CN109354209B - Modified mineral-microorganism coupling water purification material and preparation method thereof - Google Patents
Modified mineral-microorganism coupling water purification material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified mineral-microorganism coupling water purification material and a preparation method thereof, wherein the water purification material is prepared from the following raw materials in parts by mass: 75-85 parts of a carrier material A component; 15-20 parts of a carrier material B component; 5-10 parts of a carrier material C component; 1-3 parts of a modifier; 0.1-0.3 part of microbial preparation. The water purifying material of the invention couples the mineral action and the microorganism action, and the modified carrier material carries Fe3+、Al3+The surface of the carrier material particles is positively charged, the negatively charged suspended matters in the polluted water body can be more effectively adsorbed, and after adsorption and precipitation, the organic pollutants in the polluted water body can provide energy for early growth of microorganisms; after the organic matter is completely digested, the valence state of the loaded high-valence cations is reduced under the action of microorganisms, and is accompanied by H+Can be utilized by microorganisms as a biological energy source, thereby promoting the mineralization process of the sediment and finally forming a steady-state foundation bed.
Description
Technical Field
The invention relates to a water purification material, in particular to a modified mineral-microorganism coupling water purification material and a preparation method thereof.
Background
With the gradual deepening of the domestic urbanization construction, especially the extensive engineering construction carried out at the end of the last century, the infrastructure, especially the drainage facility, of many cities is not perfect, and the inland river channels of the cities are the main channels for discharging pollutants and the catchment lakes are the main sites for collecting pollutants as the inland river channels of the cities pass through buildings such as urban residential areas, commercial buildings and the like. The long-term pollution accumulation leads to the continuous weakening of the environment bearing capacity of rivers and lakes, the gradual deterioration of the water body environment is serious, the urban image and the life and the body health of surrounding residents are influenced, and the smooth implementation of the sustainable development strategy of China is restricted.
The problem of treating eutrophication of water has attracted attention of many scholars at home and abroad. However, hydrological and hydraulic conditions of water systems such as rivers and lakes are complex and variable, and the pollution degree is diversified. The treatment mode of the polluted water body is replaced by a water diversion and water supplement mode, the work is more and more than half, and the water quality is difficult to maintain. At present, natural resources are advocated at home and abroad to treat environmental pollution, natural cheap modified clay mineral materials are added in situ, and the effect of microorganisms is coupled, so that the aim of reducing the content of nitrogen and phosphorus in the water body is fulfilled under the condition of not damaging the original river channel, the eutrophication hazard of the water body is removed, and the method is one of the main approaches for treating the polluted water body.
Chinese patent document CN 106335939 a provides "a method for producing a water purification material" which is a filterable water purification material using an inorganic adsorbent mainly composed of activated carbon and a polymer modifier mainly composed of polypropylene and spun into a fiber membrane, but has problems of easy clogging, difficulty in recycling, short life, and the like. Chinese patent document CN 104628123B provides a modified biological slag microbial carrier and a preparation method thereof, wherein carbon-containing biological slag is used as a raw material, and a carbon source self-supply type modified biological slag carrier is prepared by combined modification of inorganic acid and organic matter, but the biological slag has complex components and mineral forms and has larger potential safety hazard without rinsing. Chinese patent document CN 104857930A provides a production method of modified mineral materials special for black and odorous watercourses, and the used modifiers are calcium nitrate, lanthanum chloride, polymeric ferric chloride and polymeric aluminum chloride, so that the potential safety hazard is large. Chinese patent document CN 104276670A provides a sewage treatment agent containing natural minerals and a preparation method thereof, takes clinoptilolite, kaolinite, clay minerals with high cation exchange capacity, quartz sand, volcanic ash and meadow stone as main raw materials, mainly purifies water quality in an adsorption precipitation mode, and has the problems of water quality rebound treatment and difficulty in eliminating organic pollution in sewage. Chinese patent document CN 103043803 a provides a water purifying agent and a preparation method thereof, which uses polyacrylamide, polychloride, zeolite powder and bacillus subtilis as raw materials, wherein polyacrylamide, polyaluminium chloride/iron are used as common flocculants for sewage treatment plants, and zeolite powder is used as a carrier. In the using process, floccules formed by residual polyacrylamide and polychlorid float in a water body, and serious secondary pollution is caused without cleaning treatment.
Therefore, there is a need for a modified mineral-microorganism coupled water purification material and a preparation method thereof, wherein the modified mineral-microorganism coupled water purification material can gradually mineralize suspended substances (organic pollutants and suspended silt) in water into a stable matrix under the action of microorganisms and minerals after adsorption and precipitation.
Disclosure of Invention
The invention aims to solve the defects of the background technology and provide a modified mineral-microorganism coupling water purification material which can carry out biological decomposition after chemical flocculation on nutrients in water and a preparation method thereof.
The technical scheme of the invention is as follows: the modified mineral-microorganism coupling water purification material is characterized by being prepared from the following raw materials in parts by mass:
the component A of the carrier material is any one or combination of more of kaolinite, activated clay, clinoptilolite, diatomite, attapulgite, rectorite, medical stone, vermiculite and sepiolite;
the component B of the carrier material is any one or combination of clam shells, pearl shells, mussel shells, oyster shells and scallop shells;
the carrier material C comprises the following components: one or more of quartz, plagioclase feldspar, tourmaline, illite and dolomite;
the carrier material A component, the carrier material B component and the carrier material C component are powder with the granularity less than or equal to 200 meshes;
the modifier comprises sodium silicate, citric acid and polymeric aluminum ferric silicate, and the weight ratio of the sodium silicate to the polymeric aluminum ferric silicate is as follows: citric acid: 35-60% of polymeric aluminum ferric silicate: 5-15: 100, respectively;
the microbial preparation is bacillus subtilis.
Preferably, the material is prepared from the following raw materials in parts by mass:
further, the modifier comprises sodium silicate, citric acid and polymeric aluminum ferric silicate, and the modifier comprises the following components in percentage by mass: citric acid: 35-45% of polymeric aluminum ferric silicate: 5-10: 100.
the invention also provides a preparation method of the modified mineral-microorganism coupling water purification material, which is characterized in that the carrier material A component, the carrier material B component and the carrier material C component are mixed into a carrier material and then are subjected to acid cleaning, etching and roasting ablation treatment; mixing the treated carrier material and water into slurry, sequentially adding sodium silicate, citric acid and polymeric aluminum ferric silicate in a modifier in the form of aqueous solution to perform ion exchange reaction, cleaning the carrier material after the reaction is completed, and roasting again to obtain a modified carrier material; and mixing the modified carrier material with a microbial preparation to obtain the modified mineral-microbial coupling water purification material.
When the carrier material is subjected to acid pickling and etching in the scheme: can remove impurities among pores of the A component of the carrier materialThe adsorption performance of the carrier material A is improved, meanwhile, the component B of the carrier material can generate micro bubbles in the acid washing process, so that the separation of impurities is facilitated, and the component C of the carrier material can promote the sedimentation of an adsorbent; roasting and ablating to further remove impurities among pores; when sodium silicate, citric acid and polymeric aluminum ferric silicate are used for modification, Fe in the polymeric aluminum ferric silicate3+、Al3+Na to be attached to the surface of the mineral particles+、Ca2+And carrying out ion exchange reaction, adsorbing on the surfaces of the carrier particles, and changing the ion adsorption state of the surfaces of the carrier particles.
Preferably, the steps are as follows:
(1) pretreatment of support materials
Mixing 75-85 parts of a carrier material A component, 15-20 parts of a carrier material B component and 5-10 parts of a carrier material C component in parts by weight into a carrier material, placing the carrier material into a dilute sulfuric acid solution to vibrate for acid pickling and etching, placing the acid-pickled and etched carrier material into a rotary furnace to roast and ablate, wherein the roasting temperature is 500-900 ℃, and the roasting time is 1-2 hours;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry, sequentially adding a sodium silicate solution and a citric acid solution, and stirring for later use;
2.2) continuously adding a polymeric aluminum ferric silicate solution, quickly stirring for carrying out ion exchange reaction, and aging for 1-2 h; the modifier comprises 1-3 parts by weight of sodium silicate, citric acid and polymeric aluminum ferric silicate, and the mass ratio of the sodium silicate to the citric acid to the polymeric aluminum ferric silicate is 35-60: 5-15: 100, respectively;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again, wherein the roasting temperature is 400-700 ℃, the roasting time is 3-4 hours, and naturally cooling to obtain a powdery modified carrier material;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.1-0.3 part by mass of a microbial preparation to obtain the modified mineral-microbial coupling water purification material.
Further, in the step (1), the acid-washing etching is to mix the carrier material component A, the carrier material component B and the carrier material component C in parts by mass into a carrier material, and the carrier material is put into dilute sulfuric acid with the concentration of 1-2 mol/L to vibrate for 0.5-2 h.
Furthermore, in the step 2.1), the mass fraction of the sodium silicate solution is 15-30%, and the mass fraction of the citric acid solution is 1-2%.
Furthermore, the mass fraction of the polymeric aluminum ferric silicate solution in the step 2.2) is 6-10%.
Preferably, in the step (2.1), water is added to the carrier material to form a slurry with the mass fraction of 5-10%.
The invention has the beneficial effects that:
1. the component A of the carrier material used in the invention is a main object for modification treatment, and the component A mainly has the functions of adsorbing and precipitating pollutants, and the porous surface can increase the ion exchange rate; the component B mainly has the function of generating micro bubbles after the modifier is added, and is beneficial to washing and cleaning the pores of the component A; the component C mainly has the function of improving the density of the carrier and is beneficial to the generation of adsorption precipitation.
2. The modification mode of the invention is that sodium silicate, citric acid and polymeric aluminum ferric silicate are added step by step for modification, the sodium silicate mainly plays a role in dispersing and dissociating minerals, and creates conditions for ion exchange between crystals on the surface of the minerals and the polymeric aluminum ferric silicate. The citric acid mainly plays roles of complexing, adsorbing and catalyzing, and promotes the crystal on the surface of the mineral to perform ion exchange with the polymeric aluminum ferric silicate. High-valence Fe dissolved out by poly-ferric aluminum silicate under combined action of sodium silicate and citric acid3+、Al3+And Na crystallized on the surface of the carrier particles+/K+Ion exchange occurs, thereby altering the ion adsorption characteristics of the carrier particles.
3. The water purifying material of the invention couples the mineral action and the microorganism action, and the modified carrier material carries Fe3+、Al3+The surface of the carrier material particles is positively charged, the negatively charged suspended matters in the polluted water body can be more effectively adsorbed, and after adsorption and precipitation, the organic pollutants in the polluted water body can provide energy for early growth of microorganisms; and in microorganismsUnder the action of the catalyst, the valence state of the loaded high-valence cation is reduced and is accompanied by H+Can be utilized by microorganisms as a biological energy source, thereby promoting the mineralization process of the sediment and finally forming a steady-state foundation bed.
4. The carrier material is a natural mineral material, is harmless to natural water, has low price and wide source, and adsorbs and precipitates suspended matters (including suspended organic matters and fine-particle silt) in water through cations loaded on the surface of the carrier material; under the action of microorganisms, organic matters are digested, and the bottom mud is gradually mineralized to form a stable foundation bed, so that the method has the characteristics of high water purification effect, no rebound and capability of stably maintaining and restoring the water quality of the water body for a long time.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention
Detailed Description
The following specific examples further illustrate the invention in detail. The mass parts of the raw materials in the modified mineral-microorganism coupled water purification materials in examples 1 to 8 are shown in table 1, and the specific compositions of the carrier material A component, the carrier material B component and the carrier material C component are shown in table 2.
TABLE 1 examples 1-8 parts by weight of raw materials
| Example numbering | Support Material A | Support material B | Support material C | Modifying agent | Microbial preparation |
| 1 | 81 | 16 | 6 | 2 | 0.2 |
| 2 | 76 | 15 | 6 | 2.2 | 0.25 |
| 3 | 80 | 17 | 5 | 2.5 | 0.3 |
| 4 | 78 | 15 | 7 | 3 | 0.24 |
| 5 | 75 | 19 | 8 | 1 | 0.15 |
| 6 | 83 | 18 | 8 | 1.5 | 0.1 |
| 7 | 85 | 20 | 9 | 2.8 | 0.18 |
| 8 | 85 | 20 | 10 | 3 | 0.12 |
TABLE 2 EXAMPLES 1-8 specific compositions of support material A component, support material B component, support material C component
Example 1
As shown in fig. 1, the preparation method of the modified mineral-microorganism coupled water purification material provided by the invention comprises the following steps:
(1) pretreatment of support materials
Mixing 81 parts of a carrier material A component, 16 parts of a carrier material B component and 6 parts of a carrier material C component in parts by mass into a carrier material, wherein the particle sizes of the carrier material A component, the carrier material B component and the carrier material C component are less than or equal to 200 meshes, and the specific composition is shown in Table 2, placing the carrier material into 1mol/L dilute sulfuric acid solution, oscillating for 0.5h for acid-washing etching, placing the acid-washed and etched carrier material into a rotary furnace for roasting ablation, wherein the roasting temperature is 500 ℃, and the roasting time is 2 h;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry with the mass fraction of 5%, sequentially adding a sodium silicate solution with the mass fraction of 15% and a citric acid solution with the mass fraction of 1% into the slurry, and stirring for later use;
2.2) continuously adding a polymeric aluminum ferric silicate solution with the mass fraction of 6% and rapidly stirring for ion exchange reaction, and aging for 1-2 h;
2.3) soaking and washing the aged carrier material by using deionized water until no micro foam exists on the washing liquid surface, directly placing the carrier material into a rotary furnace for roasting again at the temperature of 600 ℃ for 3 hours, and naturally cooling to obtain a powdery modified carrier material;
the modifier consisting of the sodium silicate, the citric acid and the polymeric aluminum ferric silicate is 2 parts by weight; wherein the mass ratio of the sodium silicate to the citric acid to the polymerized aluminum silicate iron is 35: 5: 100, preparing a sodium silicate solution by powdery sodium silicate and water, wherein the using amount of the sodium silicate solution can be calculated according to the mass of the sodium silicate and the mass fraction of the solution, and the citric acid and the polymeric aluminum ferric silicate are the same;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.2 part by weight of microbial preparation (bacillus subtilis) to obtain the modified mineral-microorganism coupling water purification material.
In the embodiment, the carrier material A component, the carrier material B component and the carrier material C component can be obtained by directly purchasing powder with the particle size of less than or equal to 200 meshes or crushing and grinding the raw ore material to be less than or equal to 200 meshes, and the bacillus subtilis used in the embodiment is commercial bacillus subtilis dry powder.
Example 2
As shown in fig. 1, the preparation method of the modified mineral-microorganism coupled water purification material provided by the invention comprises the following steps:
(1) pretreatment of support materials
Mixing 76 parts of a carrier material A component, 15 parts of a carrier material B component and 6 parts of a carrier material C component in parts by mass into a carrier material, wherein the particle diameters of the carrier material A component, the carrier material B component and the carrier material C component are less than or equal to 200 meshes, and the specific composition is shown in Table 2, placing the carrier material into a 1.5mol/L dilute sulfuric acid solution, oscillating for 1h for acid-washing etching, placing the acid-washed and etched carrier material into a rotary furnace for roasting ablation, wherein the roasting temperature is 600 ℃, and the roasting time is 1.5 h;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry with the mass fraction of 6%, sequentially adding a sodium silicate solution with the mass fraction of 18% and a citric acid solution with the mass fraction of 1.5% into the slurry, and stirring for later use;
2.2) continuously adding a polymeric aluminum ferric silicate solution with the mass fraction of 7% and rapidly stirring for ion exchange reaction, and aging for 1-2 h;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again at the temperature of 700 ℃ for 4 hours, and naturally cooling to obtain a powdery modified carrier material;
the modifier consisting of the sodium silicate, the citric acid and the polymeric aluminum ferric silicate is 2.2 parts by weight; wherein the mass ratio of the sodium silicate to the citric acid to the polymerized aluminum silicate iron is 40: 10: 100, preparing a sodium silicate solution by powdery sodium silicate and water, wherein the using amount of the sodium silicate solution can be calculated according to the mass of the sodium silicate and the mass fraction of the solution, and the citric acid and the polymeric aluminum ferric silicate are the same;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.25 part by weight of microbial preparation (bacillus subtilis) to obtain the modified mineral-microorganism coupling water purification material.
Example 3
As shown in fig. 1, the preparation method of the modified mineral-microorganism coupled water purification material provided by the invention comprises the following steps:
(1) pretreatment of support materials
Mixing 80 parts of a carrier material A component, 17 parts of a carrier material B component and 5 parts of a carrier material C component by mass into a carrier material, wherein the particle sizes of the carrier material A, the carrier material B and the carrier material C are less than or equal to 200 meshes, and the specific composition is shown in Table 2, placing the carrier material into a 2mol/L dilute sulfuric acid solution, oscillating for 1.5 hours for acid cleaning and etching, placing the acid cleaned and etched carrier material into a rotary furnace for roasting and ablating, wherein the roasting temperature is 700 ℃, and the roasting time is 2 hours;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry with the mass fraction of 8%, sequentially adding a sodium silicate solution with the mass fraction of 25% and a citric acid solution with the mass fraction of 1.8% into the slurry, and stirring for later use;
2.2) continuously adding 8% of polymeric aluminum ferric silicate solution by mass fraction, rapidly stirring for ion exchange reaction, and aging for 1-2 h;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again at the temperature of 450 ℃ for 3.5 hours, and naturally cooling to obtain a powdery modified carrier material;
the modifier consisting of the sodium silicate, the citric acid and the polymeric aluminum ferric silicate is 2.5 parts by weight; wherein the mass ratio of the sodium silicate to the citric acid to the polymerized aluminum silicate iron is 35: 6: 100, preparing a sodium silicate solution by powdery sodium silicate and water, wherein the using amount of the sodium silicate solution can be calculated according to the mass of the sodium silicate and the mass fraction of the solution, and the citric acid and the polymeric aluminum ferric silicate are the same;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.3 part by weight of microbial preparation (bacillus subtilis) to obtain the modified mineral-microorganism coupling water purification material.
Example 4
As shown in fig. 1, the preparation method of the modified mineral-microorganism coupled water purification material provided by the invention comprises the following steps:
(1) pretreatment of support materials
Mixing 78 parts of a carrier material A component, 15 parts of a carrier material B component and 7 parts of a carrier material C component in parts by mass into a carrier material, wherein the particle sizes of the carrier material A component, the carrier material B component and the carrier material C component are less than or equal to 200 meshes, and the specific composition is shown in Table 2, placing the carrier material into a 1mol/L dilute sulfuric acid solution, oscillating for 2 hours for acid-washing etching, placing the acid-washed and etched carrier material into a rotary furnace for roasting ablation at the roasting temperature of 800 ℃ for 1 hour;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry with the mass fraction of 9%, sequentially adding a sodium silicate solution with the mass fraction of 30% and a citric acid solution with the mass fraction of 2% into the slurry, and stirring for later use;
2.2) continuously adding a polymeric aluminum ferric silicate solution with the mass fraction of 10% and rapidly stirring for ion exchange reaction, and aging for 1-2 h;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again at the temperature of 400 ℃ for 3 hours, and naturally cooling to obtain a powdery modified carrier material;
the modifier consisting of the sodium silicate, the citric acid and the polymeric aluminum ferric silicate is 3 parts by weight; wherein the mass ratio of the sodium silicate to the citric acid to the polymerized aluminum silicate iron is 45: 9: 100, preparing a sodium silicate solution by powdery sodium silicate and water, wherein the using amount of the sodium silicate solution can be calculated according to the mass of the sodium silicate and the mass fraction of the solution, and the citric acid and the polymeric aluminum ferric silicate are the same;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.24 part by weight of microbial preparation (bacillus subtilis) to obtain the modified mineral-microorganism coupling water purification material.
Example 5
As shown in fig. 1, the preparation method of the modified mineral-microorganism coupled water purification material provided by the invention comprises the following steps:
(1) pretreatment of support materials
Mixing 75 parts of a carrier material A component, 19 parts of a carrier material B component and 8 parts of a carrier material C component by mass into a carrier material, wherein the particle diameters of the carrier material A component, the carrier material B component and the carrier material C component are less than or equal to 200 meshes, and the specific composition is shown in Table 2, placing the carrier material into a 1.5mol/L dilute sulfuric acid solution, oscillating for 0.5h for acid-washing etching, placing the acid-washed and etched carrier material into a rotary furnace for roasting ablation, wherein the roasting temperature is 900 ℃, and the roasting time is 1.5 h;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry with the mass fraction of 10%, sequentially adding a sodium silicate solution with the mass fraction of 24% and a citric acid solution with the mass fraction of 1% into the slurry, and stirring for later use;
2.2) continuously adding a polymeric aluminum ferric silicate solution with the mass fraction of 6% and rapidly stirring for ion exchange reaction, and aging for 1-2 h;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again at the temperature of 500 ℃ for 4 hours, and naturally cooling to obtain a powdery modified carrier material;
the modifier consisting of the sodium silicate, the citric acid and the polymeric aluminum ferric silicate is 1 part by weight; wherein the mass ratio of the sodium silicate to the citric acid to the polymerized aluminum silicate iron is 60: 15: 100, preparing a sodium silicate solution by powdery sodium silicate and water, wherein the using amount of the sodium silicate solution can be calculated according to the mass of the sodium silicate and the mass fraction of the solution, and the citric acid and the polymeric aluminum ferric silicate are the same;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.15 part by weight of microbial preparation (bacillus subtilis) to obtain the modified mineral-microorganism coupling water purification material.
Example 6
As shown in fig. 1, the preparation method of the modified mineral-microorganism coupled water purification material provided by the invention comprises the following steps:
(1) pretreatment of support materials
83 parts of a carrier material A component, 18 parts of a carrier material B component and 8 parts of a carrier material C component are mixed into a carrier material according to the mass parts, the particle sizes of the carrier material A component, the carrier material B component and the carrier material C component are less than or equal to 200 meshes, the specific composition is shown in table 2, the carrier material is put into a 2mol/L dilute sulfuric acid solution to be vibrated for 1 hour for acid cleaning and etching, the carrier material after acid cleaning and etching is put into a rotary furnace to be roasted and ablated, the roasting temperature is 700 ℃, and the roasting time is 2 hours;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry with the mass fraction of 5%, sequentially adding a sodium silicate solution with the mass fraction of 16% and a citric acid solution with the mass fraction of 1.5% into the slurry, and stirring for later use;
2.2) continuously adding a polymeric aluminum ferric silicate solution with the mass fraction of 7% and rapidly stirring for ion exchange reaction, and aging for 1-2 h;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again at the temperature of 700 ℃ for 3.5 hours, and naturally cooling to obtain a powdery modified carrier material;
the modifier consisting of the sodium silicate, the citric acid and the polymeric aluminum ferric silicate is 1.5 parts by weight; wherein the mass ratio of the sodium silicate to the citric acid to the polymerized aluminum silicate iron is 50: 13: 100, preparing a sodium silicate solution by powdery sodium silicate and water, wherein the using amount of the sodium silicate solution can be calculated according to the mass of the sodium silicate and the mass fraction of the solution, and the citric acid and the polymeric aluminum ferric silicate are the same;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.1 part by weight of microbial preparation (bacillus subtilis) to obtain the modified mineral-microorganism coupling water purification material.
Example 7
As shown in fig. 1, the preparation method of the modified mineral-microorganism coupled water purification material provided by the invention comprises the following steps:
(1) pretreatment of support materials
Mixing 85 parts of a carrier material A component, 20 parts of a carrier material B component and 9 parts of a carrier material C component in parts by mass into a carrier material, wherein the particle diameters of the carrier material A component, the carrier material B component and the carrier material C component are less than or equal to 200 meshes, and the specific composition is shown in Table 2, placing the carrier material into a 1mol/L dilute sulfuric acid solution, oscillating for 1.5 hours for acid-washing etching, placing the acid-washed and etched carrier material into a rotary furnace for roasting ablation, wherein the roasting temperature is 800 ℃, and the roasting time is 1 hour;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry with the mass fraction of 7%, sequentially adding a sodium silicate solution with the mass fraction of 20% and a citric acid solution with the mass fraction of 1.2% into the slurry, and stirring for later use;
2.2) continuously adding 8% of polymeric aluminum ferric silicate solution by mass fraction, rapidly stirring for ion exchange reaction, and aging for 1-2 h;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again at the temperature of 450 ℃ for 3 hours, and naturally cooling to obtain a powdery modified carrier material;
the modifier consisting of the sodium silicate, the citric acid and the polymeric aluminum ferric silicate is 2.8 parts by weight; wherein the mass ratio of the sodium silicate to the citric acid to the polymerized aluminum silicate iron is 40: 8: 100, preparing a sodium silicate solution by powdery sodium silicate and water, wherein the using amount of the sodium silicate solution can be calculated according to the mass of the sodium silicate and the mass fraction of the solution, and the citric acid and the polymeric aluminum ferric silicate are the same;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.18 parts by weight of microbial preparation (bacillus subtilis) to obtain the modified mineral-microorganism coupling water purification material.
Example 8
As shown in fig. 1, the preparation method of the modified mineral-microorganism coupled water purification material provided by the invention comprises the following steps:
(1) pretreatment of support materials
Mixing 85 parts of a carrier material A component, 20 parts of a carrier material B component and 10 parts of a carrier material C component in parts by mass into a carrier material, wherein the particle sizes of the carrier material A component, the carrier material B component and the carrier material C component are less than or equal to 200 meshes, and the specific composition is shown in Table 2, placing the carrier material into a 2mol/L dilute sulfuric acid solution, oscillating for 2 hours for acid cleaning and etching, placing the acid cleaned and etched carrier material into a rotary furnace for roasting and ablation, wherein the roasting temperature is 900 ℃, and the roasting time is 2 hours;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry with the mass fraction of 8%, sequentially adding a sodium silicate solution with the mass fraction of 30% and a citric acid solution with the mass fraction of 2% into the slurry, and stirring for later use;
2.2) continuously adding a polymeric aluminum ferric silicate solution with the mass fraction of 10% and rapidly stirring for ion exchange reaction, and aging for 1-2 h;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again at the temperature of 400 ℃ for 4 hours, and naturally cooling to obtain a powdery modified carrier material;
the modifier consisting of the sodium silicate, the citric acid and the polymeric aluminum ferric silicate is 3 parts by weight; wherein the mass ratio of the sodium silicate to the citric acid to the polymerized aluminum silicate iron is 60: 15: 100, preparing a sodium silicate solution by powdery sodium silicate and water, wherein the using amount of the sodium silicate solution can be calculated according to the mass of the sodium silicate and the mass fraction of the solution, and the citric acid and the polymeric aluminum ferric silicate are the same;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.12 part by weight of microbial preparation (bacillus subtilis) to obtain the modified mineral-microorganism coupling water purification material.
Performance testing
The water purification materials prepared in the above examples 1-8 are prepared into water solution according to the concentration of 300mg/L, and are added into each cubic polluted water body according to the proportion of 1000g after being purified and placed for 4 hours, and then are sprayed on the surface of the polluted water body. After 30 days, a water sample is taken to detect the change condition of the water quality index, which is specifically shown in Table 3.
TABLE 3 Water quality index test results
As can be seen from Table 3, the water purification material prepared by the invention has the advantages that the removal rate of TN in raw water reaches 88.75-97.58%, the removal rate of TP in raw water reaches 75.00-97.37%, the removal rate of BOD reaches 73.22-89.16%, the removal rate of COD in raw water reaches 75.73-88.00%, and the removal rate of SS in raw water reaches 90.21-94.64%, and the results show that the water purification material has good treatment effects on the sedimentation and decomposition of suspended matters in raw water.
Claims (6)
1. The modified mineral-microorganism coupling water purification material is characterized by being prepared from the following raw materials in parts by mass:
the component A of the carrier material is any one or combination of more of kaolinite, activated clay, clinoptilolite, diatomite, attapulgite, rectorite, medical stone, vermiculite and sepiolite;
the component B of the carrier material is any one or combination of clam shells, pearl shells, mussel shells, oyster shells and scallop shells;
the carrier material C component is any one or combination of quartz, microcline feldspar, tourmaline, illite and dolomite;
the carrier material A component, the carrier material B component and the carrier material C component are powder with the granularity less than or equal to 200 meshes;
the modifier comprises sodium silicate, citric acid and polymeric aluminum ferric silicate, and the weight ratio of the sodium silicate to the polymeric aluminum ferric silicate is as follows: citric acid: 35-45% of polymeric aluminum ferric silicate: 5-10: 100, respectively;
the microbial preparation is bacillus subtilis;
the preparation method of the modified mineral-microorganism coupling water purification material comprises the following steps:
(1) pretreatment of support materials
Mixing 75-85 parts of a carrier material A component, 15-20 parts of a carrier material B component and 5-10 parts of a carrier material C component in parts by weight into a carrier material, placing the carrier material into a dilute sulfuric acid solution to vibrate for acid pickling and etching, placing the acid-pickled and etched carrier material into a rotary furnace to roast and ablate, wherein the roasting temperature is 500-900 ℃, and the roasting time is 1-2 hours;
(2) modification treatment of support materials
2.1) adding water into the carrier material treated in the step (1) to form slurry, sequentially adding a sodium silicate solution and a citric acid solution, and stirring for later use;
2.2) continuously adding a polymeric aluminum ferric silicate solution, quickly stirring for carrying out ion exchange reaction, and aging for 1-2 h; the modifier comprises 1-3 parts by weight of sodium silicate, citric acid and polymeric aluminum ferric silicate, and the mass ratio of the sodium silicate to the citric acid to the polymeric aluminum ferric silicate is 35-45: 5-10: 100, respectively;
2.3) soaking and washing the aged carrier material by using deionized water, placing the carrier material into a rotary furnace for roasting again, wherein the roasting temperature is 400-700 ℃, the roasting time is 3-4 hours, and naturally cooling to obtain a powdery modified carrier material;
(3) microbial compounding
And (3) mixing the powdery modified carrier material obtained in the step (2) with 0.1-0.3 part by mass of a microbial preparation to obtain the modified mineral-microbial coupling water purification material.
2. The modified mineral-microorganism coupling water purification material of claim 1, which is prepared from the following raw materials in parts by mass:
3. the preparation method of the modified mineral-microorganism coupled water purification material as claimed in claim 1, wherein the acid-washing etching in the step (1) is to mix the carrier material A component, the carrier material B component and the carrier material C component in parts by mass into a carrier material, and to shake the carrier material in dilute sulfuric acid with a concentration of 1-2 mol/L for 0.5-2 h.
4. The preparation method of the modified mineral-microorganism coupled water purification material as claimed in claim 1, wherein the mass fraction of the sodium silicate solution in the step 2.1) is 15-30%, and the mass fraction of the citric acid solution is 1-2%.
5. The preparation method of the modified mineral-microorganism coupled water purification material as claimed in claim 1, wherein the mass fraction of the polymeric aluminum ferric silicate solution in the step 2.2) is 6-10%.
6. The preparation method of the modified mineral-microorganism coupling water purification material as claimed in claim 1, wherein water is added into the carrier material in the step 2.1) to form slurry with the mass fraction of 5-10%.
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| CN108264152A (en) * | 2018-04-04 | 2018-07-10 | 郦璋 | A kind of preparation method containing a variety of microbial inoculum biologic packing materials |
| CN108569731A (en) * | 2018-04-27 | 2018-09-25 | 佛山市日日圣科技有限公司 | A kind of compound water-purifying material preparation method |
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| CN108264152A (en) * | 2018-04-04 | 2018-07-10 | 郦璋 | A kind of preparation method containing a variety of microbial inoculum biologic packing materials |
| CN108569731A (en) * | 2018-04-27 | 2018-09-25 | 佛山市日日圣科技有限公司 | A kind of compound water-purifying material preparation method |
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