CN116639796A - Composite solid carbon source filler for low-carbon source wastewater denitrification and preparation method thereof - Google Patents
Composite solid carbon source filler for low-carbon source wastewater denitrification and preparation method thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 132
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000000945 filler Substances 0.000 title claims abstract description 89
- 239000007787 solid Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000002351 wastewater Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000881 Modified starch Polymers 0.000 claims abstract description 46
- 239000004368 Modified starch Substances 0.000 claims abstract description 46
- 235000019426 modified starch Nutrition 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 229920002472 Starch Polymers 0.000 claims abstract description 17
- 239000008107 starch Substances 0.000 claims abstract description 17
- 235000019698 starch Nutrition 0.000 claims abstract description 17
- 239000008187 granular material Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- XLSGYCWYKZCYCK-UHFFFAOYSA-N 4-(2-methylpropyl)oxane-2,6-dione Chemical compound CC(C)CC1CC(=O)OC(=O)C1 XLSGYCWYKZCYCK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 229920001592 potato starch Polymers 0.000 description 11
- 244000005700 microbiome Species 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- VRVKOZSIJXBAJG-TYYBGVCCSA-M monosodium fumarate Chemical compound [Na+].OC(=O)\C=C\C([O-])=O VRVKOZSIJXBAJG-TYYBGVCCSA-M 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 3-isobutyl glutaric anhydride ethanol Chemical compound 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 244000183278 Nephelium litchi Species 0.000 description 1
- 235000015742 Nephelium litchi Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biological Treatment Of Waste Water (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention discloses a composite solid carbon source filler for denitrification of low-carbon source wastewater and a preparation method thereof; belongs to the technical field of water treatment; the method comprises the following steps: adding modified starch particles and polyvinyl alcohol into distilled water, heating and stirring to obtain a mixed solution; adding calcium carbonate and corncob into the mixed solution, uniformly mixing, adding a cross-linking agent, uniformly stirring, standing, washing, and freeze-drying to obtain the composite solid carbon source filler. The modified starch granules are prepared by esterifying 3-isobutyl glutaric anhydride with starch. The composite solid carbon source filler prepared by the invention has higher carbon release capacity and excellent aerobic denitrification performance, and can be widely applied to the deep denitrification treatment process of low-carbon source wastewater to achieve the aim of denitrification.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a composite solid carbon source filler for low-carbon source wastewater denitrification and a preparation method thereof.
Background
In order to reduce eutrophication of water body caused by the entry of N, P and other nutrient substances into water body, the requirement of dephosphorization and denitrification on sewage becomes a necessary requirement, and the requirement becomes more and more strict. At present, the dephosphorization measures adopted by the urban sewage treatment plant usually take biological dephosphorization as a main part and chemical dephosphorization as an auxiliary part, the phosphorus can be discharged up to the standard by adding chemical agents, and the nitrogen removal completely depends on biological nitrification and denitrification, so that the standard removal is difficult to realize. According to the biological dephosphorization and denitrification theory, the sufficient organic carbon source is a necessary condition for guaranteeing the biological dephosphorization and denitrification of the sewage.
However, with the improvement of the living standard of people and the increase of water consumption, the phenomenon of low carbon source of domestic sewage is increasingly obvious, so that the problem of insufficient carbon source in the actual running process of a sewage plant is increasingly outstanding. Therefore, how to realize high standard emission of nitrogen under low carbon source water intake is a problem to be solved in the process of treating urban sewage in south China. The prior art CN 105502650A discloses a preparation method of a composite solid carbon source filler for deep denitrification of aquaculture wastewater; the preparation method comprises the following steps: adding a certain amount of powder lychee seed and sodium carbonate into the glucomannan aqueous solution, and uniformly stirring; standing at room temperature, and heating in water bath; then cooling and freezing; finally, obtaining the composite solid carbon source filler through freeze drying; it can be used as both carbon source and filler, and can be completely degraded without environmental pollution.
Disclosure of Invention
The invention aims to provide a composite solid carbon source filler with higher carbon release capacity and excellent aerobic denitrification performance, which can be widely applied to a deep denitrification treatment process of low-carbon source wastewater to achieve the aim of denitrification.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a composite solid carbon source filler comprising at least modified starch particles;
the modified starch granules are prepared by esterifying 3-isobutyl glutaric anhydride with starch.
According to the invention, 3-isobutyl glutaric anhydride and starch are esterified to prepare modified starch particles, and the modified starch particles are used as components of the composite solid carbon source filler to prepare the composite solid carbon source filler with higher carbon release capacity, so that the carbon source is released easily; the surface of the filler presents an irregular convex surface, which is beneficial to the adhesion of microorganisms, provides carbon sources for the microorganisms adhered on the filler, improves the aerobic denitrification performance of the composite solid carbon source filler, and is better applied to the deep denitrification treatment process of the low-carbon source wastewater, thereby achieving the aim of denitrification.
In some embodiments, the composite solid carbon source filler further comprises polyvinyl alcohol, calcium carbonate, corn cob, and a cross-linking agent.
In some embodiments, the weight ratio of the polyvinyl alcohol, the modified starch particles, the calcium carbonate, the corn cob and the cross-linking agent is 5-20:1-5:0.5-2:1.5-12:0.25-0.75.
In some embodiments, the cross-linking agent is a saturated boric acid solution of calcium chloride; wherein the concentration of the saturated boric acid solution of the calcium chloride is 2-5wt%.
In some embodiments, the modified starch particles are prepared by: dispersing the raw starch in distilled water, adding a sodium hydroxide solution to adjust the pH, slowly adding a 3-isobutyl glutaric anhydride solution, heating for reaction, maintaining a constant pH value, adding dilute hydrochloric acid to terminate the reaction after the reaction is finished, carrying out suction filtration, washing, drying and grinding to obtain modified starch particles.
In the preparation method of the modified starch granules, 3-isobutyl glutarate anhydride is 5-12wt% of the original starch; specifically, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% and 10wt% are selected.
In some embodiments, the average particle size of the composite solid carbon source filler is 4 to 10mm.
The invention further aims to provide the application of the composite solid carbon source filler in deep denitrification of low carbon source wastewater.
The invention also aims to provide a preparation method of the composite solid carbon source filler for denitrification of low carbon source wastewater, which comprises the following steps:
adding modified starch particles and polyvinyl alcohol into distilled water, heating and stirring to obtain a mixed solution;
adding calcium carbonate and corncob into the mixed solution, uniformly mixing, adding a cross-linking agent, uniformly stirring, standing, washing, and freeze-drying to obtain the composite solid carbon source filler.
According to the invention, 3-isobutyl glutaric anhydride and starch are esterified to prepare modified starch particles, and the modified starch particles are used as components of the composite solid carbon source filler to prepare the composite solid carbon source filler with higher carbon release capacity, so that the carbon source is released easily; the surface of the filler presents an irregular convex surface, which is beneficial to the adhesion of microorganisms, provides carbon sources for the microorganisms adhered on the filler, improves the aerobic denitrification performance of the composite solid carbon source filler, and is better applied to the deep denitrification treatment process of the low-carbon source wastewater, thereby achieving the aim of denitrification. Therefore, the composite solid carbon source filler with higher carbon release capacity and excellent aerobic denitrification performance can be widely applied to the deep denitrification treatment process of low-carbon source wastewater, and the aim of denitrification is fulfilled.
Drawings
FIG. 1 is an infrared spectrum of potato starch and modified starch in example 1;
fig. 2 is an SEM image of the composite solid carbon source filler in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Unless specifically indicated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
The preparation method of the modified starch granule is as follows: placing raw starch in a container, adding distilled water, stirring and mixing uniformly to obtain a starch dispersion liquid with the concentration of 1-5 wt%, adding a sodium hydroxide solution with the concentration of 1-2 mol/L to adjust the pH to 7.5-8.5, slowly adding a 3-isobutyl glutaric anhydride ethanol solution with the concentration of 3-6 wt%, wherein 3-isobutyl glutaric anhydride is 5-12 wt% of the raw starch, heating to 35-45 ℃ to react for 3-6 h, maintaining a constant pH value, adding a dilute hydrochloric acid with the concentration of 1-2 mol/L to terminate the reaction after the reaction is finished, filtering, washing with distilled water, drying at 45-55 ℃ for 10-12 h, and grinding to obtain modified starch particles.
In some embodiments of the present invention, a method for preparing a composite solid carbon source filler for denitrification of low carbon source wastewater includes the steps of:
adding 1-5 parts by weight of modified starch particles and 5-20 parts by weight of polyvinyl alcohol into 60-120 parts by weight of distilled water, heating to 55-80 ℃ and stirring for 1-3 hours to obtain a mixed solution;
and adding 0.5-2 parts by weight of calcium carbonate and 1.5-12 parts by weight of corncob into the mixed solution, uniformly mixing, adding 0.25-0.75 part by weight of cross-linking agent, uniformly stirring, standing to form spherical particles, washing with distilled water to remove unreacted substances, and freeze-drying to obtain the composite solid carbon source filler.
In order to optimize the denitrification performance of the composite solid carbon source filler, the invention adopts the implementation mode which further comprises the following steps: adding monosodium fumarate accounting for 5-10wt% of the weight of the polyvinyl alcohol into the preparation process of the composite solid carbon source filler, wherein the monosodium fumarate interacts with other components and interacts with other components to prepare the composite solid carbon source filler, so that the carbon release capacity of the carbon source filler is further improved, and a better carbon release effect is achieved; meanwhile, the aerobic denitrification capability of the carbon source filler is improved, and the aim of denitrification is better achieved.
The technical scheme of the invention is further described in detail below with reference to the specific embodiments:
example 1:
the preparation method of the composite solid carbon source filler for low-carbon source wastewater denitrification comprises the following steps:
adding 2.5 parts by weight of modified starch particles and 14 parts by weight of polyvinyl alcohol into 100 parts by weight of distilled water, heating to 75 ℃ and stirring for 2 hours to obtain a mixed solution;
adding 1 part by weight of calcium carbonate and 10 parts by weight of corncob (purity is more than or equal to 95%) into the mixed solution, uniformly mixing, adding 0.5 part by weight of saturated boric acid solution of 2.5wt% of calcium chloride, uniformly stirring, standing to form spherical particles, washing with distilled water to remove unreacted substances, and freeze-drying to obtain the composite solid carbon source filler, wherein the average particle size of the composite solid carbon source filler is 6mm.
Specifically, in this embodiment, the preparation method of the modified starch granule is as follows:
placing potato starch (dry basis) in a container, adding distilled water, stirring and mixing uniformly to obtain starch dispersion liquid with the concentration of 2.5wt%, adding sodium hydroxide solution with the concentration of 1mol/L to adjust the pH to 8.0, slowly adding 3-isobutyl glutaric anhydride ethanol solution with the concentration of 5wt%, wherein 3-isobutyl glutaric anhydride is 9wt% of potato starch, heating to 40 ℃ for reacting for 5 hours, maintaining a constant pH value, adding dilute hydrochloric acid with the concentration of 1mol/L after the reaction is finished, stopping the reaction, filtering, washing with distilled water, drying at 55 ℃ for 10 hours, and grinding to obtain modified starch particles.
Example 2:
the preparation method of the composite solid carbon source filler for low carbon source wastewater denitrification is the same as in example 1, and the difference from example 1 is as follows:
adding 4.5 parts by weight of modified starch particles and 16 parts by weight of polyvinyl alcohol into 120 parts by weight of distilled water, heating to 75 ℃ and stirring for 2 hours to obtain a mixed solution;
adding 2 parts by weight of calcium carbonate and 8 parts by weight of corncob (purity is more than or equal to 95%) into the mixed solution, uniformly mixing, adding 0.65 part by weight of saturated boric acid solution of 2.5wt% of calcium chloride, uniformly stirring, standing to form spherical particles, washing with distilled water to remove unreacted substances, and freeze-drying to obtain the composite solid carbon source filler, wherein the average particle size of the composite solid carbon source filler is 7mm.
In this example, modified starch granules were prepared in the same manner as in example 1.
Example 3:
the preparation method of the composite solid carbon source filler for low carbon source wastewater denitrification is the same as in example 1, and the difference from example 1 is as follows:
in this example, the modified starch granule was prepared by the following method:
placing potato starch (dry basis) in a container, adding distilled water, stirring and mixing uniformly to obtain starch dispersion liquid with the concentration of 2.5wt%, adding sodium hydroxide solution with the concentration of 1mol/L to adjust the pH to 8.0, slowly adding 3-isobutyl glutaric anhydride ethanol solution with the concentration of 5wt%, wherein 3-isobutyl glutaric anhydride is 6wt% of potato starch, heating to 40 ℃ for reacting for 5 hours, maintaining a constant pH value, adding dilute hydrochloric acid with the concentration of 1mol/L after the reaction is finished, stopping the reaction, filtering, washing with distilled water, drying at 55 ℃ for 10 hours, and grinding to obtain modified starch particles.
Example 4:
the preparation method of the composite solid carbon source filler for low carbon source wastewater denitrification is the same as in example 1, and the difference from example 1 is as follows:
adding 2.5 parts by weight of modified starch particles and 14 parts by weight of polyvinyl alcohol into 100 parts by weight of distilled water, heating to 75 ℃ and stirring for 2 hours to obtain a mixed solution;
adding 1 part by weight of calcium carbonate and 10 parts by weight of corncob (purity is more than or equal to 95%), uniformly mixing 1 part by weight of monosodium fumarate, adding 0.5 part by weight of saturated boric acid solution of 2.5wt% of calcium chloride, uniformly stirring, standing to form spherical particles, washing with distilled water to remove unreacted substances, and freeze-drying to obtain the composite solid carbon source filler.
In this example, modified starch granules were prepared in the same manner as in example 1.
Example 5:
the preparation method of the composite solid carbon source filler for low carbon source wastewater denitrification is the same as in example 1, and the difference from example 1 is as follows:
adding 2.5 parts by weight of modified starch particles and 14 parts by weight of polyvinyl alcohol into 100 parts by weight of distilled water, heating to 75 ℃ and stirring for 2 hours to obtain a mixed solution;
adding 1 part by weight of calcium carbonate and 10 parts by weight of corncob (purity is more than or equal to 95%), uniformly mixing 1.2 parts by weight of monosodium fumarate, adding 0.5 part by weight of saturated boric acid solution of 2.5wt% of calcium chloride, uniformly stirring, standing to form spherical particles, washing with distilled water to remove unreacted substances, and freeze-drying to obtain the composite solid carbon source filler.
In this example, modified starch granules were prepared in the same manner as in example 1.
Example 6:
the preparation method of the composite solid carbon source filler for low carbon source wastewater denitrification is the same as in example 1, and the difference from example 1 is as follows: the modified starch granules were replaced with potato starch (dry basis).
Example 7:
the preparation method of the composite solid carbon source filler for low carbon source wastewater denitrification is the same as in example 4, and the difference from example 4 is as follows: the modified starch granules were replaced with potato starch (dry basis).
Test example 1:
1. infrared spectroscopic testing of modified starch granules
Infrared analysis was performed on the starch structures before and after modification using a VERTEX 70 infrared spectrometer.
FIG. 1 is an infrared spectrum of potato starch and modified starch in example 1; curves I and II are potato starch and modified starch respectively; as can be seen from FIG. 1, potato starch is at 3350cm -1 The characteristic absorption peak of the nearby hydroxy is the stretching vibration of the hydroxy; at 2915cm -1 The characteristic absorption peak appearing nearby is the stretching vibration of alkane, compared with potato starch, the modified starch is 2920cm -1 The characteristic peak of alkane appearing nearby is enhanced and at 1750cm -1 Characteristic absorption peaks of the ester groups appear nearby; therefore, the modified starch is prepared by esterifying 3-isobutyl glutaric anhydride with starch.
2. Composite solid carbon source filler performance test
(1) Surface topography testing
And observing the surface morphology of the composite solid carbon source filler by using a scanning electron microscope.
FIG. 2 is an SEM image of a composite solid carbon source filler of example 1; as can be seen from fig. 2, the composite solid carbon source filler has a rugged surface with more irregular protrusions, which can utilize the attachment of microorganisms and provide carbon sources for the microorganisms.
(2) Carbon release performance test
Adding 8g of composite solid carbon source filler into a flask filled with 900mL of deionized water, setting the temperature to be 32 ℃, taking water samples at 1h and 24h respectively, measuring the COD concentration in the water samples, measuring the COD concentration by adopting a potassium dichromate digestion method, fitting the relationship between the COD concentration and time according to the carbon release process of the carbon source filler according to the secondary dynamic process, and further calculating the carbon source capacity finally released by the carbon source filler, wherein the calculation formula is as follows:
1/c-1/c m =k/t
wherein: c m The saturated concentration of COD released by the unit mass material in the solution is mg/(L.g); k is a constant, k=1/K, k=c m /t 1/2 The method comprises the steps of carrying out a first treatment on the surface of the t is the reaction time, h; t is t 1/2 H is the time taken for COD release to reach half the saturation concentration value.
TABLE 1 carbon release Properties of composite solid carbon Source Filler
As can be seen from Table 1, examples 1 to 3 were compounded with a solid carbon source filler c m The value, namely the final release COD concentration is higher than 115 mg/(L.g), which shows that the composite solid carbon source filler has higher carbon release capacity; comparing example 1 with example 7, the final release COD concentration of the composite solid carbon source filler in example 1 is higher than that of example 7, which shows that the modified starch is prepared by esterifying 3-isobutyl glutaric anhydride and starch, and the modified starch is used as a component of the composite solid carbon source filler to prepare the composite solid carbon source filler with higher carbon release capacity, which is beneficial to release of carbon source, thereby providing carbon source for microorganisms attached to the filler and better achieving the aim of denitrification; c of composite solid carbon Source Filler in examples 4 and 5 m The final release COD concentration of the composite solid carbon source filler in examples 1 and examples 4 to 5, examples 6 and 7, and the final release COD concentration of the composite solid carbon source filler in examples 4 to 5, which is higher than that in example 1, and example 7, which is higher than that in example 6, were compared to the values of 125 mg/(L.g)The monosodium fumarate is added into the bulk carbon source filler, so that the composite solid carbon source filler is prepared, the carbon release capacity of the carbon source filler is further improved, and a better carbon release effect is achieved.
(3) Aerobic denitrification Performance test
4g of composite solid carbon source filler was mixed with 90mL of test water, and NO in the test water was first measured 3 - -N、NO 2 - The N content is inoculated with 5 percent of activated and cultured aerobic denitrifying bacteria liquid, and the aerobic denitrifying bacteria liquid is cultured at the constant temperature of 30 ℃ and 150r/min, and NO in the culture liquid is measured after 5 hours 3 - -N、NO 2 - -N content, and thus its removal rate.
TABLE 2 denitrification Property of composite solid carbon Source Filler
As can be seen from Table 2, the composite solid carbon source filler of examples 1 to 3 was used for aerobic denitrification performance against NO 3 - The removal rate of the-N is higher than 90 percent, NO 2 - -the removal rate of N is higher than 93%; comparative example 1 and example 7, NO in example 1 3 - -N、NO 2 - The removal rate of N is higher than that of the embodiment 7, which shows that the modified starch is prepared by esterifying 3-isobutyl glutaric anhydride and starch, and the modified starch is used as a component of the composite solid carbon source filler to prepare the composite solid carbon source filler, so that carbon sources are provided for microorganisms attached to the filler, the aerobic denitrification performance of the composite solid carbon source filler is improved, and the modified starch is better applied to the deep denitrification treatment process of low-carbon source wastewater; NO in example 4 and example 5 3 - The removal rate of N is higher than 92%, NO 2 - The removal rate of-N is higher than 97%, and the NO in comparative examples 1 and 4-5, examples 6 and 7, examples 4-5 3 - -N、NO 2 - The removal rate of-N is higher than in example 1, example 7, NO 3 - -N、NO 2 - The removal rate of N is higher than that of example 6, which shows that monosodium fumarate is added into the composite solid carbon source filler to prepareThe composite solid carbon source filler is obtained, the aerobic denitrification capability of the carbon source filler is further improved, and the aim of denitrification is better achieved.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A composite solid carbon source filler comprising at least modified starch particles;
the modified starch granules are prepared by esterifying 3-isobutyl glutaric anhydride with starch.
2. The composite solid carbon source filler according to claim 1, characterized in that: the composite solid carbon source filler also comprises polyvinyl alcohol, calcium carbonate, corncob and a cross-linking agent.
3. The composite solid carbon source filler according to claim 2, characterized in that: the weight ratio of the polyvinyl alcohol to the modified starch particles to the calcium carbonate to the corn cob to the cross-linking agent is 5-20:1-5:0.5-2:1.5-12:0.25-0.75.
4. The composite solid carbon source filler according to claim 2, characterized in that: the cross-linking agent is saturated boric acid solution of calcium chloride; the concentration of the saturated boric acid solution of the calcium chloride is 2-5wt%.
5. The composite solid carbon source filler according to claim 1, characterized in that: the preparation method of the modified starch granule comprises the following steps: dispersing the raw starch in distilled water, adding a sodium hydroxide solution to adjust the pH, slowly adding a 3-isobutyl glutaric anhydride solution, heating for reaction, maintaining a constant pH value, adding dilute hydrochloric acid to terminate the reaction after the reaction is finished, carrying out suction filtration, washing, drying and grinding to obtain modified starch particles.
6. The composite solid carbon source filler according to claim 1, characterized in that: the average particle size of the composite solid carbon source filler is 4-10 mm.
7. The use of the composite solid carbon source filler of claim 1 in deep denitrification of low carbon source wastewater.
8. The preparation method of the solid carbon source filler for low-carbon source wastewater denitrification comprises the following steps:
adding modified starch particles and polyvinyl alcohol into distilled water, heating and stirring to obtain a mixed solution;
adding calcium carbonate and corncob into the mixed solution, uniformly mixing, adding a cross-linking agent, uniformly stirring, standing, washing, and freeze-drying to obtain the composite solid carbon source filler in claim 1.
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