ceramic particle and 1# ecology pearl to carry out microscopic appearance observation, can be seen that ecology of the invention from Fig. 1 and Fig. 2
Pearl is integrally in skeleton structure, and porosity is high, and aperture is big, is extended through between hole, can when being used as biological filtering material for waste water treatment
It improves to the adaptability of water impact load, and is conducive to sewage, oxygen, comes into full contact between biomembrane, accelerate organic dirt
Contaminate the degradation of object.
1 mechanical experimental results of table
The specific surface area of table 2 ecological pearl and biological ceramic particle
It is as described above the embodiment of the present invention.The present invention is not limited to the above-described embodiments, anyone should learn that
The structure change made under the inspiration of the present invention, the technical schemes that are same or similar to the present invention each fall within this
Within the protection scope of invention.
Claims (7)
1. a kind of ecology pearl, which is characterized in that be sintered by clay, clay, shale, mullite and additive.
2. a kind of ecological pearl according to claim 1, which is characterized in that by mass percentage, the clay, clay,
The proportion of shale, mullite and additive are as follows: 30-40% clay, 22-45% clay, 10-20% shale, 8-18% mullite,
0.38-0.85% additive；
The additive is by 0.3-0.6%Ca (OH)2, 0.05-0.1%FeSO4, 0.01-0.05%CuSO4, 0.01-0.05%
ZnSO4, 0.01-0.05%MnSO4Composition.
3. a kind of preparation method of ecological pearl as claimed in claim 1 or 2, which comprises the following steps:
(1) it by the drying of clay, clay, shale and mullite, broken, screening, is then mixed together with additive uniformly；
(2) mixture pelleting in step (1) is formed and is dried, moisture control 5-12%；
(3) particle in step (2) is sintered, it is cooling up to the ecological pearl.
4. a kind of preparation method of ecological pearl according to claim 3, which is characterized in that in the step (2), grain diameter
For 10-30mm.
5. a kind of preparation method of ecological pearl according to claim 3, which is characterized in that in the step (3), sintering process
Are as follows: in 300-500 DEG C of preheating 10-30min, then in 1100-1300 DEG C of roasting 10-15min.
6. a kind of preparation method of ecological pearl according to claim 3, which is characterized in that in the step (3), after sintering with
The mode of natural cooling obtains the ecological pearl.
7. a kind of preparation method of ecological pearl according to claim 3, which is characterized in that in the step (3), ecological pearl
Partial size is 12-35mm.
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|---|---|---|---|---|
| EP0742416A1 (en) * | 1995-05-11 | 1996-11-13 | Asahi Glass Company Ltd. | Spray operation method for monolithic refractories |
| CN101186485A (en) * | 2007-12-14 | 2008-05-28 | 重庆大业污泥处理有限公司 | Sewage sludge shale ceramsite and preparation method thereof |
| CN102575515A (en) * | 2009-07-25 | 2012-07-11 | 美国瑞博公司 | Composition and method for producing an ultra-lightweight ceramic proppant |
| CN102125786A (en) * | 2011-02-24 | 2011-07-20 | 南昌大学 | Method for preparing porous ceramsite filter material by using lepidolite extracted lithium slag |
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Application publication date: 20181218 Assignee: Shenzhen Haide Environmental Protection Technology Co., Ltd. Assignor: SHENZHEN OASIS ECOLOGICAL TECHNOLOGY CO., LTD. Contract record no.: X2020440020001 Denomination of invention: Ecological bead and preparation method thereof License type: Exclusive License Record date: 20200106 |
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