CN114212866A - Cob coagulant prepared from agricultural wastes and preparation method thereof - Google Patents
Cob coagulant prepared from agricultural wastes and preparation method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 23
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention belongs to the technical field of water treatment, and relates to a cob coagulant utilizing agricultural wastes and a preparation method thereof. The coagulant is a brown liquid product or a solid product, is non-toxic and easy to biodegrade, and formed sludge can be recycled in farmlands, so that the method conforms to the circular economy concept of treating wastes with processes of wastes against one another. The production process of the cob coagulant is normal pressure and low temperature, the energy consumption is low, the production process has no secondary pollution, the production period is short, the production equipment and the process are simple, economic and easy to realize, the initial investment is low, and the operation cost is low. The invention can be applied to the fields of urban sewage, industrial wastewater and the like, and is particularly suitable for specific targets of denitrification, algae removal and the like of low-carbon-source wastewater.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a cob coagulant utilizing agricultural wastes and a preparation method thereof.
Background
In recent decades, with the rapid development of industry, agriculture and economy, the water environment problem becomes more serious, and the water resource shortage problem becomes more and more an important factor for restricting the economic development of China. In order to relieve the water resource crisis, improve the utilization rate and water treatment efficiency of water and realize good social circulation of water, the research on water purification treatment technology must be enhanced. The first step of the water purification treatment is generally a coagulation sedimentation treatment. Coagulation is one of indispensable process units in the water treatment process, can effectively remove various pollutants in water, such as turbidity, dyes, heavy metal ions, other industrial or agricultural pollutants, algae and the like, and the quality of the coagulation effect directly influences the removal effect of the pollutants in the whole water treatment process. The quality of the coagulant is a direct key factor for determining the effect of a coagulation process unit, so that the research and development of the efficient, nontoxic and cheap coagulant becomes a key task in water treatment and has great practical significance. For a long time, the coagulants used for water treatment mainly include inorganic coagulants, organic polymer coagulants and microbial coagulants. The inorganic polymer coagulant has low price, good stability and great advantages, but has certain damage to organisms and environment. The microbial coagulant is basically nontoxic, but has a long distance to reach large-scale application from the viewpoint that the preparation, storage, use and the like of the microbial coagulant have unstable characteristics, so that the microbial coagulant is still basically in the research and exploration stages at present. The organic polymer coagulant comprises two kinds: the artificially synthesized organic coagulant is expensive, the formed sludge is easy to dehydrate, and pollutants which seriously affect the health of human bodies are also generated in the production or degradation process of the sludge, so that secondary pollution is often caused, and the application of the artificially synthesized organic coagulant in industrial production is increasingly limited.
The development of modern economy and technology has greatly improved the quality of life of people over the last fifty years, but has also greatly consumed diminishing natural resources. Excessive consumption of resources and energy poses a potentially serious threat to human survival, making the world concerned about "sustainable development" problems. Therefore, it is increasingly important to protect the environment where human beings live, reasonably and comprehensively utilize resources, and particularly efficiently utilize waste resources. In the field of water treatment, the research on natural organic polymer coagulant is one of important ideas for effectively utilizing agricultural waste resources. The natural organic coagulant has the characteristics of rich raw material sources, low price, easy degradation, no toxicity and the like, has good environmental acceptability, and can recycle sludge generated after water treatment by considering farmland aiming at raw water with low toxicity or no toxicity, so the natural organic coagulant is concerned by experts in the water treatment field of various countries in the world in recent years.
Corn is native to south america, is one of the main world food crops, and accounts for about 25% of the total world food production. China is a big agricultural country, the corn yield accounts for about one fifth of the grain yield, the corn is the second place in the world, and the yield of the corn cob (the residual cob after the corn is threshed) which is a byproduct after the corn is harvested every year is about 2000 ten thousand tons. Most of the corn cobs are abandoned in the field or directly burned as fuel, which causes serious environmental pollution and also causes great resource waste, so how to utilize the corn cobs which can be used as renewable resources has attracted high attention of researchers in various countries around the world. The corn cob is abundant and cheap in China, the product of the corn cob can be completely biodegraded, the corn cob contains a large amount of natural high molecular compounds such as cellulose and lignin, the surface of the corn cob also contains a plurality of active functional groups such as hydroxyl, carboxyl, amino and the like, and the corn cob has main components required for preparing a coagulant.
At present, the research on the corn cob mainly relates to agriculture (a method for planting agaricus bisporus by using waste agaricus bisporus fungus sticks, CN 202110799761.8; a green environment-friendly organic matrix for vegetable planting and a preparation method thereof, CN 202110780792.9), chemical industry (a synthesis method and application of a nano corn cob Ag-ZnO composite catalyst, CN 202110620712.3; biomass porous activated carbon and a preparation method thereof and application of the biomass porous activated carbon as an electrode material of an electric double layer capacitor, CN 201910041999.7), medicine industry (a process for producing terramycin by using corn raw materials, CN202110790483. X; a preparation method of medicinal activated carbon, CN202011227333. X) and related fields of the environment-friendly industry. The following patents are relevant to the research of corn cob in the environmental field: a soil remediation passivator polluted by heavy metal cadmium and a preparation method thereof (CN 202110338505.9), a biostimulation bottom mud remediation agent and a preparation method thereof (CN 202110448583.4), wherein CN202110338505.9 utilizes montmorillonite, fly ash, biochar, livestock and poultry manure, organic compost, ferrous sulfate, organic silicon, magnesium oxide, bentonite, kieselguhr powder, apatite powder, soybean straw powder, corn cob powder and water to prepare the soil remediation passivator polluted by heavy metal cadmium, CN202110448583.4 utilizes rare earth elements, a stabilizer, a nutrient co-matrix, a slow-release cosolvent and trace elements to prepare a biostimulation bottom mud remediation agent, wherein the stabilizer is at least one of calcium nitrate or iron powder, the nutrition co-matrix is at least four of sugar, carboxylic acid, fatty acid, amino acid soluble organic matter, straw, corn cob fragments, brewery waste residue, glucose, starch, acetate and lactate, and the slow-release cosolvent is any one or two of carboxymethyl cellulose or hydroxypropyl cellulose.
The application of the corn cob in the environmental protection field does not relate to a cob coagulant and a preparation method thereof. At present, no reports related to a cob coagulant taking corn cobs as a main raw material and a preparation method thereof are found in domestic and foreign literature databases.
Disclosure of Invention
The invention mainly aims to widen the application range of corn cobs in the field of environmental protection, find a realistic and practical way for agricultural wastes, and solve the technical problem of preparing a cob coagulant with wide application range and excellent application effect by using the components required by coagulants such as cellulose, lignin and the like contained in the corn cobs, and provide a corresponding preparation method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the cob coagulant comprises the following raw materials in percentage by weight:
corn cob powder is 4% -36%
33% -80% of tap water
4 to 40 percent of sodium hydroxide
0.08-0.4% of stabilizer,
all percentages are mass percentages;
the preparation method of the cob coagulant utilizing the agricultural wastes comprises the following steps:
(a) cutting the corn cob into blocks with the thickness of 4-6 cm, washing the blocks for 2-3 times by using tap water, drying the blocks for 8-14 hours at the temperature of 55-75 ℃, crushing the blocks to obtain yellow-white cob powder, and sealing and storing the yellow-white cob powder for later use;
(b) under the condition of medium-speed stirring, adding 4-40% of sodium hydroxide into 33-80% of tap water, and stirring for 1-3 minutes to obtain a sodium hydroxide solution for later use;
(c) adding 4-36% of corn cob powder into the sodium hydroxide solution under medium-speed stirring and at the temperature of 40-80 ℃, stirring for 7-20 minutes, and obtaining cob leaching mixed liquor for later use;
(d) under the condition of medium-speed stirring, adding 0.08-0.4% of stabilizer into the cob leaching mixed solution, and stirring for 2-5 minutes to obtain a cob coagulant brown liquid product;
(e) solidifying the liquid product by adopting a freezing method, a roller drying method or a vacuum drying method, wherein the freezing temperature of the freezing method is controlled to be minus 30 ℃ to minus 18 ℃, the hot air inlet temperature of the roller drying method is controlled to be 100 ℃ to 120 ℃, the temperature of the vacuum drying method is controlled to be 40 ℃ to 65 ℃, and the vacuum degree is controlled to be 85 Kpa to 95Kpa, so that a solid product of the cob coagulant is prepared.
The sodium hydroxide is industrial solid with mass content higher than 90%.
The stabilizer is BIT-20 antibacterial solution containing 1-2 benzisothiazolin-3-one as main ingredient and more than 75%, thiabendazole containing 2- (thiazole-4-yl) benzimidazole as main ingredient, and effective component>40% of the formula is C5H4Sodium olmyline of NOSNa, technical grade.
The invention has the following advantages:
1. the invention takes agricultural waste corn cob as a main preparation raw material, takes industrial-grade sodium hydroxide as a leaching agent, and the prepared cob coagulant is nontoxic and easy to biodegrade, and the formed sludge can be recycled in farmlands, thereby conforming to the circular economy concept of 'treating waste by waste'.
2. The production process of the liquid cob coagulant is normal pressure and low temperature, the energy consumption is low, the production process has no secondary pollution, the production period is short, the production equipment and the process are simple, economic and easy to realize, the initial investment is low, and the operation cost is low.
3. The invention adopts a freezing method or a vacuum drying method to solidify the liquid product of the cob coagulant, the product does not change the quality, the stable coagulation effect can be maintained, and the operation period is short and the efficiency is high when the roller drying or the vacuum drying is adopted to solidify the liquid product.
4. The cob coagulant can be applied to the fields of urban sewage, industrial wastewater and the like, and is particularly suitable for specific targets of denitrification, algae removal and the like of low-carbon-source wastewater.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Cutting the corn cob into blocks with the thickness of 4-6 cm, washing the blocks for 2-3 times by using tap water, drying the blocks for 8-14 hours at the temperature of 55-75 ℃, crushing the blocks to obtain yellow-white cob powder, and sealing and storing the yellow-white cob powder for later use. Under the condition of medium-speed stirring, 7kg of sodium hydroxide solid with the mass content of more than 90% is added into 50L of tap water, and stirring is carried out for 1-3 minutes to obtain a sodium hydroxide solution for later use. And adding 7kg of corn cob powder into the sodium hydroxide solution under the conditions of medium-speed stirring and 70 ℃, and stirring for 7-20 minutes to obtain a cob leaching mixed solution for later use. Under the condition of stirring at a medium speed, 0.08kg of BIT-20 bactericidal solution and thiabendazole are mixed according to the volume ratio of 1: adding the mixture into the cob leaching mixed solution according to the proportion of 1, and stirring for 2-5 minutes to obtain a cob coagulant brown liquid product.
Example 2
Cutting the corn cob into blocks with the thickness of 4-6 cm, washing the blocks for 2-3 times by using tap water, drying the blocks for 8-14 hours at the temperature of 55-75 ℃, crushing the blocks to obtain yellow-white cob powder, and sealing and storing the yellow-white cob powder for later use. Under the condition of medium-speed stirring, 20kg of sodium hydroxide solid with the mass content of more than 90% is added into 35L of tap water, and stirring is carried out for 1-3 minutes to obtain a sodium hydroxide solution for later use. And adding 14kg of corn cob powder into the sodium hydroxide solution under the conditions of medium-speed stirring and 50 ℃, and stirring for 7-20 minutes to obtain a cob leaching mixed solution for later use. And under the condition of stirring at a medium speed, adding 0.25kg of BIT-20 sterilization solution into the cob leaching mixed solution, and stirring for 2-5 minutes to obtain a cob coagulant dark brown liquid product.
Example 3
Cutting the corn cob into blocks with the thickness of 4-6 cm, washing the blocks for 2-3 times by using tap water, drying the blocks for 8-14 hours at the temperature of 55-75 ℃, crushing the blocks to obtain yellow-white cob powder, and sealing and storing the yellow-white cob powder for later use. Under the condition of medium-speed stirring, 10kg of sodium hydroxide solid with the mass content of more than 90% is added into 58L of tap water, and stirring is carried out for 1-3 minutes to obtain a sodium hydroxide solution for later use. And adding 5kg of corn cob powder into the sodium hydroxide solution under the conditions of medium-speed stirring and 40 ℃, and stirring for 7-20 minutes to obtain a cob leaching mixed solution for later use. Under the condition of medium-speed stirring, 0.28kg of BIT-20 bactericidal solution, thiabendazole and sodium olmesartan are added into the cob leaching mixed solution according to the volume ratio of 0.5:1:0.5, and stirring is carried out for 2-5 minutes, so as to obtain a cob coagulant light brown liquid product.
Example 4
Cutting the corn cob into blocks with the thickness of 4-6 cm, washing the blocks for 2-3 times by using tap water, drying the blocks for 8-14 hours at the temperature of 55-75 ℃, crushing the blocks to obtain yellow-white cob powder, and sealing and storing the yellow-white cob powder for later use. Under the condition of medium-speed stirring, 7kg of sodium hydroxide solid with the mass content of more than 90% is added into 50L of tap water, and stirring is carried out for 1-3 minutes to obtain a sodium hydroxide solution for later use. And adding 7kg of corn cob powder into the sodium hydroxide solution under the conditions of medium-speed stirring and 70 ℃, and stirring for 7-20 minutes to obtain a cob leaching mixed solution for later use. Under the condition of stirring at a medium speed, 0.08kg of BIT-20 bactericidal solution and thiabendazole are mixed according to the volume ratio of 1: adding the mixed solution into the cob leaching solution according to the proportion of 1, and stirring for 2-5 minutes to obtain a cob coagulant liquid product. Solidifying the liquid product by adopting a freezing method, controlling the freezing temperature to be-18 ℃ and preparing the cob coagulant solid product.
Example 5
Cutting the corn cob into blocks with the thickness of 4-6 cm, washing the blocks for 2-3 times by using tap water, drying the blocks for 8-14 hours at the temperature of 55-75 ℃, crushing the blocks to obtain yellow-white cob powder, and sealing and storing the yellow-white cob powder for later use. Under the condition of medium-speed stirring, 20kg of sodium hydroxide solid with the mass content of more than 90% is added into 35L of tap water, and stirring is carried out for 1-3 minutes to obtain a sodium hydroxide solution for later use. And adding 14kg of corn cob powder into the sodium hydroxide solution under the conditions of medium-speed stirring and 50 ℃, and stirring for 7-20 minutes to obtain a cob leaching mixed solution for later use. And under the condition of stirring at a medium speed, adding 0.25kg of BIT-20 sterilization solution into the cob leaching mixed solution, and stirring for 2-5 minutes to obtain a cob coagulant deep liquid product. And solidifying the liquid product by adopting a roller drying method, and controlling the temperature of a hot air inlet to be 100-120 ℃ to prepare a cob coagulant solidified product.
Example 3
Cutting the corn cob into blocks with the thickness of 4-6 cm, washing the blocks for 2-3 times by using tap water, drying the blocks for 8-14 hours at the temperature of 55-75 ℃, crushing the blocks to obtain yellow-white cob powder, and sealing and storing the yellow-white cob powder for later use. Under the condition of medium-speed stirring, 10kg of sodium hydroxide solid with the mass content of more than 90% is added into 58L of tap water, and stirring is carried out for 1-3 minutes to obtain a sodium hydroxide solution for later use. And adding 5kg of corn cob powder into the sodium hydroxide solution under the conditions of medium-speed stirring and 40 ℃, and stirring for 7-20 minutes to obtain a cob leaching mixed solution for later use. Under the condition of medium-speed stirring, 0.28kg of BIT-20 bactericidal solution, thiabendazole and sodium olmesartan are added into the cob leaching mixed solution according to the volume ratio of 0.5:1:0.5, and stirring is carried out for 2-5 minutes, so as to obtain a cob coagulant light brown liquid product. And solidifying the liquid product by adopting a vacuum drying method, controlling the temperature to be 50-55 ℃, and preparing a cob coagulant solid product.
The material object diagram of the cob coagulant and the floc object diagram generated in the coagulation process are shown in the attached drawings.
FIG. 1 is a schematic diagram of raw materials used in the cob coagulant of the present invention.
FIG. 2 is a schematic diagram of a pulverized powder of a raw material used in the cob coagulant of the present invention.
FIG. 3 is a pictorial view of a cob coagulant liquid product prepared in example 1.
Fig. 4 is a diagram of floc effects produced by applying the cob coagulant liquid product prepared in example 1 to humic acid simulation water (addition =1 mL/L).
Fig. 5 is a diagram of the effect of floc precipitation generated by applying the liquid product of the cob coagulant prepared in example 1 to humic acid simulation water (addition =1 mL/L).
The cob coagulant has the following coagulation effects:
the cob coagulant liquid products nos. 1, 2 and 3 prepared in the above examples 1, 2 and 3 were applied to the treatment effect of humic acid simulated water. The turbidity of the humic acid simulated water is 37.6NTU, the pH value is 8.15, the chroma is 0.351CU, and the water temperature is 18.6 ℃. The treatment results are shown in tables 1 and 2, wherein table 1 is that 1mL of the cob coagulant liquid product of the invention is added into 1L of simulated water, and table 2 is that 4mL of the cob coagulant liquid product of the invention is added into 1L of simulated water.
TABLE 1 treatment effect of liquid product of cob coagulant of the invention applied to humic acid simulated water (dosage of 1mL/L)
TABLE 2 treatment effect of the liquid product of cob coagulant of the invention applied to humic acid simulated water (dosage of 4mL/L)
From the treatment results, the cob coagulant has excellent turbidity removal and decoloration performances.
Claims (4)
1. A cob coagulant utilizing agricultural wastes comprises the following raw materials in percentage by weight:
corn cob powder is 4% -36%
33% -80% of tap water
4 to 40 percent of sodium hydroxide
0.08-0.4% of stabilizer,
all percentages are mass percentages;
the preparation method of the cob coagulant utilizing the agricultural wastes comprises the following steps:
(a) cutting the corn cob into blocks with the thickness of 4-6 cm, washing the blocks for 2-3 times by using tap water, drying the blocks for 8-14 hours at the temperature of 55-75 ℃, crushing the blocks to obtain yellow-white cob powder, and sealing and storing the yellow-white cob powder for later use;
(b) under the condition of medium-speed stirring, adding 4-40% of sodium hydroxide into 33-80% of tap water, and stirring for 1-3 minutes to obtain a sodium hydroxide solution for later use;
(c) adding 4-36% of corn cob powder into the sodium hydroxide solution under medium-speed stirring and at the temperature of 40-80 ℃, stirring for 7-20 minutes, and obtaining cob leaching mixed liquor for later use;
(d) under the condition of medium-speed stirring, adding 0.08-0.4% of stabilizer into the cob leaching mixed solution, and stirring for 2-5 minutes to obtain a cob coagulant brown liquid product;
(e) solidifying the liquid product by adopting a freezing method, a roller drying method or a vacuum drying method, wherein the freezing temperature of the freezing method is controlled to be minus 30 ℃ to minus 18 ℃, the hot air inlet temperature of the roller drying method is controlled to be 100 ℃ to 120 ℃, the temperature of the vacuum drying method is controlled to be 40 ℃ to 65 ℃, and the vacuum degree is controlled to be 85 Kpa to 95Kpa, so that a solid product of the cob coagulant is prepared.
2. The cob coagulant of claim 1 wherein the sodium hydroxide used is technical grade solid with a mass content of greater than 90%.
3. The cob coagulant of claim 1, wherein the stabilizer is BIT-20 bactericidal liquid whose main ingredient is 1-2 benzisothiazolin-3-one and whose effective component is more than 75%, thiabendazole whose main ingredient is 2- (thiazol-4-yl) benzimidazole, and effective component>40% of the formula is C5H4Sodium olmyline of NOSNa, technical grade.
4. The cob coagulant of agricultural waste according to claim 1 is applicable to the fields of municipal sewage, industrial wastewater and the like, and is particularly applicable to specific targets of denitrification, algae removal and the like of low-carbon-source wastewater.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250293A (en) * | 2011-05-25 | 2011-11-23 | 重庆工商大学 | Preparation method and application of acrylamide modified grafted corn cob |
| CN111875230A (en) * | 2020-07-29 | 2020-11-03 | 中国计量大学 | Full biomass flocculant and preparation method thereof |
| CN112551667A (en) * | 2020-11-13 | 2021-03-26 | 济南大学 | Preparation technology of natural polymer type pineapple peel residue coagulant |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250293A (en) * | 2011-05-25 | 2011-11-23 | 重庆工商大学 | Preparation method and application of acrylamide modified grafted corn cob |
| CN111875230A (en) * | 2020-07-29 | 2020-11-03 | 中国计量大学 | Full biomass flocculant and preparation method thereof |
| CN112551667A (en) * | 2020-11-13 | 2021-03-26 | 济南大学 | Preparation technology of natural polymer type pineapple peel residue coagulant |
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