CN110902950A - Treatment method of starch industrial wastewater - Google Patents
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- 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
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
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Abstract
The invention belongs to the technical field of environmental protection, and discloses a method for treating starch industrial wastewater, which comprises the following steps: filtering wastewater by a net fence to remove large-particle impurities, then entering an air floatation tank to remove suspended matters and oil-fat substances in the wastewater, then entering a flocculation sedimentation tank, adding a chitosan solution, uniformly stirring, standing for 1-3h, then entering an acid-base neutralization tank, adjusting the pH to 6-7, finally entering a biological reaction tank, adding a biological agent, treating for 48-60h, filtering by a filter screen, and discharging. The treatment method disclosed by the invention can be used for quickly and efficiently treating pollutants, can also be used for recovering protein in wastewater, and can be used for the field of feeds.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a treatment method of starch industrial wastewater.
Background
The starch is produced by using corn as a raw material, wherein 60 percent of corn in dry basis becomes commercial starch, 30 percent of corn becomes a byproduct, and the rest part becomes waste liquid to be discharged out of a factory. The by-products are mainly powder residue (containing fiber and residual starch) and embryo which are discharged in a solid state, and the waste liquid is mainly two high-concentration organic waste waters, namely soaking water with the solid concentration of 5 percent and yellow slurry water with the solid concentration of more than 2 percent. The steep water of large enterprises is concentrated into corn steep liquor which is used as a nutrient source for producing antibiotics, but most of small factories do not recover the corn steep liquor. The discharge amount of the soaking water is 0.5-1% of the raw materials, while the discharge amount of the yellow serofluid reaches about 30 times of the raw materials (or 20 times of the product starch), and about 600t of yellow serofluid is discharged every day in a starch factory which treats 1 ten thousand tons of corn in one year. The high-concentration organic wastewater mainly contains protein, sugar, fat and the like, and also contains a large amount of nitrogen-carbon inorganic compounds.
A large amount of waste water can be generated in the starch processing process, and the method has the following main characteristics: high COD, high organic matter, high nitrogen phosphorus and sulfur, good biodegradability, suitability for biological treatment and easy waste of organic matter. At present, conventional starch wastewater treatment methods at home and abroad mainly comprise a physical chemical method and a biological method, and the two methods have respective advantages and disadvantages in practical application. The physicochemical methods include a natural treatment method, a simple aeration method and a flocculation precipitation method. Biological treatment method: the starch wastewater contains a large amount of suspended, soluble or colloidal organic pollutants, does not contain toxic substances, has good biodegradability, and can achieve ideal removal effect by adopting biological treatment. The methods have various advantages and disadvantages, and how to optimally combine the methods to improve the wastewater treatment efficiency and reduce the cost is a technical problem to be solved by starch processing enterprises. At present, most biochemical treatment methods do not recover protein, so that protein waste is caused. The organic substances such as protein in the recovered starch wastewater can be used as feed protein, fertilizer and algae culture medium components, and can reduce the load of subsequent biological treatment.
The prior patent technology 'CN 105000676B' of the applicant discloses a method for treating starch processing wastewater, which comprises the following steps: step 1) preparing a biological carrier, step 2) preparing a biological preparation, and step 3) biologically treating; the biological agent uses bacillus subtilis liquid, acidophilic ferrous oxide thiobacillus liquid, acinetobacter baumannii liquid, sphingosine monospore liquid, scenedesmus obliquus liquid and chlorella liquid, and has a good treatment effect on pollutants. However, the above research results mainly have the following three problems: 1. the culture process of the contained more types of microorganisms is complicated, once one microorganism has the problems of pollution and the like, the whole biological preparation process is stopped, and the burden of enterprises is increased; 2. the organic matter in the wastewater contains a large amount of starch and carbohydrate, and the value of the organic matter is not fully utilized; 3. the treatment period is long, and the biological agent is easy to deposit to the bottom to form sludge, so that the treatment difficulty is increased.
The patent technology 'CN 107265687A' discloses a corn starch process water recycling process, which comprises the following steps: enabling waste water generated in the corn starch processing technology to flow through a multiple grid, then entering a sedimentation tank, standing, then entering a chemical adsorption tank, adding a chemical adsorbent, stirring, then stopping stirring, performing adsorption treatment, filtering through an ultrafiltration membrane to obtain permeate, and finally entering a corn starch processing water system for reuse. The process can be recycled after purifying the wastewater, saves water resources and avoids the pollution of the wastewater to the environment; however, membrane treatment is required in the operation process, and the burden is heavy for small and medium-sized enterprises.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a treatment method of starch industrial wastewater, which can quickly and efficiently treat pollutants and recover protein in the wastewater, is used for the field of feeds and achieves two purposes.
In order to achieve the purpose of the invention, the following technical scheme is adopted.
The treatment method of the starch industrial wastewater comprises the following steps:
the method comprises the following steps of filtering wastewater through a net-shaped fence to remove large-particle impurities, then enabling the wastewater to enter an air floatation tank to remove suspended matters and oil-fat substances in the wastewater, then enabling the wastewater to enter a flocculation sedimentation tank, adding a chitosan solution, stirring uniformly, standing for 1-3h, then enabling the wastewater to enter an acid-base neutralization tank, adjusting the pH to 6-7, and finally enabling the wastewater to enter a biological reaction tank according to the weight of 10-100 g: 1m3Adding biological agent in the proportion ofTreating for 48-60h, filtering with a filter screen, and discharging.
Preferably, the ratio is in the range of 0.5-1L: 1m3The chitosan solution was added in the ratio of (1).
Preferably, the ratio is in the range of 10-100 g: 1m3Adding biological agent according to the ratio.
Preferably, the aperture of the filter screen is 0.5-1 mm.
Preferably, the chitosan solution is prepared according to the following steps: the deacetylation degree of the selected chitosan is 80-90%; adding chitosan into 1% acetic acid solution by volume ratio to prepare chitosan solution with concentration of 5-20 g/L.
Further, the biological agent is prepared according to the following steps:
1) mixing organic bentonite according to the proportion of 1 g: adding 1-5ml of the mixture into hydrochloric acid, uniformly stirring, heating to 50-60 ℃, preserving heat for 30min, then adding 20-40 mass percent of rice hull powder and 2-8 mass percent of urea which account for the organic bentonite, uniformly stirring, then entering a wet granulator for granulation to obtain particles with the particle size of 2-4mm, then placing the particles at 500-600 ℃ for roasting for 1h, taking out, and cooling to room temperature to obtain the product;
2) mixing Clostridium perfringens acclimation solution and modified organic bentonite, culturing for 4-10h under anaerobic condition, adding Candida utilis acclimation solution, culturing for 4-10h, oven drying at 20 deg.C until water content is 10-20%, and preserving at 4 deg.C.
Preferably, the preparation method of the candida utilis domestication liquid comprises the following steps: inoculating the Candida utilis seed solution into an acclimatization culture medium according to the inoculation amount of 10%, and carrying out acclimatization culture for 12h at the temperature of 30 ℃ to obtain the Candida utilis acclimatization solution.
Preferably, the preparation method of the clostridium perfringens domestication liquid comprises the following steps: inoculating the clostridium perfringens seed liquid into an acclimatization culture medium according to the inoculation amount of 10%, and carrying out acclimatization culture for 12h at 33 ℃ to obtain the clostridium perfringens acclimatization liquid.
Preferably, the ratio of the clostridium perfringens domestication liquid to the candida utilis domestication liquid to the modified organic bentonite is 1 ml: 1 ml: 1-4 g.
Preferably, the acclimatization medium is prepared from the YPD medium and the wastewater at a volume ratio of 1: 1.
Preferably, the domesticated culture medium is an FTG liquid culture medium and the wastewater is prepared according to the volume ratio of 1: 1.
Preferably, the concentration of the hydrochloric acid is 0.4-1.0M.
Compared with the prior art, the invention mainly has the following advantages that:
the invention relates to a treatment method of starch industrial wastewater, which comprises the steps of filtering the starch industrial wastewater through a mesh fence, removing large-particle impurities from the mesh fence which comprises a large mesh fence and a small mesh fence, then entering an air floatation tank, removing suspended matters and grease substances in the wastewater, then entering a flocculation sedimentation tank, adding a chitosan solution for flocculating and precipitating protein, then entering an acid-base neutralization tank, adjusting the pH value to be suitable for microbial biochemical reaction, and finally entering a biological reaction tank; the treatment method can not only quickly and efficiently treat pollutants, but also recover protein in the wastewater, and is used in the field of feeds, thereby achieving two purposes.
The biochemical preparation used in the treatment method comprises chitosan and a biological preparation, wherein the chitosan and the biological preparation are separately used, the chitosan is used for flocculating and precipitating protein, and the chitosan is non-toxic and has no secondary pollution, so that the protein obtained by flocculation can be used as a nitrogen source of animal feed or culture medium, the industrial added value is improved, most of the protein is recovered by flocculation, and the pressure of subsequent processes is reduced; the biological agent is used for degrading pollutants, can be repeatedly used for many times, and reduces the cost.
The biological preparation comprises modified organic bentonite and two microorganisms, and the degradation efficiency is improved by modifying the organic bentonite and selecting proper microorganisms for domestication and compatibility.
The organic bentonite is prepared by the steps of activating the organic bentonite, removing partial hydroxyl groups to form broken bonds so as to enhance activity, adding a certain amount of additives, namely rice hull powder and urea, and then roasting, wherein the crystal structure and the crystal form of the organic bentonite are changed and become orderly arranged, the surface of the organic bentonite becomes loose and rough, more porous structures are formed, the pore distribution is uniform, the specific surface area of the organic bentonite is improved, the organic bentonite has better pollutant adsorption performance, and the organic bentonite is favorable for attachment of strains.
The clostridium perfringens is an anaerobic bacterium, lacks a complete metabolic enzyme system, the energy metabolism is carried out in an anaerobic fermentation mode, the oxygen content in the wastewater is low, and the strain is wrapped in a carrier and cannot be contacted with oxygen, so that the proliferation and anaerobic biochemical reaction of the strain are facilitated; the candida utilis is facultative anaerobe, comprises two metabolic pathways, and can be propagated and biochemically reacted under the conditions of sufficient oxygen and insufficient oxygen; in view of the property of candida utilis, the candida utilis is coated on the surface of the modified organic bentonite, so that pollutants can be fermented under aerobic and anaerobic conditions, and clostridium perfringens in the modified organic bentonite degrades the pollutants under the anaerobic condition; the two strains are attached to different parts of the modified organic bentonite according to different requirements on oxygen, can be symbiotically coordinated, and treat pollutants through different mechanisms.
Drawings
FIG. 1: influence of strain selection on COD removal rate;
FIG. 2: influence of strain selection on SS removal rate;
FIG. 3: influence of strain selection on TN removal rate;
FIG. 4: influence of strain selection on TP removal Rate.
Detailed Description
Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the products and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and modifications, or appropriate alterations and combinations, of the products and methods described herein may be made and utilized without departing from the spirit, scope, and spirit of the invention. For a further understanding of the present invention, reference will now be made in detail to the following examples.
Example 1
A biochemical preparation for repairing starch industrial wastewater comprises a chitosan solution and a biological agent, wherein the ratio of the chitosan solution to the biological agent is 10L: 1 kg; the chitosan solution and the biological preparation are used separately, the chitosan solution is used for flocculating and precipitating protein, and the biological preparation is used for degrading pollutants.
The chitosan solution is prepared according to the following steps:
the deacetylation degree of the selected chitosan is 87%, and the chitosan is added into an acetic acid solution with the volume ratio of 1% to prepare a chitosan solution with the concentration of 10 g/L.
The biological agent is prepared according to the following steps:
1) mixing organic bentonite according to the proportion of 1 g: adding 2ml of the mixture into 0.5M hydrochloric acid, uniformly stirring, heating to 55 ℃, preserving heat for 30min, adding 30 mass parts of rice hull powder and 5 mass parts of urea in the organic bentonite, uniformly stirring, granulating in a wet granulator to obtain particles with the particle size of 2mm, roasting at 550 ℃ for 1h, taking out, and cooling to room temperature to obtain the product;
2) mixing Clostridium perfringens acclimation solution and modified organic bentonite, culturing for 6h under anaerobic condition, adding Candida utilis acclimation solution, culturing for 6h, drying at 20 deg.C until water content is 15%, and preserving at 4 deg.C; the ratio of the clostridium perfringens domestication liquid to the candida utilis domestication liquid to the modified organic bentonite is 1 ml: 1 ml: 2g of the total weight.
The preparation method of the candida utilis domestication liquid comprises the following steps: selecting Candida utilis (ATCC22023) single colony, inoculating into YPD medium, culturing at 30 deg.C and 200rpm for 12 hr, transferring into 1L YPD medium, culturing at 30 deg.C and 200rpm for 24 hr, inoculating into 10L YPD medium at 5%, and culturing to 1 × 109cfu/ml to obtain candida utilis seed liquid; seed to be plantedInoculating the seed solution into an acclimation culture medium (the volume ratio of the YPD culture medium to the starch industrial wastewater is 1: 1) according to the inoculation amount of 10%, and carrying out acclimation culture at 30 ℃ for 12h to obtain an acclimation solution of the Candida utilis;
the preparation method of the clostridium perfringens domestication liquid comprises the following steps: inoculating Clostridium perfringens (ATCC 13124) into FTG liquid culture medium, placing into 33 deg.C anaerobic incubator (nitrogen 87%, carbon dioxide 7%, hydrogen 6%), culturing under anaerobic condition until the concentration is 1 × 108cfu/ml, and obtaining clostridium perfringens seed liquid; inoculating the strain into an acclimation culture medium (volume ratio of FTG liquid culture medium to starch industrial wastewater is 1: 1) according to the inoculation amount of 10%, and carrying out acclimation culture at 33 ℃ for 12h to obtain the clostridium perfringens acclimation solution.
Example 2
A biochemical preparation for repairing starch industrial wastewater comprises a chitosan solution and a biological agent, wherein the ratio of the chitosan solution to the biological agent is 10L: 2 kg; the chitosan solution and the biological preparation are used separately, the chitosan solution is used for flocculating and precipitating protein, and the biological preparation is used for degrading pollutants.
The chitosan solution is prepared according to the following steps:
the deacetylation degree of the selected chitosan is 90%, and the chitosan is added into an acetic acid solution with the volume ratio of 1% to prepare a chitosan solution with the concentration of 8 g/L.
The biological agent is prepared according to the following steps:
1) mixing organic bentonite according to the weight ratio of 2 g: adding 3ml of the mixture into 1M hydrochloric acid, uniformly stirring, heating to 60 ℃, preserving heat for 30min, adding rice hull powder accounting for 35 mass percent of the organic bentonite and urea accounting for 6 mass percent of the organic bentonite, uniformly stirring, granulating in a wet granulator to obtain particles with the particle size of 3mm, roasting at 600 ℃ for 1h, taking out, and cooling to room temperature to obtain the organic bentonite-based organic fertilizer;
2) mixing Clostridium perfringens acclimation solution and modified organic bentonite, culturing for 6h under anaerobic condition, adding Candida utilis acclimation solution, culturing for 6h, drying at 25 deg.C until water content is 15%, and preserving at 4 deg.C; the ratio of the clostridium perfringens domestication liquid to the candida utilis domestication liquid to the modified organic bentonite is 1 ml: 1 ml: 3g of the total weight.
Example 3
The treatment method of the starch industrial wastewater comprises the following steps:
waste water filters through netted fence, and netted fence includes big net fence and little net fence, gets rid of large granule impurity, then gets into the air supporting pond, gets rid of suspended solid and grease class material in the waste water, reentrants flocculation and precipitation pond, according to 1L: 1m3Adding a chitosan solution according to the proportion, uniformly stirring, standing for 2 hours, then entering an acid-base neutralization tank, adjusting the pH to 6.5, and finally entering a biological reaction tank, wherein the weight ratio of the chitosan solution to the acid-base neutralization tank is 100 g: 1m3Adding biological agent according to the proportion, treating for 48h, filtering by a filter screen with the aperture of 1mm, and discharging.
Example 4
1. Taking wastewater of a certain batch in a corn starch processing workshop as an example, the treatment process adopts the example 3, the biochemical preparation adopts the example 1, and the indexes of partial components are compared before and after, and are shown in the table 1.
TABLE 1
| Index (I) | Before treatment | After flocculation and precipitation treatment |
| Protein mg/L | 3521 | 1407 |
| Solid suspension mg/L | 8950 | 2769 |
Therefore, large-particle solid matters can be removed through fence filtration, suspended matters and grease substances in wastewater can be removed through the air floatation tank, most of protein can be precipitated through flocculation precipitation of chitosan, and the method is non-toxic and can be applied to feeds.
2. The water inlet indexes of the biological reaction tank are as follows: COD was 4135, SS was 560, TN was 416, TP was 172, in mg/L. And monitoring the effluent indexes after being filtered by the filter screen, and calculating the removal rate of main pollutants of COD, SS, TN and TP (water inlet index-effluent index/water inlet index) x 100 percent.
The effect of different combinations of strains on major contaminants.
Group 1: only candida utilis is adopted;
group 2: clostridium perfringens + candida utilis;
group 3: clostridium perfringens + rhodosporidium palustum;
group 4: clostridium perfringens + angel yeast.
The removal rate of each pollutant is shown in figures 1-4, and comprehensive observation shows that the removal efficiency of the pollutants in the first 12 hours is higher, mainly because the modified organic bentonite has larger adsorption volume to the pollutants, and then gradually reaches saturation, the pollutants need to be degraded by bacterial strains, and then the pollutants can be adsorbed again by the modified organic bentonite; the wastewater also contains a certain amount of protein and starch sugar, and the strain can simultaneously utilize the protein and starch sugar while degrading the pollutants, thereby prolonging the degradation period of the whole pollutants. As shown in fig. 1 and 3, among different strain combination modes, the combination mode of clostridium perfringens and candida utilis has the best effect of removing COD and TN, the removal rate is close to the peak value after 60 hours, the removal rate is superior to other combinations, and the removal rate is the candida utilis group which is only about 70 percent; as shown in fig. 2, in the mode of combining clostridium perfringens with three kinds of yeast respectively, the removal rate of SS is not greatly different and reaches about 95% in 60 hours; as shown in figure 4, the concentration of TP in the wastewater is relatively low, at 48h, the three combination modes of clostridium perfringens and yeast are close to the peak value, the best treatment effect is clostridium perfringens + candida utilis, clostridium perfringens + rhodosporidium palustum, the degradation capability of the clostridium perfringens + Angel yeast group to TP is weak, and 48h can only reach about 89%. And combining the results, the clostridium perfringens and candida utilis are selected to have the best degradation effect on various main pollutants.
3. The influence of the modification mode of the organic bentonite on the physicochemical property.
Mode 1: unmodified organobentonite;
mode 2: the same procedure as in example 1 was repeated except that the treatment was not carried out;
mode 3: the rest of the procedure was the same as in example 1, except that no rice hull powder was added;
mode 4: inventive example 1.
The density and specific surface area indexes of the four types of organobentonite are shown in table 2.
TABLE 2
| High density g/cm | Specific surface area m2/g | |
| Mode 1 | 1.71 | 23.5 |
| Mode 2 | 1.03 | 64.1 |
| Mode 3 | 1.29 | 56.9 |
| Mode 4 | 1.05 | 97.2 |
And (4) conclusion: according to the invention, the surface of the organic bentonite is loosened and rough by acid treatment, rice husk and urea are added for roasting to carry out modification treatment, so that more porous structures are formed, the pore distribution is uniform, the specific surface area is improved, the pollutant adsorption performance is better, and the bacterial strain adhesion is facilitated; the density of the modified organic bentonite is equivalent to that of liquid, the modified organic bentonite is suspended and dispersed in the liquid, and the adsorption range of pollutants can be improved, so that the pollutants are adsorbed more quickly.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The treatment method of the starch industrial wastewater comprises the following steps:
filtering wastewater by a net fence to remove large-particle impurities, then entering an air floatation tank to remove suspended matters and oil-fat substances in the wastewater, then entering a flocculation sedimentation tank, adding a chitosan solution, uniformly stirring, standing for 1-3h, then entering an acid-base neutralization tank, adjusting the pH to 6-7, finally entering a biological reaction tank, adding a biological agent, treating for 48-60h, filtering by a filter screen, and discharging.
2. The process according to claim 1, characterized in that the ratio of the total amount of the components in the mixture is 0.5-1L: 1m3The chitosan solution was added in the ratio of (1).
3. The process according to claim 1, characterized in that the ratio of the total weight of the mixture of 10 to 100 g: 1m3Adding biological agent according to the ratio.
4. The process according to claim 1, wherein the filter mesh has a pore size of 0.5 to 1 mm.
5. The process according to claim 1 or 2, characterized in that the chitosan solution is prepared by the following steps: the deacetylation degree of the chitosan is 80-90%; adding chitosan into 1% acetic acid solution by volume ratio to prepare chitosan solution with concentration of 5-20 g/L.
6. The process of claim 1 or 3, wherein the biological agent is prepared by the steps of:
1) mixing organic bentonite according to the proportion of 1 g: adding 1-5ml of the mixture into hydrochloric acid, uniformly stirring, heating to 50-60 ℃, preserving heat for 30min, then adding 20-40 mass percent of rice hull powder and 2-8 mass percent of urea which account for the organic bentonite, uniformly stirring, then entering a wet granulator for granulation to obtain particles with the particle size of 2-4mm, then placing the particles at 500-600 ℃ for roasting for 1h, taking out, and cooling to room temperature to obtain the product;
2) mixing Clostridium perfringens acclimation solution and modified organic bentonite, culturing for 4-10h under anaerobic condition, adding Candida utilis acclimation solution, culturing for 4-10h, drying at 20 deg.C until water content is 10-20%, and preserving at 4 deg.C; the ratio of the clostridium perfringens domestication liquid to the candida utilis domestication liquid to the modified organic bentonite is 1 ml: 1 ml: 1-4 g.
7. The treatment method of claim 6, wherein the Candida utilis acclimation solution is prepared by the following steps: inoculating the Candida utilis seed solution into an acclimatization culture medium according to the inoculation amount of 10%, and carrying out acclimatization culture for 12h at the temperature of 30 ℃ to obtain the Candida utilis acclimatization solution.
8. The processing method according to claim 6, wherein the Clostridium perfringens domesticated liquid is prepared by: inoculating the clostridium perfringens seed liquid into an acclimatization culture medium according to the inoculation amount of 10%, and carrying out acclimatization culture for 12h at 33 ℃ to obtain the clostridium perfringens acclimatization liquid.
9. The treatment method according to claim 7, wherein the acclimatization medium is prepared from YPD medium and wastewater at a volume ratio of 1: 1.
10. The treatment method according to claim 8, wherein the acclimatization medium is an FTG liquid medium and the wastewater is prepared at a volume ratio of 1: 1.
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| CN110923184A (en) * | 2019-12-01 | 2020-03-27 | 齐齐哈尔龙江阜丰生物科技有限公司 | Biological agent for repairing threonine fermentation wastewater |
| CN114538695A (en) * | 2020-11-24 | 2022-05-27 | 山东福洋生物科技股份有限公司 | Method for treating modified starch industrial wastewater by using microorganisms |
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