CN116495898A - Ecological restoration agent and water body treatment method - Google Patents

Ecological restoration agent and water body treatment method Download PDF

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Publication number
CN116495898A
CN116495898A CN202310661384.0A CN202310661384A CN116495898A CN 116495898 A CN116495898 A CN 116495898A CN 202310661384 A CN202310661384 A CN 202310661384A CN 116495898 A CN116495898 A CN 116495898A
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ecological restoration
restoration agent
graphene oxide
water body
washing
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CN202310661384.0A
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CN116495898B (en
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郑晓霞
王永灿
陈蕾
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Suzhou Shuoya Ep Technology Co ltd
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Suzhou Shuoya Ep Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/342Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used

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  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

The invention relates to the technical field of ecological restoration, in particular to an ecological restoration agent and a water body treatment method, which comprise the following components in percentage by weight: 2 to 6: 0.5-1 percent of xylitol enzyme, alkaline phosphatase, laccase and graphene oxide/straw composite aerogel carrier, the ecological restoration agent has good treatment effect on river sewage, wherein COD Cr The removal rate is more than 70 percent, NH 3 The removal rate of N is more than 85 percent, the removal rate of TP is more than 50 percent, and the method is suitable for large-scale application.

Description

Ecological restoration agent and water body treatment method
Technical Field
The invention relates to the technical field of ecological restoration, in particular to an ecological restoration agent and a water body treatment method.
Background
Due to the fact that urban sewage is discharged on two sides of a river channel, pollutants in the atmosphere, ground garbage and the like enter the river channel along with rainfall runoff flushing, the concentration of organic matters in the river channel is increased, the concentration of nitrogen and phosphorus is increased, the concentration of dissolved oxygen is reduced, aquatic animals and plants in the water body die, the self-cleaning capability of the water body is lost, and the water quality is deteriorated and smelly.
At present, river water treatment methods mainly comprise three types of physical methods, chemical methods and ecological restoration methods, wherein the physical methods comprise ecological water regulation, sediment dredging, garbage salvage and the like, but usually treat the symptoms and the root cause, the cost is higher, the chemical methods comprise medicament algae removal, flocculation precipitation and the like, secondary pollution is easy to cause, ecological unbalance can be caused by long-term use, the ecological restoration method has the advantages of no energy consumption or low energy consumption, low operation cost and the like, and is widely used at present, in the ecological restoration method, the removal of pollutants in water is mainly finished through the oxidative degradation of microorganisms, so the oxidative degradation capability of the microorganisms is directly related to the quality of the treatment effect.
At present, researches are focused on screening out microorganisms with higher degradation activity or compounding strains, and the symbiotic proliferation relationship is utilized to improve the oxidative degradation capability of the microorganisms, so that reports on water body treatment through enzyme preparations are few.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides an ecological restoration agent and a water body treatment method.
The technical scheme adopted is as follows:
an ecological restoration agent comprises the following components in percentage by weight: 2 to 6: xylitol enzyme, alkaline phosphatase and laccase in 0.5-1 proportion.
Further, the composite aerogel further comprises a carrier, wherein the carrier is graphene oxide/straw composite aerogel.
Further, the preparation method of the graphene oxide/straw composite aerogel comprises the following steps:
mixing graphene oxide and straw powder, ball milling, dispersing in water, adding triethylamine to obtain a dispersion liquid, transferring the dispersion liquid into a hydrothermal reaction kettle, sealing and heating to 140-160 ℃ for reaction for 18-24 h, recovering room temperature, filtering, washing the obtained product, and freeze-drying at low temperature for 48-75 h.
Further, the weight ratio of the graphene oxide to the straw powder is 1:1 to 5.
Further, the graphene oxide is an epoxidized graphene oxide.
Further, the preparation method of the epoxidized graphene oxide comprises the following steps:
dispersing graphene oxide in DMF, adding potassium fluoride and potassium iodide, uniformly mixing, then dripping epichlorohydrin, heating to reflux reaction for 15-24 h after dripping, recovering room temperature, separating out a product, washing and drying.
Further, the straw powder is carboxylated straw powder.
Further, the preparation method of the carboxylated straw powder comprises the following steps:
crushing crop straws, drying, adding the crushed crop straws into a sodium hydroxide-ethanol-water composite solution, carrying out ultrasonic vibration dispersion, heating to 60-80 ℃, dropwise adding chloroacetic acid solution into the reaction solution, carrying out heat preservation reaction for 2-4 hours after dropwise adding, recovering the room temperature, filtering, washing the product with water, washing with sodium chloride solution and ethanol in sequence, and finally drying.
The invention also provides a preparation method of the ecological restoration agent, which comprises the following steps:
fixing xylitol enzyme, alkaline phosphatase and laccase on graphene oxide/straw composite aerogel by adopting a physical adsorption method, dispersing the graphene oxide/straw composite aerogel in water, mixing the graphene oxide/straw composite aerogel with acetic acid solution of chitosan to obtain mixed solution, dripping the mixed solution into sodium hydroxide solution, standing for 24-48 h after dripping, filtering, washing the obtained product until the product is neutral, adding the product into methanol, adding glutaraldehyde for crosslinking, filtering out and washing after 3-5 h, and finally freezing and drying at a low temperature.
The invention also provides a water body treatment method:
the ecological restoration agent is put into a water body, the water body is treated at the temperature of-5-40 ℃, and aeration is carried out on the water body while the treatment is carried out, so that the content of dissolved oxygen in the water body is ensured to be 1-10 mg/L.
The invention also discloses application of the ecological restoration agent in aquaculture, which can continuously play a role in purifying water areas in aquaculture, and the compound enzyme consisting of xylitol enzyme, alkaline phosphatase and laccase can selectively activate PGPR microorganisms in the water body, after the activation, the activity of the PGPR microorganisms is enhanced, the types are increased, the quantity is greatly improved, the characteristics of the PGPR are utilized to promote the decomposition of organic matters, purify water quality and restore ecology, and the ecological restoration agent has the effects of degrading eutrophic ammonia nitrogen and phosphorus, inhibiting the growth of harmful microorganisms, removing phosphorus and nitrogen from polluted water bodies, dredging organisms and the like.
The invention has the beneficial effects that:
the invention provides an ecological restoration agent, wherein, a composite enzyme composed of xylitol enzyme, alkaline phosphatase and laccase can selectively activate PGPR microorganisms in water, after the activation, the activity of the PGPR microorganisms is enhanced, the variety is increased, the quantity is greatly improved, the characteristics of the PGPR are utilized to promote the decomposition of organic matters, purify water quality and restore ecology, and the increase of the quantity and the activity of beneficial microorganisms are enhanced, so that the beneficial microorganisms establish population advantages, inhibit the growth and propagation of pathogenic bacteria, mould, viruses and other harmful microorganisms, thereby playing roles in regulating the balance of bacterial groups and inhibiting the growth of harmful microorganisms;
the graphene oxide/straw composite aerogel tape has carboxyl, epoxy and other reactive groups, and can be subjected to certain chemical bonding with enzyme in the immobilization process, so that the stability of the immobilized enzyme is improved, the physical adsorption and entrapment of the macroporous morphology of the immobilized enzyme are beneficial to the metabolic proliferation of PGPR microorganisms, excellent mass transfer performance is also presented, and the immobilized graphene/straw composite aerogel tape has excellent mechanical properties and large enzyme load capacity as a carrier due to the crosslinking of the epoxy and the carboxyl, and the straw can be used as an additional carbon source by microorganisms.
The ecological restoration agent has good treatment effect on river sewage, wherein COD Cr The removal rate is more than 70 percent, NH 3 The removal rate of N is more than 85 percent, the removal rate of TP is more than 50 percent, and the method is suitable for large-scale application.
Drawings
FIG. 1 is a comparison of the front and rear of the treatment of river sewage by the ecological restoration agent in the embodiment 1 of the present invention.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The technology not mentioned in the present invention refers to the prior art, and unless otherwise indicated, the following examples and comparative examples are parallel tests, employing the same processing steps and parameters.
Example 1:
the preparation method of the ecological restoration agent comprises the following steps:
adding 500mL of DMF into a 1L flask with a charged stirrer, a thermometer and a reflux condenser, adding 2.2g of graphene oxide, 75.2g of potassium fluoride and 20g of potassium iodide, stirring and mixing uniformly, then dropwise adding 80mL of epichlorohydrin, heating to reflux reaction for 18h after dripping, recovering room temperature, filtering, repeatedly washing the obtained product with ethanol and deionized water, drying at 80 ℃ for 10h to obtain epoxidized graphene oxide, crushing 12g of wheat straw, putting the crushed wheat straw into a 200-mesh screen, drying at 100 ℃ for 24h in a baking oven, adding the crushed wheat straw into a composite solution consisting of 50g of sodium hydroxide, 375mL of ethanol and 125mL of water, ultrasonically oscillating for 30min, heating to 70 ℃, dropwise adding 200mL of chloroacetic acid solution with the mass fraction of 50% into the reaction solution, carrying out heat preservation reaction for 4 hours after dropwise adding, recovering the room temperature, filtering, washing a product to be neutral by using water, washing the product by using 5% of sodium chloride solution and ethanol in sequence, finally drying the product at 80 ℃ for 10 hours to obtain carboxylated straw powder, mixing 2g of epoxy graphene oxide and 8g of carboxylated straw powder, ball-milling for 2 hours, dispersing the mixture into 250mL of water, adding 5g of triethylamine to obtain a dispersion liquid, transferring the dispersion liquid into a hydrothermal reaction kettle, carrying out sealing heating to 150 ℃ for reaction for 24 hours, filtering after recovering the room temperature, washing the obtained product to be neutral by using water, and carrying out low-temperature freeze drying for 48 hours at-40 ℃ to obtain graphene oxide/straw composite aerogel; adding 0.4g of xylitol enzyme, 1g of alkaline phosphatase and 0.15g of laccase into 50mL of phosphate buffer solution, stirring for 15min, adding the graphene oxide/straw composite aerogel, carrying out heat preservation and adsorption for 60min, vacuum drying until the moisture content is 8%, obtaining a semi-finished product, dispersing the semi-finished product into 100mL of water, mixing the semi-finished product with 50mL of 2% acetic acid solution dissolved with 5g of chitosan to obtain a mixed solution, adding 150mL of 4% sodium hydroxide solution into the mixed solution, standing for 48h after dripping, filtering, washing the obtained product until the product is neutral, adding into 250mL of methanol, adding 1g of glutaraldehyde for crosslinking, filtering out after 4h, repeatedly washing with ethanol and deionized water, and finally carrying out low-temperature freeze drying for 24h at-40 ℃.
Example 2:
substantially the same as in example 1, except that 0.6g of xylitol enzyme, 1.2g of alkaline phosphatase and 0.2g of laccase were added.
Example 3:
substantially the same as in example 1, except that 0.2g of xylitol enzyme, 0.4g of alkaline phosphatase and 0.1g of laccase were added.
Example 4:
substantially the same as in example 1, except that 0.6g of xylitol enzyme, 0.4g of alkaline phosphatase and 0.2g of laccase were added.
Example 5:
substantially the same as in example 1, except that 0.2g of xylitol enzyme, 1.2g of alkaline phosphatase and 0.1g of laccase were added.
Comparative example 1:
substantially the same as in example 1, except that xylitol enzyme was not added.
Comparative example 2:
substantially the same as in example 1, except that alkaline phosphatase was not added.
Comparative example 3:
substantially the same as in example 1, except that no laccase was added.
Performance test:
river sewage is taken from a river in Hunan, and the water quality index is shown in table 1;
table 1:
COD Cr /(mg/L) NH 3 -N/(mg/L) TP/(mg/L)
river sewage 185.3 32.8 6.9
Wherein, COD Cr The method is measured by adopting a dichromate oxidation method, and the specific reference standard GB-11914-89; NH (NH) 3 -N is determined by a nano reagent colorimetric method, specific reference standard GB 7479-87; the total phosphorus is measured by adopting a potassium persulfate oxidation-molybdenum antimony anti-spectrophotometry method, and the standard GB 11893-89 is specifically referred to.
The ecological restoration agent prepared in the examples 1-5 and the comparative examples 1-3 of the invention is used as a sample, an organic glass cylinder with the effective volume of 8L is used as a reaction vessel, river sewage is injected into the reaction vessel, a microporous aeration head is respectively added into the reaction vessel, the microporous aeration head is connected with an air compressor, the air compressor is started, an air inlet valve is regulated to ensure that the aeration amount in all the reaction vessels is basically consistent, the sample is put into the reaction vessel with the dosage of 0.15g/L, the water body is treated at room temperature, the operation is continued for 15d, aeration is carried out for 6h at the ratio of 10:00 to 16:00 per day, water quality detection is carried out after precipitation for 1h, and the removal rate (%) is calculated, and the results are shown in the table 2:
table 2:
as can be seen from the above Table 2, the ecological restoration agent of the invention has good treatment effect on river sewage, wherein COD Cr The removal rate is more than 70 percent, NH 3 The removal rate of N is more than 85 percent, the removal rate of TP is more than 50 percent, and the method is suitable for large-scale application.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. An ecological restoration agent is characterized by comprising the following components in percentage by weight: 2 to 6: xylitol enzyme, alkaline phosphatase and laccase in 0.5-1 proportion.
2. The ecological restoration agent according to claim 1, further comprising a carrier, wherein the carrier is graphene oxide/straw composite aerogel.
3. The ecological restoration agent as recited in claim 2, wherein the preparation method of the graphene oxide/straw composite aerogel is as follows:
mixing graphene oxide and straw powder, ball milling, dispersing in water, adding triethylamine to obtain a dispersion liquid, transferring the dispersion liquid into a hydrothermal reaction kettle, sealing and heating to 140-160 ℃ for reaction for 18-24 h, recovering room temperature, filtering, washing the obtained product, and freeze-drying at low temperature for 48-75 h.
4. The ecological restoration agent as recited in claim 3, wherein a weight ratio of said graphene oxide to straw powder is 1:1 to 5.
5. The ecological restoration agent according to claim 3, wherein said graphene oxide is an epoxidized graphene oxide.
6. The ecological restoration agent according to claim 5, wherein the preparation method of the epoxidized graphene oxide is as follows:
dispersing graphene oxide in DMF, adding potassium fluoride and potassium iodide, uniformly mixing, then dripping epichlorohydrin, heating to reflux reaction for 15-24 h after dripping, recovering room temperature, separating out a product, washing and drying.
7. The ecological restoration agent as defined in claim 3, wherein said straw powder is carboxylated straw powder.
8. The ecological restoration agent as defined in claim 7, wherein the preparation method of the carboxylated straw powder is as follows:
crushing crop straws, drying, adding the crushed crop straws into a sodium hydroxide-ethanol-water composite solution, carrying out ultrasonic vibration dispersion, heating to 60-80 ℃, dropwise adding chloroacetic acid solution into the reaction solution, carrying out heat preservation reaction for 2-4 hours after dropwise adding, recovering the room temperature, filtering, washing the product with water, washing with sodium chloride solution and ethanol in sequence, and finally drying.
9. The method for preparing the ecological restoration agent according to claim 2, which is characterized in that xylitol enzyme, alkaline phosphatase and laccase are fixed on graphene oxide/straw composite aerogel by adopting a physical adsorption method, dispersed in water, mixed with acetic acid solution of chitosan to obtain mixed solution, the mixed solution is added into sodium hydroxide solution in a liquid drop manner, standing for 24-48 h after the dripping, filtering, washing the obtained product until the product is neutral, adding into methanol, adding glutaraldehyde for crosslinking, filtering out and washing after 3-5 h, and finally freezing and drying at a low temperature.
10. A water body treatment method, which is characterized in that the ecological restoration agent of any one of claims 1 to 8 is put into a water body, the water body is treated at the temperature of-5 to 40 ℃, and aeration is carried out on the water body while the treatment is carried out, so that the content of dissolved oxygen in the water body is ensured to be 1 to 10mg/L.
CN202310661384.0A 2023-06-06 2023-06-06 Ecological restoration agent and water body treatment method Active CN116495898B (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104909467A (en) * 2015-06-02 2015-09-16 陕西科技大学 Bio-stimulant for biochemical treatment of paper-making wastewater
CN108636357A (en) * 2018-06-07 2018-10-12 石梦成 A kind of use in waste water treatment cross-linking type graphite oxide aerogel and preparation method thereof
CN109354217A (en) * 2018-12-21 2019-02-19 江西省科学院 A kind of river water body and bed mud comprehensive treatment agent and preparation method
CN110255810A (en) * 2019-05-31 2019-09-20 广东五色时空生态环境科技有限公司 Black-odor riverway biology in situ ecology synthesis intervenes sewage quality lifting process
CN111672432A (en) * 2020-06-12 2020-09-18 西北大学 Preparation method of graphene oxide/chitosan composite aerogel for enzyme immobilization
US20200298202A1 (en) * 2017-12-12 2020-09-24 Jiangsu Academy Of Agricultural Sciences Preparation Method for Combined Modified Straw Active Particulate Carbon Adsorption Material and Use of Same
CN112159061A (en) * 2020-09-07 2021-01-01 中国环境科学研究院 Method for accurately positioning and in-situ treating pollutants on mud-water interface
CN113264633A (en) * 2021-04-20 2021-08-17 广西壮族自治区环境保护科学研究院 Ecological restoration method for black and odorous river channel
CN114871266A (en) * 2022-04-29 2022-08-09 天津城建大学 Method for repairing soil polluted by refractory organic matters by using immobilized laccase in cooperation with soil microbial electrochemical system

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104909467A (en) * 2015-06-02 2015-09-16 陕西科技大学 Bio-stimulant for biochemical treatment of paper-making wastewater
US20200298202A1 (en) * 2017-12-12 2020-09-24 Jiangsu Academy Of Agricultural Sciences Preparation Method for Combined Modified Straw Active Particulate Carbon Adsorption Material and Use of Same
CN108636357A (en) * 2018-06-07 2018-10-12 石梦成 A kind of use in waste water treatment cross-linking type graphite oxide aerogel and preparation method thereof
CN109354217A (en) * 2018-12-21 2019-02-19 江西省科学院 A kind of river water body and bed mud comprehensive treatment agent and preparation method
CN110255810A (en) * 2019-05-31 2019-09-20 广东五色时空生态环境科技有限公司 Black-odor riverway biology in situ ecology synthesis intervenes sewage quality lifting process
CN111672432A (en) * 2020-06-12 2020-09-18 西北大学 Preparation method of graphene oxide/chitosan composite aerogel for enzyme immobilization
CN112159061A (en) * 2020-09-07 2021-01-01 中国环境科学研究院 Method for accurately positioning and in-situ treating pollutants on mud-water interface
CN113264633A (en) * 2021-04-20 2021-08-17 广西壮族自治区环境保护科学研究院 Ecological restoration method for black and odorous river channel
CN114871266A (en) * 2022-04-29 2022-08-09 天津城建大学 Method for repairing soil polluted by refractory organic matters by using immobilized laccase in cooperation with soil microbial electrochemical system

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