CN113548769A - Method for preparing biological composite carbon source by using citric acid fermentation wastewater and application - Google Patents
Method for preparing biological composite carbon source by using citric acid fermentation wastewater and application Download PDFInfo
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Abstract
The invention relates to a method for preparing a biological composite carbon source by using citric acid fermentation wastewater and application thereof. When the biological composite carbon source is prepared, the phosphorus source and the magnesium source are added after fermentation to generate struvite precipitate, which is an excellent nitrogen-phosphorus fertilizer and can be recycled as a resource.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a biological composite carbon source prepared by using citric acid fermentation wastewater, and a preparation method and application thereof.
Background
The shortage of carbon source in the denitrification stage is a problem faced by most sewage treatment plants in China. At present, commercial carbon sources such as acetic acid, ethanol, methanol, sodium acetate and the like are used as supplementary carbon sources and are added into sewage treatment by sewage plants so as to ensure that the quality of effluent water reaches the standard. However, the above supplementary carbon source is generally expensive, increases the running cost of sewage treatment, is essentially a chemical product, is greatly limited in the transportation, storage and use processes, and does not conform to the development direction of global carbon peak reaching and carbon neutralization.
The citric acid is obtained by fermenting, purifying, concentrating, crystallizing and the like the sweet potatoes, the corns and the starch which are used as production raw materials, is the organic acid with the maximum global production capacity, and according to statistics, about 40 tons of citric acid fermentation wastewater can be discharged when 1 ton of citric acid products are produced. As typical high-concentration organic wastewater, the citric acid fermentation wastewater mainly comprises organic acids, carbohydrates, fats, proteins and the like which are not completely utilized in the fermentation process, and if the citric acid fermentation wastewater is directly thrown into the wastewater, some macromolecular organic matters cannot be directly utilized by denitrifying bacteria, so that the propagation and development of the macromolecular organic matters are not facilitated, and the denitrification rate is further influenced. Crude glycerol is a byproduct in the production process of biodiesel, consists of glycerol, methanol, inorganic salt, ash and other multi-species, and is widely used as a surfactant, a wetting agent and other auxiliary agents, fertilizer raw materials and other fields due to the advantages of solubility, dispersibility, no toxicity, no harm and the like. The citric acid fermentation wastewater and the crude glycerol not only increase the cost but also cause the waste of a large amount of resources if directly biochemically treated and discharged.
Disclosure of Invention
The invention aims to provide a method for preparing a biological composite carbon source by using citric acid fermentation wastewater on the basis of the prior art.
Another object of the present invention is to provide a biocomposite carbon source prepared by the above method.
The third purpose of the invention is to provide the application of the biological composite carbon source as a carbon source in the denitrification process of wastewater.
The technical scheme of the invention is as follows:
a method for preparing a biological composite carbon source by using citric acid fermentation wastewater comprises the following steps:
(1) adjusting the pH value of the citric acid fermentation wastewater to 9-11 by adopting a sodium hydroxide solution, adding a flocculating agent polyaluminium chloride, stirring for reacting for 1-3 h, standing and filtering;
wherein the mass volume ratio of the polyaluminium chloride to the citric acid fermentation wastewater is 1.5-4.5: 1 g/L;
(2) adjusting the pH value of the filtrate obtained in the step (1) to 8-11, and then performing fermentation treatment, wherein the fermentation temperature is 30-50 ℃, and the fermentation time is 9-12 days; after the fermentation is finished, adding a phosphorus source NaH into the mixture2PO4And a source of magnesium MgCl2·6H2O, stirring and reacting for 1-2 hours to obtain struvite sediment, and filtering; then, adding CaO into the obtained filtrate, continuously stirring and reacting for 1-2 hours to obtain calcium phosphate precipitate, and filtering again;
wherein, NaH2PO4The mass volume ratio of the citric acid fermentation wastewater to the citric acid fermentation wastewater in the step (1) is 2.5-4.5: 1 g/L; MgCl2·6H2The mass-to-volume ratio of the O to the citric acid fermentation wastewater in the step (1) is 6.0-10.0: 1 g/L; the mass-to-volume ratio of CaO to the citric acid fermentation wastewater in the step (1) is 2.0-4.0: 1 g/L;
(3) concentrating the filtrate obtained in the step (2) by using solar energy, wherein the concentration temperature is 30-50 ℃, and the concentration multiple is 10-40 times;
(4) uniformly mixing the concentrated solution obtained in the step (3), crude glycerol and water at 35-45 ℃ to obtain a mixture, and continuously stirring for 2-4 h to obtain a biological composite carbon source;
wherein the percentage content of the concentrated solution is 35-45% based on the total volume of the mixture as 100%; the percentage content of the crude glycerol is 30-40%.
In a preferred embodiment, the citric acid fermentation wastewater in the step (1) comprises the following components: citric acid 10-50 mg/L, COD 20000-25000 mg/L, BOD5 13000～17000mg/L，TN 200～400mg/L，TP 100～300mg/L，SS 200～400mg/L。
In a more preferable embodiment, the citric acid fermentation wastewater in the step (1) comprises the following components: citric acid 25mg/L, COD 22000mg/L, BOD5 15000mg/L，TN 300mg/L，TP 200mg/L，SS 280mg/L。
For the invention, in the step (1), the pH value of the citric acid fermentation wastewater is adjusted to 9-11 by adopting a sodium hydroxide solution, and the mass content of the sodium hydroxide solution is 10-30%, preferably 20%.
For the invention, in the step (2), the filtrate obtained in the step (1) is added into a hydrolysis acidification tank, the pH value is adjusted to 8-11, then fermentation is carried out, a hydraulic transmission system is arranged at the bottom of the hydrolysis acidification tank, and the wastewater to be fermented is slowly stirred at a constant speed by a stirring device arranged in the tank. The fermentation temperature is 30-50 ℃, and the fermentation time is 9-12 days; in the fermentation process of the wastewater to be fermented, macromolecules such as carbohydrates, fats and proteins in the wastewater are degraded into micromolecular organic matters such as monosaccharides, organic acids such as acetic acid, propionic acid and butyric acid, amino acids, fatty acids and glycerol, so that the prepared biological composite carbon source is beneficial to utilization of denitrifying bacteria when being used as a carbon source in the biological nitrogen and phosphorus removal process of the wastewater, and the nitrogen and phosphorus removal efficiency is improved.
For the purposes of the present invention, in step (2), NaH2PO4、MgCl2·6H2The amounts of O and CaO are important, NaH2PO4And MgCl2·6H2The higher or lower dosage of O is not beneficial to removing ammonia nitrogen in the wastewater. The higher or lower CaO dosage is not beneficial to removing the phosphorus in the wastewater.
In a preferred embodiment, in step (2), NaH2PO4The mass-to-volume ratio of the citric acid fermentation wastewater in the step (1) to the citric acid fermentation wastewater is 3.5-4.0: 1g/L, and preferably 3.6:1 g/L.
Further, MgCl2·6H2The mass-volume ratio of the O to the citric acid fermentation wastewater in the step (1) is 7.5-8.5: 1g/L, and 8:1g/L is preferred.
Further, the mass-volume ratio of CaO to the citric acid fermentation wastewater in the step (1) is 2.5-3.0: 1g/L, and preferably 2.8:1 g/L.
In a preferable scheme, in the step (3), the concentration temperature is 50 ℃, and the concentration multiple is 20-30, preferably 25.
For the present invention, in the step (4), the temperature at the time of mixing is 40 ℃.
In the step (4), the concentrated solution obtained in the step (3), the crude glycerol and water are uniformly mixed to obtain a mixture, wherein the content of the crude glycerol in the mixture is important for preparing the biological composite carbon source. For example, when the content of crude glycerin is relatively high, not only is the cost increased, but also secondary pollution is easily caused; when the content of the crude glycerol is low, the organic matter content of the whole biological composite carbon source is low, so that the efficiency of the subsequent water treatment process is influenced.
In a preferred embodiment, the percentage of the concentrate is 40% based on 100% of the total volume of the mixture; the percentage content of the crude glycerol is 35%.
In a preferred embodiment, the percentage of the concentrate is 35% based on 100% of the total volume of the mixture; the percentage content of the crude glycerol is 30%.
In a preferred embodiment, the percentage of the concentrate is 45% based on 100% of the total volume of the mixture; the percentage content of the crude glycerol is 40%.
For the present invention, in the step (4), the concentrated solution comprises the following components in parts by weight: 40-60 parts of organic acid, 10-25 parts of total sugar and inorganic salt, 0.5-0.8 part of TN and 0.4-0.8 part of TP.
In a preferable scheme, in the step (4), the concentrated solution comprises the following components in parts by weight: 50 parts of organic acid, 20 parts of total sugar and inorganic salt, 0.8 part of TN and 0.5 part of TP.
In the step (4), the crude glycerol provided by the invention comprises the following components in parts by weight: 70-90 parts of glycerol, 5-30 parts of methanol and 1-15 parts of inorganic salt.
In a preferred embodiment, in the step (4), the raw glycerol comprises the following components in parts by weight: 80 parts of glycerol, 10 parts of methanol and 5 parts of inorganic salt.
The preparation method of the biological composite carbon source comprises the following more detailed steps:
(1) adding citric acid fermentation wastewater into a reaction tank, and adding a NaOH solution with the mass content of 10-30% (w/w) for regulationAnd (3) adding flocculant polyaluminium chloride (PAC) to react for 1-3 h after the pH value is 9-11. After the reaction is finished, standing for 1h and then filtering to remove PO in the wastewater4 3-、SO4 2-Ions and Solid Suspensions (SS). Wherein the mass volume ratio of the polyaluminium chloride to the citric acid fermentation wastewater is 1.5-4.5: 1 g/L.
(2) Adding the filtrate obtained in the step (1) into a hydrolysis acidification tank, adjusting the pH value of the hydrolysis acidification tank to 8-11, and then fermenting, wherein a hydraulic transmission system is installed at the bottom of the hydrolysis acidification tank, and the wastewater to be fermented is slowly stirred at a constant speed by a stirring device arranged in the tank. The fermentation temperature is 30-50 ℃, and the fermentation time is 9-12 days. In the fermentation process of the wastewater to be fermented, macromolecules such as carbohydrates, fat, proteins and the like in the wastewater are degraded into micromolecular organic matters such as organic acids such as monosaccharides, acetic acid, propionic acid, butyric acid and the like, amino acids, fatty acids, glycerol and the like.
After the fermentation is finished, adding a phosphorus source NaH into the mixture2PO4And a source of magnesium MgCl2·6H2And O, stirring and reacting for 1-2 h to obtain struvite precipitate so as to remove ammonia nitrogen in the wastewater, and filtering. Then, adding CaO into the obtained filtrate, continuously stirring and reacting for 1-2 hours to obtain calcium phosphate precipitate to remove phosphorus in the wastewater, and filtering again.
Wherein, the NaH2PO4The mass volume ratio of the citric acid fermentation wastewater to the citric acid fermentation wastewater in the step (1) is 2.5-4.5: 1 g/L; said MgCl2·6H2The mass-to-volume ratio of the O to the citric acid fermentation wastewater in the step (1) is 6.0-10.0: 1 g/L; the mass-volume ratio of the CaO to the citric acid fermentation wastewater in the step (1) is 2.0-4.0: 1 g/L.
(3) And (3) concentrating the filtrate obtained in the step (2) by using solar energy, wherein the concentration temperature is 30-50 ℃, and the concentration multiple is 10-40 times.
(4) And (3) uniformly mixing the concentrated solution obtained in the step (3), crude glycerol and water at 35-45 ℃ to obtain a mixture, continuously stirring for 2-4 h, and cooling to room temperature to obtain the biological composite carbon source. The percentage content of the concentrated solution is 35-45% based on the total volume of the mixture as 100%; the percentage content of the crude glycerol is 30-40%.
The biological composite carbon source is a mixture consisting of citric acid fermentation wastewater concentrated solution, crude glycerol and water. Wherein the percentage content of the concentrated solution is 35-45% based on the total volume of the mixture as 100%; the percentage content of the crude glycerol is 30-40%. In a preferred embodiment, the percentage of the concentrate is 40% based on 100% of the total volume of the mixture; the percentage content of crude glycerol was 35%.
The concentrated solution comprises the following components in parts by weight: 40-60 parts of organic acid, 10-25 parts of total sugar and inorganic salt, 0.5-0.8 part of TN and 0.4-0.8 part of TP. Preferably, the concentrated solution comprises the following components in parts by weight: 50 parts of organic acid, 20 parts of total sugar and inorganic salt, 0.8 part of TN and 0.5 part of TP.
The crude glycerol comprises the following components in parts by weight: 70-90 parts of glycerol, 5-30 parts of methanol and 1-15 parts of inorganic salt. Preferably, the crude glycerol comprises the following components in parts by weight: 80 parts of glycerol, 10 parts of methanol and 5 parts of inorganic salt.
The invention inherits the principle of 'treating waste by waste', prepares a biological composite carbon source by mixing the citric acid fermentation wastewater concentrated solution and the crude glycerol, is used as a carbon source in the wastewater denitrification process, has an efficient removal effect on nitrogen and phosphorus in the denitrification process, and can lead effluent to reach the first-grade A standard of urban sewage. The biological composite carbon source provided by the invention not only solves the problems of complexity, high cost and secondary pollution of the existing carbon source preparation method, but also can save resources and reduce the sewage treatment cost, and has important guiding significance for expanding the development and application field of biomass resources and improving the sewage treatment economy.
By adopting the technical scheme of the invention, the advantages are as follows:
(1) according to the method for preparing the biological composite carbon source by using the citric acid fermentation wastewater, provided by the invention, the wastewater after flocculation treatment is fermented, so that macromolecules such as carbohydrates, fat and proteins in the wastewater are degraded into organic matters such as organic acids, amino acids and fatty acids with small molecular weights, the utilization of denitrifying bacteria is facilitated, and the nitrogen and phosphorus removal efficiency is further improved.
(2) When the biological composite carbon source is prepared, the phosphorus source and the magnesium source are added after fermentation to generate struvite precipitate, which is an excellent nitrogen-phosphorus fertilizer and can be recycled as a resource.
(3) The invention utilizes solar energy to concentrate the citric acid fermentation wastewater after flocculation, fermentation and chemical sedimentation treatment, thereby reducing the concentration cost.
(4) The method takes the citric acid fermentation wastewater as a raw material to prepare the biological composite carbon source, thereby not only changing waste into valuable and saving resources, but also reducing the treatment cost of the citric acid fermentation wastewater.
(5) The method prepares the biological composite carbon source by mixing the treated citric acid fermentation wastewater concentrated solution and the crude glycerol, strictly controls the content of the concentrated solution and the crude glycerol in the biological composite carbon source, has high-efficiency removal effect on nitrogen and phosphorus in the denitrification process when being used as the carbon source for wastewater treatment, and can ensure that effluent can reach the first-grade A standard of urban sewage.
Drawings
FIG. 1 is a flow chart of the present invention for preparing a biological composite carbon source by using citric acid fermentation wastewater.
Detailed Description
The biocomposite carbon source and the method for producing the same according to the present invention will be further illustrated by the following examples in conjunction with the drawings, but the present invention is not limited to these examples.
Example 1
A method for preparing a biological composite carbon source by using citric acid fermentation wastewater comprises the following steps:
(1) adding 50L of citric acid fermentation wastewater into a reaction tank, adding 20% (w/w) NaOH solution by mass content to adjust the pH value to 9-11, adding 150g of flocculant polyaluminum chloride (PAC), and stirring for reaction for 1 h. After the reaction is finished, standing for 1h and then filtering to remove PO in the wastewater4 3-、SO4 2-Ions and Solid Suspensions (SS).
(2) Adding the filtrate obtained in the step (1) into a hydrolysis acidification tank, adjusting the pH value of the hydrolysis acidification tank to 8-11, and then fermenting, wherein a hydraulic transmission system is installed at the bottom of the hydrolysis acidification tank, and the wastewater to be fermented is slowly stirred at a constant speed by a stirring device arranged in the tank. The fermentation temperature is 35 ℃, and the fermentation time is 10 days. In the fermentation process of the wastewater to be fermented, macromolecules such as carbohydrates, fat, proteins and the like in the wastewater are degraded into micromolecular organic matters such as organic acids such as monosaccharides, acetic acid, propionic acid, butyric acid and the like, amino acids, fatty acids, glycerol and the like.
After the fermentation is finished, 180g of NaH as a phosphorus source is added2PO4And 405g of MgCl as a source of magnesium2·6H2And O, stirring and reacting for 1.5 hours to obtain struvite sediment for removing ammonia nitrogen in the wastewater, and filtering. And then, adding 140g of calcium source CaO into the obtained filtrate, continuously stirring and reacting for 1-2 h to obtain calcium phosphate precipitate to remove phosphorus in the wastewater, and filtering again.
The contents and removal rates of indexes in the wastewater before and after the citric acid fermentation wastewater is subjected to fermentation and chemical precipitation reaction are shown in the following table:
| detecting items | CODcr | BOD5 | TN | TP | SS |
| Content before treatment (mg/L) | 22000 | 15000 | 300 | 200 | 280 |
| Content after treatment (mg/L) | 20570 | 13920 | 35 | 15 | 26 |
| Removal Rate (%) | 6.5 | 7.2 | 88.3 | 92.5 | 90.7 |
(3) And (3) concentrating the filtrate obtained in the step (2) by using solar energy, wherein the concentration temperature is 50 ℃, and the concentration multiple is 25 times.
(4) And (3) uniformly mixing the concentrated solution obtained in the step (3), crude glycerol and water at 40 ℃ to obtain a mixture, continuously stirring for 2-4 h, and cooling to room temperature to obtain the biological composite carbon source. The percentage content of the concentrated solution is 35 percent based on the total volume of the mixture as 100 percent; the percentage content of crude glycerol is 30%; the percentage of water is 35%. Wherein the concentrated solution comprises the following components in parts by weight: 50 parts of organic acid, 20 parts of total sugar and inorganic salt, 0.8 part of TN and 0.5 part of TP; the crude glycerol comprises the following components in parts by weight: 80 parts of glycerol, 10 parts of methanol and 5 parts of inorganic salt.
Example 2
This example differs from example 1 in that in step (4), the percentage of concentrate is 40%, based on 100% of the total volume of the mixture; the percentage content of crude glycerol is 35%; the percentage of water is 25%. Other steps and parameter conditions were the same as in example 1.
Example 3
This example differs from example 1 in that in step (4), the percentage of concentrate is 45%, based on 100% of the total volume of the mixture; the percentage content of the crude glycerol is 40 percent; the percentage of water is 15%. Other steps and parameter conditions were the same as in example 1.
Comparative example 1
The difference between the comparative example and the example 1 is that in the step (4), crude glycerin is not added, the concentrated solution obtained in the step (3) and water are directly and uniformly mixed to obtain a mixture, and the percentage content of the concentrated solution is 45 percent based on the total volume of the mixture as 100 percent; the percentage of water is 55%.
Comparative example 2
In the comparative example, the crude glycerol and water are directly and uniformly mixed to obtain a mixture, the mixture is continuously stirred for 2-4 hours, and the mixture is cooled to room temperature, so that the biological composite carbon source is obtained. The percentage content of crude glycerol is 40% based on the total volume of the mixture being 100%; the percentage of water is 60%.
Comparative example 3
The comparative example differs from example 1 in that the filtrate obtained in step (1) was concentrated directly by solar energy at 50 ℃ with a concentration factor of 25, excluding step (2). Other procedures and parameters were as in example 1. Wherein the concentrated solution comprises the following components in parts by weight: 40 parts of organic acid, 20 parts of total sugar and inorganic salt, 2 parts of TN and 3.5 parts of TP; the crude glycerol comprises the following components in parts by weight: 80 parts of glycerol, 10 parts of methanol and 5 parts of inorganic salt.
Since the comparative example does not include the step (2), the content and removal rate of each index in the wastewater before and after the flocculation treatment of the citric acid fermentation wastewater in the step (1) are as follows:
| detecting items | CODcr | BOD5 | TN | TP | SS |
| Content before treatment (mg/L) | 22000 | 15000 | 300 | 200 | 280 |
| Content after treatment (mg/L) | 20700 | 14900 | 290 | 180 | 30 |
| Removal Rate (%) | 5.9 | 6.7 | 3.3 | 10.0 | 89.3 |
Comparative example 4
This comparative example differs from example 1 in that in step (2), the source of NaH is a phosphorus source2PO4MgCl as magnesium source2·6H2Addition of O and CaOThe amount was adjusted as follows: phosphorous source NaH2PO480g of MgCl, a source of magnesium2·6H2O200 g and CaO 50g, and other steps and parameter conditions were the same as in example 1.
The contents and removal rates of indexes in the wastewater before and after the citric acid fermentation wastewater is subjected to fermentation and chemical precipitation reaction are shown in the following table:
| detecting items | CODcr | BOD5 | TN | TP | SS |
| Content before treatment (mg/L) | 22000 | 15000 | 300 | 200 | 280 |
| Content after treatment (mg/L) | 20560 | 13900 | 160 | 150 | 30 |
| Removal rate (%) | 6.5 | 7.3 | 46.6 | 25.0 | 89.2 |
Wherein the concentrated solution comprises the following components in parts by weight: 45 parts of organic acid, 15 parts of total sugar and inorganic salt, 1.5 parts of TN and 1.2 parts of TP; the crude glycerol comprises the following components in parts by weight: 80 parts of glycerol, 10 parts of methanol and 5 parts of inorganic salt.
Comparative example 5
This comparative example differs from example 1 in that in step (2), the source of NaH is a phosphorus source2PO4MgCl as magnesium source2·6H2The addition amounts of O and CaO were adjusted as follows: phosphorous source NaH2PO4300g of MgCl, source of magnesium2·6H2O600 g and CaO 350g, and other steps and parameter conditions were the same as in example 1.
The contents and removal rates of indexes in the wastewater before and after the citric acid fermentation wastewater is subjected to fermentation and chemical precipitation reaction are shown in the following table:
| detecting items | CODcr | BOD5 | TN | TP | SS |
| Content before treatment (mg/L) | 22000 | 15000 | 300 | 200 | 280 |
| Content after treatment (mg/L) | 20650 | 13950 | 150 | 135 | 40 |
| Removal Rate (%) | 6.1 | 7.0 | 50.0 | 32.5 | 85.7 |
Wherein the concentrated solution comprises the following components in parts by weight: 50 parts of organic acid, 20 parts of total sugar and inorganic salt, 1.0 part of TN and 0.3 part of TP; the crude glycerol comprises the following components in parts by weight: 80 parts of glycerol, 10 parts of methanol and 5 parts of inorganic salt.
Comparative example 6
The comparative example differs from example 1 in that in step (4), the amount of crude glycerin added was adjusted as follows: the percentage content of the concentrated solution is 40 percent based on the total volume of the mixture as 100 percent; the percentage content of crude glycerol is 20%; the percentage of water is 40%. Other steps and parameter conditions were the same as in example 1.
Comparative example 7
The comparative example differs from example 1 in that in step (4), the amount of crude glycerin added was adjusted as follows: the percentage content of the concentrated solution is 40 percent based on the total volume of the mixture as 100 percent; the percentage content of crude glycerol is 50%; the percentage of water is 10%. Other steps and parameter conditions were the same as in example 1.
The biological composite carbon source prepared in the examples 1 to 3 and the comparative examples 1 to 7 and sodium acetate, methanol and glucose as carbon sources are respectively used in the biological nitrogen and phosphorus removal process of wastewater for the verification of the denitrification effect, which is specifically as follows:
the contents of all indexes in the wastewater to be treated with the temperature of 25 ℃ and the pH value of 9 are as follows: the ammonia nitrogen concentration is 360mg/L, the BOD is 400mg/L, the COD is 150mg/L, and 100mL of the ammonia nitrogen is addedComposite carbon source/LWaste waterTreating for 12-24h, wherein the effluent can reach the first-grade A standard of urban sewage according to the concentration of ammonia nitrogen in the denitrification process.
The carbon source in the examples and the comparative examples is subjected to denitrification effect verification, and the results are as follows:
as can be seen from the above table, the biological composite carbon source prepared in the embodiment of the invention has significantly better denitrification and dephosphorization effects than the comparative example. Particularly, in example 2, the removal rate of ammonia nitrogen was 98.6%, and COD and BOD in the effluent thereof were found to be5The nitrogen and nitrogen removal rate is the lowest, namely the nitrogen and phosphorus removal effect is the best. In comparative examples 1 to 7, COD in the effluent was high and the removal rate of nitrate and nitrogen was low, and the denitrification and dephosphorization effects were much lower than those of examples 1 to 3 and the single carbon source. Therefore, the adding amount of the phosphorus source, the magnesium source and the calcium source and the proportion of the crude glycerol in the biological composite carbon source provided by the invention have great influence. Although the removal rates of COD and nitro-nitrogen in the effluent water were equivalent to those of sodium acetate, methanol and glucose as single carbon sources in the biological composite carbon source in example 1-2, most of sodium acetate was liquidThe adding amount is large, the transportation cost is high, the sludge yield is high, and pressure is caused on subsequent sludge treatment; the methanol is not only flammable and explosive, but also has certain toxic action on the growth and the propagation of microorganisms when being added as a carbon source; glucose is a multi-molecular organic matter, sludge bulking is easily caused, COD of effluent is increased, and accumulation of nitrite nitrogen is easy to occur. The biological composite carbon source provided by the invention not only saves resources, but also is non-toxic and harmless, avoids the defects of the single carbon source, and shows excellent removal effect on denitrification nitrate nitrogen and COD of sewage.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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: modifications of the technical solutions described in the foregoing embodiments are still possible, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing a biological composite carbon source by using citric acid fermentation wastewater is characterized by comprising the following steps:
(1) adjusting the pH value of the citric acid fermentation wastewater to 9-11 by adopting a sodium hydroxide solution, adding a flocculating agent polyaluminium chloride, stirring for reacting for 1-3 h, standing and filtering;
wherein the mass volume ratio of the polyaluminium chloride to the citric acid fermentation wastewater is 1.5-4.5: 1 g/L;
(2) adjusting the pH value of the filtrate obtained in the step (1) to 8-11, and then performing fermentation treatment, wherein the fermentation temperature is 30-50 ℃, and the fermentation time is 9-12 days; after the fermentation is finished, adding a phosphorus source NaH into the mixture2PO4And a source of magnesium MgCl2·6H2O, stirring and reacting for 1-2 hours to obtain struvite sediment, and filtering; then, adding CaO into the obtained filtrate, continuously stirring and reacting for 1-2 hours to obtain calcium phosphate precipitate, and filtering again;
wherein, the NaH2PO4The mass volume of the citric acid fermentation wastewater in the step (1)The ratio is 2.5-4.5: 1 g/L; said MgCl2·6H2The mass-to-volume ratio of the O to the citric acid fermentation wastewater in the step (1) is 6.0-10.0: 1 g/L; the mass-to-volume ratio of the CaO to the citric acid fermentation wastewater in the step (1) is 2.0-4.0: 1 g/L;
(3) concentrating the filtrate obtained in the step (2) by using solar energy, wherein the concentration temperature is 30-50 ℃, and the concentration volume multiple is 10-40 times;
(4) uniformly mixing the concentrated solution obtained in the step (3), crude glycerol and water at 35-45 ℃ to obtain a mixture, and continuously stirring for 2-4 h to obtain a biological composite carbon source;
wherein the percentage content of the concentrated solution is 35-45% based on the total volume of the mixture as 100%; the percentage content of the crude glycerol is 30-40%.
2. The method according to claim 1, wherein in the step (1), the citric acid fermentation wastewater comprises the following components: citric acid 10-50 mg/L, COD 20000-25000 mg/L, BOD513000-17000 mg/L, TN 200-400 mg/L, TP 100-300 mg/L, and SS 200-400 mg/L; preferably, the citric acid fermentation wastewater comprises the following components: citric acid 25mg/L, COD 22000mg/L, BOD5 15000mg/L，TN 300mg/L，TP 200mg/L，SS 280mg/L。
3. The preparation method according to claim 1, wherein in the step (1), the mass volume ratio of the polyaluminium chloride to the citric acid fermentation wastewater is 2.5-3.5: 1g/L, preferably 3.0:1 g/L; the mass content of the sodium hydroxide solution is 10-30%, and preferably 20%.
4. The method as claimed in claim 1, wherein in step (2), the NaH is added2PO4The mass-to-volume ratio of the citric acid fermentation wastewater in the step (1) to the citric acid fermentation wastewater is 3.5-4.0: 1g/L, and preferably 3.6:1 g/L; said MgCl2·6H2The mass-volume ratio of the O to the citric acid fermentation wastewater in the step (1) is 7.5-8.5: 1g/L, and preferably 8:1 g/L; the CaO and the citric acid fermentation waste in the step (1)The mass-volume ratio of the water is 2.5-3.0: 1g/L, and preferably 2.8:1 g/L.
5. The method according to claim 1, wherein in the step (3), the concentration temperature is 50 ℃ and the concentration multiple is 20-30, preferably 25.
6. The method according to claim 1, wherein, in the step (4), the temperature at the time of mixing is 40 ℃; the percentage of the concentrated solution is 40 percent based on the total volume of the mixture as 100 percent; the percentage content of the crude glycerol is 35%.
7. The method as claimed in claim 1, wherein in the step (4), the concentrated solution comprises the following components in parts by weight: 40-60 parts of organic acid, 10-25 parts of total sugar and inorganic salt, 0.5-0.8 part of TN and 0.4-0.8 part of TP; the crude glycerol comprises the following components in parts by weight: 70-90 parts of glycerol, 5-30 parts of methanol and 1-15 parts of inorganic salt.
8. The method as claimed in claim 7, wherein in the step (4), the concentrated solution comprises the following components in parts by weight: 50 parts of organic acid, 20 parts of total sugar and inorganic salt, 0.8 part of TN and 0.5 part of TP; the crude glycerol comprises the following components in parts by weight: 80 parts of glycerol, 10 parts of methanol and 5 parts of inorganic salt.
9. A biocomposite carbon source prepared by the method of any one of claims 1-7.
10. Use of the biocomposite carbon source of claim 1 as a carbon source in wastewater denitrification processes.
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