CN117718011A - Method for removing chemical oxygen demand in sewage by using modified corn straw biochar - Google Patents
Method for removing chemical oxygen demand in sewage by using modified corn straw biochar Download PDFInfo
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- CN117718011A CN117718011A CN202410015564.6A CN202410015564A CN117718011A CN 117718011 A CN117718011 A CN 117718011A CN 202410015564 A CN202410015564 A CN 202410015564A CN 117718011 A CN117718011 A CN 117718011A
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- chemical oxygen
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- 240000008042 Zea mays Species 0.000 title claims abstract description 57
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 title claims abstract description 57
- 235000002017 Zea mays subsp mays Nutrition 0.000 title claims abstract description 57
- 235000005822 corn Nutrition 0.000 title claims abstract description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000001301 oxygen Substances 0.000 title claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 46
- 239000000126 substance Substances 0.000 title claims abstract description 46
- 239000010865 sewage Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000010902 straw Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 5
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010907 stover Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Water Treatment By Sorption (AREA)
Abstract
A method for removing chemical oxygen demand in sewage by utilizing modified corn stalk biochar relates to a method for removing chemical oxygen demand in sewage to be treated. The invention aims to solve the problems of high cost, poor effect, complex preparation process and the like of the traditional chemical oxygen demand treatment method and overcome the current situation that the waste of corn straw resources is serious. The method comprises the following steps: the method comprises the steps of using corn straw as a raw material, modifying the corn straw by using urea and kaolin, obtaining modified corn straw biochar through pyrolysis, adding the modified corn straw biochar into sewage to be treated, and oscillating to remove chemical oxygen demand in the sewage to be treated. The invention has simple preparation process and low cost. The method has obvious effect of removing the sewage to be treated and has good application prospect.
Description
Technical Field
The invention relates to a method for removing chemical oxygen demand in sewage by using modified corn stalk biochar.
Background
Chemical oxygen demand is the amount of oxidant consumed when a water sample is treated with a strong oxidant under certain conditions. It reflects the degree of pollution of substances in water, and the larger the chemical oxygen demand is, the more serious the pollution of organic substances in water is. Too high a chemical oxygen demand can cause serious harm to the water body and also can have serious influence on ecological balance. Therefore, how to effectively remove chemical oxygen demand from sewage is a currently hot environmental problem. However, since chemical oxygen demand has a very complex composition and is not easily degraded under conventional conditions, it is difficult to effectively remove chemical oxygen demand by conventional methods. Various methods for removing chemical oxygen demand have been developed, such as adsorption, coagulation, advanced oxidation (ozone, fenton), and the like. Adsorption is considered to be an excellent physicochemical method for removing chemical oxygen demand in sewage because of its advantages of high efficiency, simple operation, and wide applicability. However, the existing adsorption method generally has the problems of high cost, poor effect and complex preparation process, so that it is important to develop an adsorption material with strong capability of removing chemical oxygen demand, low cost and simple preparation process.
Straw is a part left by harvesting seeds of crops, such as corn straw and the like, and is a renewable biomass resource. However, the main method of treating straw is incineration, which not only damages the environment, but also wastes a great amount of reusable biomass resources. Therefore, searching for a low-cost, environment-friendly, simple and convenient method for recycling straw is the focus of current research. The biochar is a highly aromatic indissolvable solid carbon-rich product obtained by thermochemical reaction of agricultural and forestry wastes such as straws, wood chips, livestock manure and other biomass resources under the condition of complete hypoxia or oxygen limitation. The catalyst has large specific surface area, strong adsorption performance and various surface functional groups such as carboxyl, hydroxyl, lactone groups and the like, and can be used for removing pollutants. The invention discloses a method for treating chemical oxygen demand in sewage by catalytic oxidation by using rare earth ore, hydrochloric acid and active carbon as raw materials in the preparation method of rare earth-active carbon biocatalysis oxidized sludge (application number CN 201410691929.3), but the method has the problems of higher raw material cost, low biological safety, longer preparation process and the like. The disclosed patent of graphene oxide COD adsorption fixing agent, a preparation method and application thereof (application number CN 202010530965.7) discloses a preparation method of the graphene oxide COD adsorption fixing agent, but the raw material graphene oxide of the method is very expensive, and the preparation process is complex in operation and has a certain potential safety hazard. The invention provides a method for removing chemical oxygen demand in sewage by using modified corn straw biochar, which has the advantages of wide material source, low cost, obvious effect, simple preparation and wide application prospect.
Disclosure of Invention
The invention aims to solve the problems of low chemical oxygen demand removal rate, high cost, complicated preparation method and serious waste of corn straw resources of the conventional method at present.
The preparation method of the modified corn stalk biochar is specifically completed according to the following steps:
cutting corn stalks into small blocks, washing with distilled water to remove impurities on the surfaces of the corn stalks, drying the corn stalks in an oven at 45-55 ℃ for 23-25 hours, and crushing the dried corn stalks by a crusher; dissolving 0.5 g-1.5 g urea in distilled water, adding 0.5 g-1.0 g kaolin for mixing, adding 4.5 g-5.5 g crushed corn straw, uniformly stirring, drying in a baking oven at 45-55 ℃ for 10-12 h, putting the obtained mixture into a porcelain boat, then putting the porcelain boat into a tube furnace, preparing at 575-625 ℃ at a heating rate of 9 ℃/min-11 ℃/min, keeping the constant temperature for 1.5-2.5 h and N 2 The preparation is carried out under the condition that the flow rate is 45 mL/min-55 mL/min; and after the preparation is finished and cooled, obtaining the modified corn stalk biochar.
The method for removing the chemical oxygen demand in the sewage by using the modified corn stalk biochar comprises the following steps:
firstly, sewage to be treated is taken, modified corn stalk biochar is added into the sewage to be treated, and then constant-temperature oscillation is carried out for 50-70 min under the condition that the constant oscillation speed is 140-160 rpm. And then, filtering and separating the mixed solution, thereby completing the removal of the chemical oxygen demand in the sewage to be treated and finally obtaining the treated sewage.
The invention has the advantages that:
1. according to the invention, corn straw is used as a biomass carbon source, cheap biomass waste is converted into biochar resources, and the method is environment-friendly, so that the recycling of solid waste is realized; 2. the invention provides a method for removing chemical oxygen demand in sewage by using modified corn stalk biochar, which has low cost, obvious removal effect and higher feasibility; 3. the preparation method of the modified corn stalk biochar is simple, and the conditions are easy to control; 4. in the preparation process, urea and kaolin are used for modifying the biochar, so that the adsorption sites are increased, and the removal rate of the modified corn straw biochar on chemical oxygen demand is further increased in the modes of forming micropores, generating more functional groups and the like; 5. the invention has faster removal efficiency, can be completed within 50-70 min, and the removal reaches 69%; 6. the separated modified corn straw can be reused for more than 5 times through desorption, so that the recycling of materials is realized.
Drawings
FIG. 1 is a scanning electron microscope image of the modified corn stalk biochar prepared in example 1; as can be seen from fig. 1, the surface of the modified corn stalk biochar has more microporous structures and more adsorption sites, which is more beneficial to removing chemical oxygen demand in sewage;
FIG. 2 is an X-ray photoelectron spectrum of the modified corn stalk biochar prepared in example 1; in FIG. 2, five peaks appear at 531.3eV,399.7eV,284.3eV,101.5eV and 73.5eV, respectively, due to O1s, N1s, C1s, si2p and Al2p, which illustrate that nitrogen and aluminum elements are successfully doped into the modified corn stalk biochar;
FIG. 3 is a Fourier infrared spectrum of the modified corn stover biochar prepared in example 1; as can be seen from fig. 3, 3400cm -1 The broad peak at the position is caused by the stretching vibration of O-H, and the distance is 500cm -1 The peak strength of Si-O-Si is due to bending vibration, and is additionally 1350cm -1 at-COOH and 1050cm -1 The strong peak of the-CO is generated, which indicates that the modification generates more oxygen-containing functional groups and is more beneficial to removing the chemical oxygen demand in the sewage to be treated;
FIG. 4 is a graph showing the change of the chemical oxygen demand removal rate with time in the treatment of wastewater to be treated with the modified corn stover biochar prepared in example 1. According to the national standard of the people's republic of China, the method for measuring chemical oxygen demand (chemical oxygen demand) in industrial circulating cooling water, namely the permanganate index method, the method for measuring the chemical oxygen demand concentration in sewage to be treated is adopted; according to the formulaCalculating the chemical oxygen demand removal rate R, wherein C 0 Ce is the equilibrium concentration of chemical oxygen demand, which is the initial concentration of chemical oxygen demand; the removal rate R is taken as an ordinate, the time t is taken as an abscissa, and the graph is drawn by using Origin2018 software, and the specific result is shown in FIG. 4; the modified corn stalk biochar prepared by the method has the advantages that the time for removing the chemical oxygen demand in the sewage to be treated is quick, and the balance of removal can be achieved within 60 minutes;
FIG. 5 is a graph showing the chemical oxygen demand removal capacity of the modified corn stalk biochar prepared in example 1 under different dosage conditions; according to the formulaCalculating the chemical oxygen demand removal rate, plotting by Origin2018 plotting software with the removal rate as an ordinate and the addition amount as an abscissa, and the result is shown in FIG. 5; the removal rate gradually increases with the addition amount, and when the addition amount is 0.50g.L -1 When the removal rate reaches an equilibrium state and reaches 69%, the modified corn stalk biochar has a good removal effect on chemical oxygen demand in sewage to be treated;
FIG. 6 is a graph showing the removal of the modified corn stover biochar prepared in example 1 for treatmentAnd (3) recycling the chemical oxygen demand in the sewage for a plurality of times. In each cycle, 0.1 mol.L was used -1 The hydrochloric acid solution of (2) is used for eluting the modified corn stalk biochar adsorbed with the chemical oxygen demand, and the removal rate is calculated according to a specific formula, wherein n represents the cycle number. Drawing by using Origin2018 software with n as an abscissa and the removal rate as an ordinate, wherein the specific result is shown in fig. 6; by observing fig. 6, it can be concluded that: the modified corn stalk biochar is used for adsorbing chemical oxygen demand in sewage to be treated, and after 5 times of desorption and adsorption recycling, the removal rate is not obviously reduced and is kept at a level not lower than 65%.
Detailed Description
Example 1:
the embodiment is a preparation method of modified corn stalk biochar, which is specifically completed by the following steps:
cutting corn stalks into small pieces, washing with distilled water to remove impurities on the surfaces of the corn stalks, drying the corn stalks in a drying oven at 50 ℃ for 24 hours, and crushing the dried corn stalks by a crusher; dissolving 1.0g of urea in distilled water, adding 0.75g of kaolin for mixing, adding 5.0g of crushed corn straw, uniformly stirring, drying in a 50 ℃ oven for 10 hours, putting the obtained mixture into a porcelain boat, putting the porcelain boat into a tube furnace, preparing the mixture at 600 ℃, heating up at 10 ℃/min for 1.0 hour, and keeping the temperature constant for N 2 The preparation is carried out under the condition of 50mL/min flow rate; and after the preparation is finished and cooled, obtaining the modified corn stalk biochar.
Example 2:
the embodiment is a method for removing chemical oxygen demand in sewage by using modified corn stalk biochar, which specifically comprises the following steps:
firstly, sewage to be treated is taken, filtered, and solid impurities in the sewage to be treated are removed. Adding the modified corn stalk biochar into sewage to be treated, and then carrying out constant-temperature oscillation for 60min under the condition that the constant oscillation speed is 150 rpm. And then, filtering and separating the mixed solution, thereby completing the removal of the chemical oxygen demand in the sewage to be treated and finally obtaining the treated sewage.
Claims (2)
1. The preparation method of the modified corn stalk biochar is characterized by comprising the following steps of:
cutting corn stalks into small blocks, washing with distilled water to remove impurities on the surfaces of the corn stalks, drying the corn stalks in an oven at 45-55 ℃ for 23-25 hours, and crushing the dried corn stalks by a crusher; dissolving 0.5 g-1.5 g urea in distilled water, adding 0.5 g-1.0 g kaolin for mixing, adding 4.5 g-5.5 g crushed corn straw, uniformly stirring, drying in a baking oven at 45-55 ℃ for 10-12 h, putting the obtained mixture into a porcelain boat, then putting the porcelain boat into a tube furnace, preparing at 575-625 ℃ at a heating rate of 9 ℃/min-11 ℃/min, keeping the constant temperature for 1.5-2.5 h and N 2 The preparation is carried out under the condition that the flow rate is 45 mL/min-55 mL/min; and after the preparation is finished and cooled, obtaining the modified corn stalk biochar.
2. A method for removing chemical oxygen demand in sewage by using modified corn stalk biochar is characterized in that the modified corn stalk biochar is used as an adsorbent for removing chemical oxygen demand in sewage to be treated; the method specifically comprises the following steps: firstly, sewage to be treated is taken, modified corn stalk biochar is added into the sewage to be treated, and then constant-temperature oscillation is carried out for 50-70 min under the condition that the constant oscillation speed is 140-160 rpm. And then, filtering and separating the mixed solution, thereby completing the removal of the chemical oxygen demand in the sewage to be treated and finally obtaining the treated sewage.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410015564.6A CN117718011A (en) | 2024-01-05 | 2024-01-05 | Method for removing chemical oxygen demand in sewage by using modified corn straw biochar |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410015564.6A CN117718011A (en) | 2024-01-05 | 2024-01-05 | Method for removing chemical oxygen demand in sewage by using modified corn straw biochar |
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| Publication Number | Publication Date |
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| CN117718011A true CN117718011A (en) | 2024-03-19 |
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| CN202410015564.6A Pending CN117718011A (en) | 2024-01-05 | 2024-01-05 | Method for removing chemical oxygen demand in sewage by using modified corn straw biochar |
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| CN (1) | CN117718011A (en) |
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- 2024-01-05 CN CN202410015564.6A patent/CN117718011A/en active Pending
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