CN113562846A - Denitrification efficient carbon source and processing technology thereof - Google Patents
Denitrification efficient carbon source and processing technology thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 115
- 238000005516 engineering process Methods 0.000 title claims abstract description 9
- 238000012545 processing Methods 0.000 title claims abstract description 8
- 238000000855 fermentation Methods 0.000 claims abstract description 40
- 230000004151 fermentation Effects 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000002028 Biomass Substances 0.000 claims abstract description 24
- 239000003610 charcoal Substances 0.000 claims abstract description 23
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004343 Calcium peroxide Substances 0.000 claims abstract description 20
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000019402 calcium peroxide Nutrition 0.000 claims abstract description 20
- 150000004676 glycans Chemical class 0.000 claims abstract description 18
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 18
- 239000005017 polysaccharide Substances 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 241001646834 Mesona Species 0.000 claims abstract description 8
- 241000195493 Cryptophyta Species 0.000 claims description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 244000183278 Nephelium litchi Species 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 244000060011 Cocos nucifera Species 0.000 claims description 11
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000010802 sludge Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 241001646828 Platostoma chinense Species 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229940012466 egg shell membrane Drugs 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000011081 inoculation Methods 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000013268 sustained release Methods 0.000 claims description 5
- 239000012730 sustained-release form Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 241000192700 Cyanobacteria Species 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 150000004666 short chain fatty acids Chemical class 0.000 abstract description 22
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 230000002829 reductive effect Effects 0.000 abstract description 11
- 230000002708 enhancing effect Effects 0.000 abstract description 5
- 230000002860 competitive effect Effects 0.000 abstract description 4
- 238000005538 encapsulation Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 241001629511 Litchi Species 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 235000021391 short chain fatty acids Nutrition 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000002407 ATP formation Effects 0.000 description 2
- 102000004157 Hydrolases Human genes 0.000 description 2
- 108090000604 Hydrolases Proteins 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000010065 bacterial adhesion Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000035425 carbon utilization Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a denitrification high-efficiency carbon source and a processing technology thereof. A processing technology of a denitrification high-efficiency carbon source comprises the following steps: s1: preparing an organic carbon source; s2: preparing a slow release carrier; s3: and (3) preparing a high-efficiency carbon source. Has the advantages that: (1) the combination of potassium ferrate and calcium peroxide obviously enhances the abundance of short-chain fatty acid and reduces the competitive adsorption, thereby using Fe0Adsorbing the/Ca-Al-LDH to obtain a carbon source A. (2) The carbon source A and the litchi powder are mixed and encapsulated by using the Mesona polysaccharide and the algal polysaccharide to form a double slow-release carbon source, so that the use efficiency of the carbon source is effectively enhanced. (3) The mixed biomass charcoal is added, so that the fermentation rate is obviously enhanced, and meanwhile, the use amount of sodium hydroxide is reduced. (4) Enhancing powdered Fe Using encapsulation techniques0The use convenience of the/Ca-Al-LDH is realized, and effective separation can be realized after the carbon source is completely released.
Description
Technical Field
The invention relates to the technical field of denitrification, in particular to a denitrification efficient carbon source and a processing technology thereof.
Background
High nitrogen wastewater is always the key point in the field of water treatment, and microbial denitrification treatment is one of the common processes. In the microbial denitrification process, a carbon source is required to be provided to promote the denitrification of the microorganisms. The carbon source comprises an organic carbon source, a natural carbon source, a polymer carbon source and the like, and the traditional organic carbon source is a large and medium liquid carbon source, so that the dosage is not easy to control, the sewage quality is unstable, and secondary pollution is easy to generate. The short-chain fatty acid obtained by biological fermentation is used as a carbon source and is fixed by an adsorbent, so that the process is stable and controllable. However, the carbon source produced by fermentation contains heavy metals and other harmful substances in the fermentation broth, and the direct addition of the carbon source not only increases the nitrogen load, but also causes harm to the denitrifying agent. Meanwhile, most carriers for adsorbing the short-chain fatty acid are powder, so that the carrier is not recycled and is limited in use. In addition, the common carbon source has the problem of difficult control of effective addition amount, influences the denitrification efficiency of the carbon source, causes waste of the carbon source, and causes sewage to need secondary treatment.
Therefore, the preparation of a denitrification efficient carbon source has important significance for solving the problems.
Disclosure of Invention
The invention aims to provide a denitrification efficient carbon source and a processing technology thereof, and aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a processing technology of a denitrification high-efficiency carbon source comprises the following steps:
s1: preparation of organic carbon source: crushing and concentrating blue algae to obtain blue algae mixed solution, placing the blue algae mixed solution into a reaction tank, and sequentially adding calcium peroxide, potassium ferrate and citric acid for pretreatment; adding mixed biomass charcoal, inoculating activated sludge, adjusting pH, purifying and deoxidizing with nitrogen, fermenting, and filtering to obtain fermentation liquor;
s2: preparation of the sustained-release carrier: cleaning eggshell membrane, drying, pulverizing, and heat treating; dissolving the powder in deionized water, grinding to obtain a calcium hydroxide solution, dropwise adding an aluminum hydroxide solution, mixing, performing ultrasonic treatment, precipitating and aging to obtain Ca-Al-LDH; soaking the Fe-B-Fe alloy in a ferrous sulfate solution, stirring, dropwise adding sodium borohydride, and drying a sample to obtain Fe0/Ca-Al-LDH；
S3: preparing a high-efficiency carbon source: mixing Fe0Soaking the/Ca-Al-LDH in fermentation liquor, and freeze-drying to obtain a carbon source A; mixing the carbon source A with litchi powder and Mesona chinensis Benth polysaccharide; adding into sodium alginate solution to form suspension, adding calcium chloride solution to form micro gel; extruding the carbon source into calcium chloride solution to be solidified and crosslinked to obtain the microspherical efficient carbon source.
Preferably, in step S1, the addition amount of the calcium peroxide is 4-8% of the solid content in the blue algae mixed solution; the adding amount of the biomass charcoal is 30-50% of the solid content in the blue algae mixed liquid; the inoculation amount of the activated sludge is 10-12% of the blue algae mixed liquid.
Preferably, in step S1, the mixed biomass charcoal is prepared by mixing coconut shells and blue-green algae, and the mass ratio of the coconut shells to the blue-green algae is (2-3): 1.
Preferably, in the step S1, the pretreatment temperature is 20-21 ℃, and the pretreatment time is 12-24 hours; the adding ratio of the calcium peroxide, the potassium ferrate and the citric acid is 1 (1.2-1.5) to 0.2-0.3.
Preferably, in step S1, the pH adjusted by sodium hydroxide is 9.5 to 10, the purification and deoxidation time is 20 to 40 minutes, the fermentation temperature is 35 to 38 ℃, and the fermentation time is 3 to 6 days.
Preferably, in step S2, the concentration of the ferrous sulfate solution is 0.3-0.5 mmol/L; the concentration of sodium borohydride was 0.1 mol/L.
Preferably, in step S3, the dipping temperature is 10 to 30 ℃, and the dipping time is 3 to 5 hours.
Preferably, in the step S3, the mass ratio of the carbon source A to the litchi powder is 2 (0.8-1.2); the adding amount of the mesona polysaccharide is 1-2 times of the total mass of the carbon source A and the litchi powder.
Preferably, the high-efficiency carbon source is microspheres, and the particle size is 0.8-1.2 mu m.
In the scheme, the carbon source A adsorbed with the short-chain fatty acid is mixed with the litchi powder with the starch base to form a mixed carbon source, and compared with a single carbon source, the denitrification performance and the denitrification efficiency are obviously enhanced. Meanwhile, the utilization rate of the carbon source is improved by using a slow release process.
(1) In recent years, due to water eutrophication, the pollution of blue algae is serious, so in the scheme, the blue algae waste of a polluting species is utilized for fermentation preparation of short-chain fatty acid, and then the short-chain fatty acid is adsorbed by an adsorbent to obtain a denitrification carbon source A. The anaerobic fermentation is seriously hindered due to the rigid cell wall structure of the algae, so that the surface morphology and the cell structure of the blue algae are damaged by adding potassium ferrate, the solubilization of the blue algae is promoted, more short-chain fatty acids are produced by fermentation, the generation of methane is inhibited, and the pH is adjusted to be 9.5-10 in the scheme; (generally, the yield of fatty acid produced is highest when the pH value of the algae is 11, the yield of methane is highest when the pH value is 7-9, the yield of methane is equivalent to that when the pH value is 9-10; therefore, the pH value is generally adjusted to 10-11, and a large amount of short-chain fatty acid is generated by fermentation.) in addition, the abundance of hydrolytic bacteria can be increased by about 4-5 times due to the potassium ferrate, so the generation of the short-chain fatty acid is remarkably enhanced.
On the other hand, because the blue algae is obtained by water eutrophication, a large amount of metal ions such as phosphorus, arsenic and the like can be generated, and potassium ferrate can oxidize and precipitate the ions such as phosphorus, arsenic and the like, thereby reducing the impurities of the fermentation liquor. In addition, more carbonate is generated after fermentation, and the carbonate competes with short-chain fatty acid for adsorption, so that subsequent adsorption and extraction are influenced.
Therefore, calcium peroxide is also added in the scheme, and can be used for enhancing the generation of short-chain fatty acids in cooperation with potassium ferrate. On the one hand, it is more reactive with carbonic acid in the calcium hydroxide produced, so that most of the carbonate in the fermentation broth is removed. On the other hand, in the presence of citric acid, potassium ferrate generates ferric ions in the fermentation liquor, so that the potassium ferrate generates an activating effect on calcium peroxide and enhances the adsorption and precipitation of organic impurities.
In addition, the activity of hydrolase produced in the fermentation process can be enhanced by adding the mixed biomass charcoal, and meanwhile, due to the porous structure of the mixed biomass charcoal, the microorganism is favorably attached and accumulated to form a micro-fermentation reactor, so that the electron transmission and ATP synthesis are enhanced, the growth and metabolism of anaerobic bacteria are accelerated in the fermentation process, and the fermentation rate is obviously increased. Wherein, the coconut shell ash increases the alkalinity of fermentation and reduces the usage amount of sodium hydroxide in pH adjustment.
In conclusion, on the basis of increasing the fermentation rate, the abundance of short-chain fatty acids in the fermentation liquor is obviously enhanced, and the toxicity and competitive adsorption of subsequent adsorption are reduced.
(2) Prepare the toolThe anion adsorbent Ca-Al-LDH with strong adsorption performance is used for adsorbing short-chain fatty acid and is embedded with nano zero-valent iron to form Fe0The embedding of the nano zero-valent iron enhances the gaps among the layered structures, thereby enhancing the fluidity of the medium and increasing the adsorption area of the short-chain fatty acid, and certainly, the loading of the nano zero-valent iron is not easy to be too high, and the optimal loading is 1-1.6 percent, which exceeds the adsorption quantity which can influence the short-chain fatty acid. Meanwhile, the nano zero-valent iron can be used as an electron donor to enhance the removal efficiency of the nitrate and play a role in denitrification. In addition, the fatty acid embedded between the layered structures can effectively generate slow release and enhance the utilization rate of the carbon source.
(3) Adsorbing short chain fatty acid-adsorbed Fe0the/Ca-Al-LDH is used as a carbon source A and forms a mixture with litchi powder made of litchi shells. The litchi powder contains about 50% of starch, can be absorbed by microorganisms, but has low porosity, high decomposition rate and poor bacterial adhesion. Therefore, the carbon source A is mixed with the carbon source A with pores, so that the litchi powder forms a looser carbon source. And aiming at the high dissolution rate, slow release is carried out, and the carbon source A is mixed with the litchi powder, so that the short-chain fatty acid leaching resistance is increased, the use time is delayed, the slow release of two gradients of the carbon source is realized, and the efficient utilization of the carbon source is realized.
The Mesona polysaccharide (polysaccharide of Mesona chinensis Benth with acetyl group removed beforehand) is a high molecular weight water-soluble nonionic polysaccharide, is a stable gel with elasticity and heat resistance, and can enhance adhesion of bacteria, and its aqueous solution can be coated on its surface due to electrostatic adsorption and mixed with the mixture, so as to be cross-linked with algal polysaccharide and coated on its surface. Then an injection head with a certain aperture is used for injecting the carbon source into calcium chloride solution, and the calcium chloride solution is solidified and crosslinked to form the microspherical high-efficiency carbon source.
The purpose of encapsulation is to slow release and improve the utilization rate and to obtain powdery Fe0The effective separation of the/Ca-Al-LDH is realized. Thereby realizing secondary utilization.
Compared with the prior art, the invention has the following beneficial effects: (1) the potassium ferrate and the calcium peroxide are used in combination to obviously enhance the short-chain fatty acidOf Fe, lowering competitive adsorption, thereby using Fe0Adsorbing the/Ca-Al-LDH to obtain a carbon source A. (2) The carbon source A and the litchi powder are mixed and encapsulated by using the Mesona polysaccharide and the algal polysaccharide to form a double slow-release carbon source, so that the use efficiency of the carbon source is effectively enhanced. (3) The mixed biomass charcoal is added, so that the fermentation rate is obviously enhanced, and meanwhile, the use amount of sodium hydroxide is reduced. (4) Enhancing powdered Fe Using encapsulation techniques0The use convenience of the/Ca-Al-LDH is realized, and meanwhile, effective separation can be realized after the carbon source is completely released, so that the secondary utilization is facilitated.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
s1: preparation of organic carbon source: crushing and concentrating blue algae to obtain blue algae mixed solution, placing the blue algae mixed solution into a reaction tank, sequentially adding calcium peroxide, potassium ferrate and citric acid, setting the temperature at 20 ℃ for 24 hours, and carrying out pretreatment; adding mixed biomass charcoal, inoculating activated sludge, adjusting pH to 9.8, purifying and deoxidizing with nitrogen for 30 minutes, fermenting for 5 days at 36 ℃, and filtering to obtain fermentation liquor;
s2: preparation of the sustained-release carrier: cleaning eggshell membrane, drying, pulverizing, and heat treating; dissolving the powder in deionized water, grinding to obtain a calcium hydroxide solution, dropwise adding an aluminum hydroxide solution, mixing, performing ultrasonic treatment, precipitating and aging to obtain Ca-Al-LDH; soaking the sample in 0.4mmol/L ferrous sulfate solution, stirring, dropwise adding 0.1mol/L sodium borohydride, and drying the sample to obtain Fe0/Ca-Al-LDH；
S3: preparing a high-efficiency carbon source: mixing Fe0Putting Ca-Al-LDH into fermentation liquor, soaking for 4 hours at the set temperature of 20 ℃, and freeze-drying to obtain a carbon source A; mixing the carbon source A with litchi powder and Mesona chinensis Benth polysaccharide; adding into medium sodium alginate solution to form suspensionAdding calcium chloride solution into the floating liquid to form micro gel; extruding the carbon source into calcium chloride solution to be solidified and crosslinked to obtain the microspherical efficient carbon source.
In the scheme, the high-efficiency carbon source is microspheres, and the particle size is 1.1 mu m.
In the step S1, the addition amount of the calcium peroxide is 6% of the solid content in the blue algae mixed liquid; the adding amount of the biomass charcoal is 40% of the solid content in the blue algae mixed liquid; the inoculation amount of the activated sludge is 11% of the blue algae mixed liquid; the mixed biomass charcoal is prepared by mixing coconut shells and blue algae, and the mass ratio of the coconut shells to the blue algae is 2.8: 1; the ratio of the calcium peroxide to the potassium ferrate to the citric acid is 1:1.4: 0.25. In the step S3, the mass ratio of the carbon source A to the litchi powder is 2: 1; the adding amount of the mesona polysaccharide is 1.5 times of the total mass of the carbon source A and the litchi powder.
Example 2:
s1: preparation of organic carbon source: crushing and concentrating blue algae to obtain blue algae mixed solution, placing the blue algae mixed solution into a reaction tank, sequentially adding calcium peroxide, potassium ferrate and citric acid, setting the temperature at 21 ℃ and the time at 12 hours, and carrying out pretreatment; adding mixed biomass charcoal, inoculating activated sludge, adjusting the pH to 9.5, purifying and deoxidizing for 20 minutes by nitrogen, fermenting for 3-6 days at the set temperature of 35 ℃, and filtering to obtain fermentation liquor;
s2: preparation of the sustained-release carrier: cleaning eggshell membrane, drying, pulverizing, and heat treating; dissolving the powder in deionized water, grinding to obtain a calcium hydroxide solution, dropwise adding an aluminum hydroxide solution, mixing, performing ultrasonic treatment, precipitating and aging to obtain Ca-Al-LDH; soaking the sample in 0.3mmol/L ferrous sulfate solution, stirring, dropwise adding 0.1mol/L sodium borohydride, and drying the sample to obtain Fe0/Ca-Al-LDH；
S3: preparing a high-efficiency carbon source: mixing Fe0Putting Ca-Al-LDH into fermentation liquor, soaking for 3 hours at the set temperature of 10 ℃, and freeze-drying to obtain a carbon source A; mixing the carbon source A with litchi powder and Mesona chinensis Benth polysaccharide; adding into sodium alginate solution to form suspension, adding calcium chloride solution to form micro gel; extruding the carbon source into calcium chloride solution to be solidified and crosslinked to obtain the microspherical efficient carbon source.
In the scheme, the high-efficiency carbon source is microspheres, and the particle size is 0.8 mu m.
In step S1, the addition amount of the calcium peroxide is 4% of the solid content in the blue algae mixed liquid; the adding amount of the biomass charcoal is 30% of the solid content in the blue algae mixed liquid; the inoculation amount of the activated sludge is 10 percent of the blue algae mixed liquid; the mixed biomass charcoal is prepared by mixing coconut shells and blue algae, and the mass ratio of the coconut shells to the blue algae is 2: 1; the ratio of the calcium peroxide to the potassium ferrate to the citric acid is 1:1.2: 0.2. In the step S3, the mass ratio of the carbon source A to the litchi powder is 2: 0.8; the adding amount of the mesona polysaccharide is 1 time of the total mass of the carbon source A and the litchi powder.
Example 3:
s1: preparation of organic carbon source: crushing and concentrating blue algae to obtain blue algae mixed solution, placing the blue algae mixed solution into a reaction tank, sequentially adding calcium peroxide, potassium ferrate and citric acid, setting the temperature at 21 ℃ and the time at 20 hours, and carrying out pretreatment; adding mixed biomass charcoal, inoculating activated sludge, adjusting pH to 10, purifying and deoxidizing with nitrogen for 40 minutes, fermenting for 6 days at 38 ℃, and filtering to obtain fermentation liquor;
s2: preparation of the sustained-release carrier: cleaning eggshell membrane, drying, pulverizing, and heat treating; dissolving the powder in deionized water, grinding to obtain a calcium hydroxide solution, dropwise adding an aluminum hydroxide solution, mixing, performing ultrasonic treatment, precipitating and aging to obtain Ca-Al-LDH; soaking the sample in 0.5mmol/L ferrous sulfate solution, stirring, dropwise adding 0.1mol/L sodium borohydride, and drying the sample to obtain Fe0/Ca-Al-LDH；
S3: preparing a high-efficiency carbon source: mixing Fe0Putting Ca-Al-LDH into fermentation liquor, soaking for 3 hours at the set temperature of 10 ℃, and freeze-drying to obtain a carbon source A; mixing the carbon source A with litchi powder and Mesona chinensis Benth polysaccharide; adding into sodium alginate solution to form suspension, adding calcium chloride solution to form micro gel; extruding the carbon source into calcium chloride solution to be solidified and crosslinked to obtain the microspherical efficient carbon source.
In the scheme, the high-efficiency carbon source is microspheres, and the particle size is 1.2 mu m.
In the step S1, the addition amount of the calcium peroxide is 8% of the solid content in the blue algae mixed liquid; the adding amount of the biomass charcoal is 50% of the solid content in the blue algae mixed solution; the inoculation amount of the activated sludge is 12 percent of the blue algae mixed liquid; the mixed biomass charcoal is prepared by mixing coconut shells and blue algae, and the mass ratio of the coconut shells to the blue algae is 3: 1; the ratio of the calcium peroxide to the potassium ferrate to the citric acid is 1:1.5: 0.3. In the step S3, the mass ratio of the carbon source A to the litchi powder is 2: 1.2; the adding amount of the mesona polysaccharide is 2 times of the total mass of the carbon source A and the litchi powder.
Comparative example 1: the adding amount of the mixed biomass charcoal is reduced to 10 percent, and the rest is the same as that of the embodiment 1;
comparative example 2: the same procedure as in example 1 was repeated except that potassium ferrate was not added;
comparative example 3: the rest is the same as the embodiment 1 without loading zero-valent nano iron;
comparative example 4: the rest is the same as the embodiment 1 without adding litchi powder;
experiment 1:
the carbon source in example 1 was subjected to a release test at 60 hours, and the results of the test were analyzed using a gas chromatograph, and it was found that: within 60 hours, the release rate of the short-chain fatty acid is 62.1 percent, and the release rate of the litchi powder is 83.1 percent. The mixed carbon source has good slow release performance.
Experiment 2:
and (3) taking the fermentation liquor obtained in the processes of the examples 1 to 3 and the comparative examples 1 to 4, measuring the content of the short-chain fatty acid in the fermentation liquor by using a gas chromatography, measuring again after adsorption, and calculating to obtain the adsorption rate. The prepared denitrification high-efficiency carbon source is used for sewage treatment, the concentration of the carbon source is 5g/L, the total nitrogen content in the sewage is 85.6mg/L, the treatment temperature is 25 ℃, the treatment time is 80 hours, the concentration of the carbon source and the content of nitrate are monitored, and the removal rate of the nitrate and the utilization rate of the carbon source are obtained through calculation. The data obtained are shown in the following table:
and (4) conclusion: the data for comparative examples 1 to 3 show that: example 1 has the best nitrate removal rate and has excellent slow release performance and high carbon source utilization rate.
Comparing with the data of comparative example 1, it can be seen that: the reduction of the amount of mixed biomass char results in a reduction of the short chain fatty acid content due to: the activity of hydrolase produced in the fermentation process can be enhanced by adding the mixed biomass charcoal, and simultaneously, due to the porous structure of the mixed biomass charcoal, the microorganism attachment and accumulation are facilitated to form a micro-fermentation reactor, so that the electron transmission and ATP synthesis are enhanced, the growth and metabolism of anaerobic bacteria in the fermentation process are accelerated, the fermentation rate is obviously increased, and when the biomass charcoal content is reduced, the abundance of short-chain fatty chains is reduced, so that the nitrate removal rate is reduced.
As compared with the data of comparative example 2, it is understood that the addition of potassium ferrate reduced the content of short-chain fatty acids, and at the same time, the adsorption amount decreased, resulting in a decrease in the content of short-chain fatty acids, and thus a decrease in the nitrate removal rate, because: the potassium ferrate has the advantages of solubilizing, inhibiting the generation of methane and increasing the abundance of hydrolytic bacteria, thereby remarkably enhancing the generation of short-chain fatty acid, simultaneously activating calcium peroxide, thereby reducing organic impurities, reducing metal impurities in the reduction process of iron ions, and sequentially reducing the competitive adsorption force of subsequent adsorption.
Comparing with the data of comparative example 3, it can be seen that: the nitrate removal rate and the carbon utilization rate are slightly reduced because: the nanometer zero-valent iron can be used as an electron donor to enhance the removal efficiency of nitrate and play a role in denitrification. In addition, the fatty acid embedded between the layered structures can effectively improve the slow release rate of the carbon source and enhance the high-efficiency utilization rate of the carbon source.
Comparing with the data of comparative example 4, it can be seen that: the litchi powder is not added, so that the carbon source production is reduced, the early release rate is low, the nitrate removal rate is reduced within 80 hours, but the utilization rate is increased. The carbon source A is shown to have better slow release performance than the litchi powder.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A processing technology of a denitrification high-efficiency carbon source is characterized by comprising the following steps: the method comprises the following steps:
s1: preparation of organic carbon source: crushing and concentrating blue algae to obtain blue algae mixed solution, placing the blue algae mixed solution into a reaction tank, and sequentially adding calcium peroxide, potassium ferrate and citric acid for pretreatment; adding mixed biomass charcoal, inoculating activated sludge, adjusting pH, purifying and deoxidizing with nitrogen, fermenting, and filtering to obtain fermentation liquor;
s2: preparation of the sustained-release carrier: cleaning eggshell membrane, drying, pulverizing, and heat treating; dissolving the powder in deionized water, grinding to obtain a calcium hydroxide solution, dropwise adding an aluminum hydroxide solution, mixing, performing ultrasonic treatment, precipitating and aging to obtain Ca-Al-LDH; soaking the Fe-B-Fe alloy in a ferrous sulfate solution, stirring, dropwise adding sodium borohydride, and drying a sample to obtain Fe0/Ca-Al-LDH；
S3: preparing a high-efficiency carbon source: mixing Fe0Soaking the/Ca-Al-LDH in fermentation liquor, and freeze-drying to obtain a carbon source A; mixing the carbon source A with litchi powder and Mesona chinensis Benth polysaccharide; adding into sodium alginate solution to form suspension, adding calcium chloride solution to form micro gel; extruding the carbon source into calcium chloride solution to be solidified and crosslinked to obtain the microspherical efficient carbon source.
2. The process for preparing a denitrifying efficient carbon source according to claim 1, wherein: in the step S1, the addition amount of the calcium peroxide is 4-8% of the solid content in the blue algae mixed liquid; the adding amount of the biomass charcoal is 30-50% of the solid content in the blue algae mixed liquid; the inoculation amount of the activated sludge is 10-12% of the blue algae mixed liquid.
3. The process for preparing a denitrifying efficient carbon source according to claim 1, wherein: in the step S1, the mixed biomass charcoal is prepared by mixing coconut shells and blue-green algae, and the mass ratio of the coconut shells to the blue-green algae is (2-3): 1.
4. The process for preparing a denitrifying efficient carbon source according to claim 1, wherein: in the step S1, the pretreatment temperature is 20-21 ℃, and the pretreatment time is 12-24 hours; the adding ratio of the calcium peroxide, the potassium ferrate and the citric acid is 1 (1.2-1.5) to 0.2-0.3.
5. The process for preparing a denitrifying efficient carbon source according to claim 1, wherein: in step S1, the pH adjusted by sodium hydroxide is 9.5 to 10, the purification and deoxidation time is 20 to 40 minutes, the fermentation temperature is 35 to 38 ℃, and the fermentation time is 3 to 6 days.
6. The process for preparing a denitrifying efficient carbon source according to claim 1, wherein: in the step S2, the concentration of the ferrous sulfate solution is 0.3-0.5 mmol/L; the concentration of sodium borohydride was 0.1 mol/L.
7. The process for preparing a denitrifying efficient carbon source according to claim 1, wherein: in step S3, the dipping temperature is 10-30 ℃, and the dipping time is 3-5 hours.
8. The process for preparing a denitrifying efficient carbon source according to claim 1, wherein: in the step S3, the mass ratio of the carbon source A to the litchi powder is 2 (0.8-1.2); the adding amount of the mesona polysaccharide is 1-2 times of the total mass of the carbon source A and the litchi powder.
9. The process for preparing a denitrifying efficient carbon source according to claim 1, wherein: the high-efficiency carbon source is microspheres, and the particle size is 0.8-1.2 mu m.
10. A denitrification carbon source produced by the process for producing a denitrification efficient carbon source according to any one of claims 1 to 9.
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