CN110835172A - Method for preparing eutrophic water body remediation material by using decolored waste soil - Google Patents
Method for preparing eutrophic water body remediation material by using decolored waste soil Download PDFInfo
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- CN110835172A CN110835172A CN201911231624.3A CN201911231624A CN110835172A CN 110835172 A CN110835172 A CN 110835172A CN 201911231624 A CN201911231624 A CN 201911231624A CN 110835172 A CN110835172 A CN 110835172A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/347—Use of yeasts or fungi
Abstract
The invention discloses a method for preparing a eutrophic water body restoration material by using decolored waste soil, which comprises the steps of feeding the decolored attapulgite waste soil into a rotary kiln, carbonizing at 300-600 ℃ for 1-3 h under nitrogen atmosphere, and cooling to obtain carbonized decolored attapulgite waste soil; and uniformly mixing carbonized and decolored attapulgite waste soil and composite bacteria, culturing at 28-30 ℃ for 6-24 h, and air-drying and granulating to obtain the eutrophic water body remediation material of the attapulgite carbonized waste soil-biological bacteria denitrifying bacteria coupling system. The water body repairing material prepared by the invention has good adsorption performance on nitrogen and phosphorus molecules in wastewater; the water body repairing material for adsorbing nitrogen and phosphorus is used as a nutrient bank for soil environment repairing, and has good slow-release nutrient performance. Therefore, the method realizes treatment of the eutrophic wastewater, realizes effective utilization of nitrogen and phosphorus nutrients, obtains the repairing material, and has wide application prospects in the aspects of water body purification, soil environment repair and the like.
Description
Technical Field
The invention relates to a preparation method of a eutrophic water body restoration material, in particular to a method for preparing a eutrophic water body restoration material by using decolored attapulgite waste soil, and belongs to the technical field of resource recycling of solid wastes and environment restoration materials.
Technical Field
Eutrophication of water is one of the more serious problems in the field of water pollution in the world at present. In the river with formed eutrophication, a repair strategy can be adopted, which mainly comprises three methods, namely a physical method, a chemical method and a biological method. The biological method is one of the economic and effective methods for removing nitrogen and phosphorus at present. However, the efficiency is lower compared with the adsorption method because the metabolism period of the biological bacteria is longer, the conditions required to be controlled by the biological reaction are different, the concentration of nitrogen and phosphorus needs to be in the acceptable range of microorganisms, and the like. The adsorption technology mainly utilizes the special surface structure and porosity of the adsorbent to adsorb and remove nitrate and phosphate in water, and in recent years, a plurality of low-cost adsorbent materials are widely applied to the removal of nitrate and phosphate.
Attapulgite is a layered chain type water-rich magnesium-rich aluminosilicate clay mineral with a unique nano fibrous structure. The attapulgite has a good purification function on water due to the existence of special channels and active centers. For example, CN 101973615A and CN 103691404A disclose attapulgite water purification materials for purifying drinking water and aquaculture water respectively, and the modified attapulgite can effectively remove the contents of ammonia nitrogen, phosphorus salt, algal toxins, heavy metals and the like in the drinking water. Attapulgite is widely applied in oil product decolorization, but the decolorized waste soil is not effectively treated.
Biochar can be used as a redox mediator and shows excellent mediated reduction capability in the electron transfer process of chemical and biological reduction pollutants, CN105289494A, CN104667875A and ZL201510097602.8 respectively disclose that active carbon is loaded on attapulgite rod crystals in situ by adopting different raw materials and modes to prepare a biochar/attapulgite composite material, the adsorption performance of attapulgite and carbon materials is fully utilized, the adsorption capability of heavy metals, organic molecules and the like is effectively improved, but the material processing capacity is limited, and the remediation of a eutrophic environment can not be continuously and effectively carried out.
In recent years, solidified microbial technology is adopted to provide a good growing environment for slow-growing bacteria, so that the concentration of the bacteria in a treatment device is increased, and the wastewater treatment efficiency is improved. If polyvinyl alcohol, sodium alginate, activated carbon and the like are used as curing carrier materials to prepare bacillus-based curing microorganisms for treating large-scale pig farm wastewater, the removal rates of COD, ammonia nitrogen and total phosphorus of the wastewater can respectively reach 83.1%, 88.6% and 45% after 21d treatment, and the final COD and ammonia nitrogen concentrations of effluent are 292.5 mg.L-1And 77.9 mg. L-1Meeting the discharge value of COD and ammonia nitrogen in the wastewater discharge Standard for livestock and poultry Breeding (GB 18596-2001) (Wudamei, Yemeifeng, Wufeilong, etc.. Experimental research on the treatment of wastewater in large-scale pig farms by immobilized microorganisms [ J]. Energy and environment, 2017, (01): 14-15.). Therefore, the decolorized attapulgite waste soil is carbonized and then used as a carrier for fixing microbial bacteria, eutrophic water body purification is carried out, and the nutritional soil remediation material is prepared after nitrogen and phosphorus are adsorbed, so that the treatment of the eutrophic water body is realized, and the utilization rate of the nitrogen and phosphorus can be effectively improved.
Disclosure of Invention
The invention aims to provide a method for preparing a eutrophic water body remediation material by using decolored waste soil.
Preparation of eutrophic water body repairing material
Feeding the decolorized attapulgite waste soil into a rotary kiln, carbonizing at 300-600 ℃ for 1-3 h under the atmosphere of nitrogen, and cooling to obtain carbonized decolorized attapulgite waste soil; and uniformly mixing carbonized and decolored attapulgite waste soil and composite bacteria according to the weight ratio of 100: 1-150: 1, culturing for 6-24 h at 28-30 ℃, and air-drying and granulating (the particle size is controlled to be 1-5 mm) to obtain the eutrophic water body remediation material of the attapulgite carbonized waste soil-biological bacteria denitrifying bacteria coupling system.
The attapulgite decolored waste soil is attapulgite waste soil obtained by decoloring soybean oil, palm oil and waste engine oil, and the oil content of the attapulgite waste soil is not less than 10%.
The compound bacteria are at least two of nitrobacteria, bacillus subtilis, bacillus licheniformis, saccharomycetes, denitrifying bacteria, lactic acid bacteria and pseudomonas. In the compound bacteria, all the strains can be compounded according to any proportion.
FIG. 1 is an infrared spectrum of the eutrophic water body remediation material prepared by the invention. The attapulgite rod crystals are loaded with biochar, the biochar endows the surface functional groups with most oxygen-containing functional groups including-OH, -COOH and the like, and the oxygen-containing functional groups generate surface negative charges, so that the biochar has more active sites, and the synergistic and complementary effects are achieved. The infrared spectrum has 2849 cm-1And 2925cm-1Characteristic peak (CH)2C-H stretching vibration of) and 1648cm-1The characteristic peak (acylamino-CONH-), which shows that the microorganism is successfully fixed in the waste soil for carbonization and decoloration, and the waste soil for carbonization and decoloration can provide an effective 'bacteria niche' for biological bacteria.
Secondly, the capability of the water body repairing material in removing total nitrogen and total phosphorus in the eutrophic wastewater
FIG. 2 shows the simulation of eutrophic nitrogen-containing wastewater (nitrogen content 50 mg. multidot.L) by using eutrophic water restoration material, biological bacteria and carbonized and decolored waste soil-1) Medium total nitrogen removal profile. As can be seen from FIG. 2, the carbonized and decolorized waste soil/microorganism bacterium has the best effect of removing total nitrogen in the wastewater and has good denitrification effect, and the total nitrogen removal amount is 43.5 mg.L-1。
FIG. 3 shows the eutrophic water restoration material pair simulating eutrophic phosphorus-containing wastewater (phosphorus content 50 mg. L)-1) Adsorption kinetics curve of total phosphorus in (1). As can be seen from fig. 3, the amount of phosphorus adsorbed by the repair material gradually increases with time; after 48h reaction, the adsorption capacity tends to be stable, the adsorption balance is achieved, and the phosphorus adsorption capacity is 34.09 mg L-1。
Experiments also show that the removal rate of ammonia nitrogen and phosphate radical in the aquaculture wastewater by the water body repairing material prepared by the invention respectively reaches 87% and 68%.
The principle of the invention is as follows: the structural change of the decolored attapulgite waste soil inevitably influences the number of Si-OH, -COOH and other groups on the surface in the heat treatment carbonization process, and the attapulgite waste soil is subjected to moderate heat treatment to form a load charcoal material, so that the adsorption performance of the attapulgite can be further activated; on the other hand, more oxygen-containing functional groups are endowed on the surface of the charcoal, so that the synergistic and complementary effects are achieved, the adsorption performance of the charcoal on nitrogen and phosphorus molecules is effectively improved, and the slow-release and controlled-release performance of the attapulgite on nutrient components in soil is remarkably improved. In the process of fixing microorganisms by using the carbonized and decolored waste soil, on one hand, the purification material prepared from the carbonized and decolored waste soil and NO can be increased3 -The specific surface area of the contact of-N, on the other hand, the biological bacteria denitrification process mainly takes nitrification and denitrification, and the biochar provides an electron donor for biological denitrification to improve NO3 --N removal effect. Particularly, as the microorganisms are adsorbed on the surface of the carbonized and decolored waste soil, a microorganism attachment film is formed, the metabolic activity of the microorganisms is ensured, and the removal rate of nitrogen and phosphorus is improved through the processes of microorganism absorption and conversion, physical deposition, chemical precipitation and the like.
Thirdly, the nutrition slow release performance of the obtained nutrition type soil remediation material
The water body repairing material prepared by the invention is put into eutrophic wastewater to be adsorbed and treated to purify nitrogen and phosphorus in the wastewater, and then is recovered and dried. The detection shows that the nitrogen adsorption amount is not less than 210 g N/Kg, the phosphorus adsorption amount is not less than 70 gP/Kg, in addition, the water body repairing material has rich microporous structure and huge specific surface area, and can slowly release adsorbed nutrient substances, and the slow decomposition process is beneficial to the formation of humus, so the water body repairing material can be used for soil repair as a nutritional type repairing material to realize the cyclic recycle of nutrients.
FIG. 4 shows the effect of different addition amounts of eutrophic soil remediation materials on the total nitrogen leaching amount in soil. As can be seen from fig. 4, the leaching amount of total nitrogen in the soil gradually decreases during the whole leaching process; along with the increase of the addition amount of the slow release fertilizer, the leaching amount of the total nitrogen is obviously reduced, and the downward leaching loss of the total nitrogen also tends to be reduced along with the increase of the leaching times.
FIG. 5 shows the effect of different addition amounts of the obtained nutritional soil remediation material on the total phosphorus leaching amount in soil. As can be seen from FIG. 5, the addition of the soil remediation material can effectively reduce the leaching loss of total phosphorus in the soil, mainly because the biochar/attapulgite/biological bacteria has strong adsorption and fixation effects on phosphate and soluble organic phosphorus, which is beneficial to controlling the leaching loss of phosphorus.
In conclusion, the method treats the decolored waste soil through carbonization, so that the attapulgite rod crystals are loaded with the biochar, and the carbonized decolored waste soil is used as a carrier to fix biological bacteria, so that the eutrophic wastewater is treated, the adsorption performance of the wastewater on nitrogen and phosphorus molecules is improved, the synergistic and complementary effects can be achieved, and the removal capacity of nitrogen and phosphorus in the wastewater is further improved; and then taking the eutrophic water body purification material adsorbing nitrogen and phosphorus as a nutrient reservoir for soil environment restoration so as to realize the cyclic recycling of nutrients. Therefore, the method realizes treatment of the eutrophic wastewater, realizes effective utilization of nitrogen and phosphorus nutrients, obtains the material with good slow-release nutrient environment restoration, and has wide application prospect in the aspects of water body purification, soil environment restoration and the like.
Drawings
FIG. 1 is an infrared spectrum of a carbonized and decolored waste soil and eutrophic water restoration material prepared by the invention;
FIG. 2 shows the simulated eutrophic wastewater (nitrogen content 50 mg. L) prepared by the water body repairing and purifying material, biological bacteria and carbonized and decolored waste soil of the invention-1) Removal profile of medium total nitrogen the removal profile of total nitrogen;
FIG. 3 shows the purification material pair simulated eutrophic wastewater (phosphorus content 50 mg. multidot.L)-1) The adsorption power curve diagram of medium total phosphorus;
FIG. 4 shows the influence of different addition amounts of the obtained nutritional soil remediation material on the total nitrogen leaching amount in soil;
FIG. 5 shows the effect of different addition amounts of the obtained nutritional soil remediation material on the total phosphorus leaching amount in soil.
Detailed Description
The preparation and application of the eutrophic water body remediation material are further explained by the following specific examples.
Example 1: calcining soybean oil decolorized attapulgite waste soil at 350 ℃ for 3h under nitrogen atmosphere to obtain a carrier material, mixing the carrier material with nitrobacteria, bacillus subtilis and pseudomonas composite bacteria (the mass ratio is 1:1: 1) in a weight ratio of 120:1, culturing for 8h at 30 ℃, and air-drying and granulating to obtain the purification material with the granularity of 3 mm. The purification material is put into nutrient-rich wastewater for adsorption treatment, nitrogen and phosphorus in the wastewater are purified and then recovered, and the obtained nutrient soil improvement material is dried in a drying oven at 80 ℃, wherein the nitrogen content is 243.8 g N/Kg, and the phosphorus content is 78.6 gP/Kg.
Example 2: calcining the palm oil decolorized attapulgite waste soil for 1h at 600 ℃ in a nitrogen atmosphere to obtain a carrier material, mixing the carrier material with nitrobacteria, bacillus licheniformis and pseudomonas composite bacteria (the mass ratio is 1:2: 1) in a weight ratio of 150:1, culturing for 12h at 30 ℃, and air-drying and granulating to obtain the purification material with the granularity of 4 mm. The purification material is put into nutrient-rich wastewater for adsorption treatment, nitrogen and phosphorus in the wastewater are purified and then recovered, and the obtained nutrient soil improvement material is dried in a drying oven at 80 ℃, wherein the nitrogen content is 226.5 g N/Kg, and the phosphorus content is 73.4 gP/Kg.
Example 3: calcining attapulgite waste soil obtained by decoloring waste engine oil at 500 ℃ for 2 hours in a nitrogen atmosphere to obtain a carrier material, mixing the carrier material with nitrobacteria, bacillus licheniformis, denitrifying bacteria and pseudomonas composite bacteria (the mass ratio is 1:1:1: 1) in a weight ratio of 100:1, culturing for 24 hours at 30 ℃, and air-drying and granulating to obtain a purification material with the particle size of 2.5 mm. The purification material is put into nutrient-rich wastewater for adsorption treatment, nitrogen and phosphorus in the wastewater are purified and then recovered, and the obtained nutrient soil improvement material is dried in a drying oven at 80 ℃, wherein the nitrogen content is 218.4 g N/Kg, and the phosphorus content is 78.3 gP/Kg.
Example 4: calcining soybean oil decolorized attapulgite waste soil at 500 ℃ for 3h under nitrogen atmosphere to obtain a carrier material, mixing with denitrifying bacteria and pseudomonas composite bacteria (mass ratio is 1: 1) in a weight ratio of 130:1, culturing at 30 ℃ for 20h, and air-drying and granulating to obtain a purification material with the particle size of 2 mm. The purification material is put into nutrient-rich wastewater for adsorption treatment, nitrogen and phosphorus in the wastewater are purified and then recovered, and the obtained nutrient soil improvement material is dried in a drying oven at 80 ℃, wherein the nitrogen content of the obtained nutrient soil improvement material is 230.8 g N/Kg, and the phosphorus content of the obtained nutrient soil improvement material is 76.2 gP/Kg.
Example 5: calcining the palm oil decolorized attapulgite waste soil at 300 ℃ for 3h in a nitrogen atmosphere to obtain a carrier material, mixing the carrier material with composite bacteria of nitrobacteria, bacillus licheniformis and denitrifying bacteria (the mass ratio is 1:1: 1) in a weight ratio of 100:1, culturing for 12h at 30 ℃, and air-drying and granulating to obtain the purification material with the granularity of 1 mm. The purification material is put into eutrophic wastewater for adsorption treatment, nitrogen and phosphorus in the wastewater are purified and then recovered, and the material is dried in a drying oven at 80 ℃, so that the obtained nutritional soil improvement material has the nitrogen content of 240.1mg N/g and the phosphorus content of 73.7mg P/g.
Claims (5)
1. The method for preparing the eutrophic water body restoration material by using the decolored waste soil comprises the steps of feeding the decolored attapulgite waste soil into a rotary kiln, carbonizing at 300-600 ℃ for 1-3 hours under the atmosphere of nitrogen, and cooling to obtain carbonized decolored attapulgite waste soil; and uniformly mixing carbonized and decolored attapulgite waste soil and the composite bacteria, culturing for 6-24 h at 28-30 ℃, and air-drying and granulating to obtain the eutrophic water body remediation material of the attapulgite carbonized waste soil-biological bacteria denitrifying bacteria coupling system.
2. The method for preparing the eutrophic water body restoration material by using the decolored waste soil as set forth in claim 1, wherein the method comprises the following steps: the decolorized attapulgite waste soil is attapulgite waste soil decolorized by soybean oil, palm oil and used engine oil, and the oil content of the decolorized attapulgite waste soil is not less than 10%.
3. The method for preparing the eutrophic water body restoration material by using the decolored waste soil as set forth in claim 1, wherein the method comprises the following steps: the compound bacteria are at least two of nitrobacteria, bacillus subtilis, bacillus licheniformis, saccharomycetes, denitrifying bacteria, lactic acid bacteria and pseudomonas.
4. The method for preparing the eutrophic water body restoration material by using the decolored waste soil as set forth in claim 1, wherein the method comprises the following steps: the carbonized and decolored attapulgite waste soil and the composite bacteria are mixed according to the weight ratio of 100: 1-150: 1.
5. The method for preparing the eutrophic water body restoration material by using the decolored waste soil as set forth in claim 1, wherein the method comprises the following steps: the granulation granularity is 1-5 mm.
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Cited By (3)
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| CN112239267A (en) * | 2020-10-13 | 2021-01-19 | 兰州交通大学 | Preparation method and application of carbon/attapulgite/polyurethane composite immobilized carrier |
| CN113415897A (en) * | 2021-06-02 | 2021-09-21 | 南京公诚节能新材料研究院有限公司 | Technical method of ecological culture medium based on attapulgite |
| CN114272894A (en) * | 2021-11-27 | 2022-04-05 | 嵊州炭鼎炭素科技有限公司 | Environment-friendly degradable biomass-based active carbon composite adsorption material and preparation process thereof |
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Effective date of registration: 20210812 Address after: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou Applicant after: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Address before: 211700 No. 1, Xianglan Avenue, Aotu science and Technology Industrial Park, Xuyi county, Huai'an City, Jiangsu Province Applicant before: XUYI R & D CENTER FOR APPLICATION OF ATTAPULGITE CLAY, LANZHOU INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES Applicant before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences |
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