CN111072132A - Sulfur-iron autotrophic denitrification suspended filler and preparation method thereof - Google Patents
Sulfur-iron autotrophic denitrification suspended filler and preparation method thereof Download PDFInfo
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- CN111072132A CN111072132A CN202010022137.2A CN202010022137A CN111072132A CN 111072132 A CN111072132 A CN 111072132A CN 202010022137 A CN202010022137 A CN 202010022137A CN 111072132 A CN111072132 A CN 111072132A
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- 239000000945 filler Substances 0.000 title claims abstract description 69
- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 60
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002068 microbial inoculum Substances 0.000 claims abstract description 23
- 239000000661 sodium alginate Substances 0.000 claims abstract description 21
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 21
- 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 abstract description 20
- 229920002472 Starch Polymers 0.000 claims abstract description 20
- 239000012792 core layer Substances 0.000 claims abstract description 20
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 20
- 239000008107 starch Substances 0.000 claims abstract description 20
- 235000019698 starch Nutrition 0.000 claims abstract description 20
- 125000002091 cationic group Chemical group 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 17
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 238000005728 strengthening Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 3
- 238000001879 gelation Methods 0.000 claims description 3
- 238000004659 sterilization and disinfection Methods 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- 230000001580 bacterial effect Effects 0.000 claims description 2
- 239000002054 inoculum Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims 3
- 229910052683 pyrite Inorganic materials 0.000 claims 3
- 239000011028 pyrite Substances 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 3
- 230000002787 reinforcement Effects 0.000 claims 1
- 239000000375 suspending agent Substances 0.000 claims 1
- 244000005700 microbiome Species 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000001965 increasing effect Effects 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000007888 film coating Substances 0.000 abstract description 3
- 238000009501 film coating Methods 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 4
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 3
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 108090000913 Nitrate Reductases Proteins 0.000 description 1
- 108010025915 Nitrite Reductases Proteins 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/08—Radiation
- A61L2/10—Ultraviolet radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
-
- 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
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Biodiversity & Conservation Biology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses a sulfur-iron autotrophic denitrification suspended filler and a preparation method thereof, belonging to the technical field of water pollution control. The sulfur-iron autotrophic denitrification suspended filler comprises: the core layer comprises the following raw materials in parts by weight: 5-10 parts of microbial inoculum, 30-80 parts of fixed carrier, 1-4 parts of elemental sulfur, 1-3 parts of iron powder, 0.1-0.5 part of carbon powder and 0.1-0.5 part of pH buffering agent; a cationic starch film layer; a sodium alginate film layer. The preparation method of the suspended filler comprises the following steps: weighing raw materials; preparing a first mixed solution; preparing a second mixed solution; preparing gel balls; coating with cationic starch, coating with sodium alginate, strengthening, washing and storing. The invention utilizes the advantage of sulfur and iron in cooperation with autotrophic denitrification, improves the concentration of microorganisms in the filler, improves the mechanical strength of the filler through secondary film coating, and enhances the adaptability of the filler to different sewages. The invention is applied to a fluidized bed reactor, can quickly start autotrophic denitrification reaction, and improves the wastewater treatment effect by increasing the contact area of the filler and pollutants.
Description
Technical Field
The invention relates to the technical field of water pollution control, in particular to a sulfur-iron autotrophic denitrification suspended filler and a preparation method thereof.
Background
With the continuous improvement of the sewage discharge standard in China, the sewage treatment technology is also rapidly developed. In the deep denitrification technology for sewage treatment, the autotrophic denitrification technology gradually becomes a hot technology due to lower operation cost and better treatment effect, the autotrophic denitrification does not need to provide additional organic carbon sources, and the autotrophic denitrification bacteria can utilize reducing substances such as ammonia, sulfur, iron and the like as electron donors and reduce nitrate into nitrogen through metabolic activity under the action of a series of biological enzymes such as nitrate reductase, nitrite reductase and the like.
Because the price of elemental sulfur is low, the prior deep denitrification of sewage mostly adopts a sulfur autotrophic denitrification technology, but the sulfur autotrophic denitrification technology has the defects of sulfur powder loss, the need of adding a large amount of alkali to maintain the reaction rate, the generation of sulfate and the like. In addition, some technologies utilize iron autotrophic denitrification technology to perform denitrification, but the iron autotrophic denitrification technology has the defects of hydroxyl ion generation, easy passivation of fillers, low reaction efficiency and the like.
The autotrophic denitrification process mostly adopts a form of a fixed bed reactor, and autotrophic denitrification microorganisms are continuously attached to the surface of the fixed filler to form a biological film, so that denitrification reaction is carried out. Because autotrophic denitrifying microorganisms cannot enter the filler, the amount of denitrifying microorganisms in the fixed bed reactor is small, the treatment load is low, and the occupied area is large.
Disclosure of Invention
The invention mainly solves the technical problem of providing a sulfur-iron autotrophic denitrification suspended filler and a preparation method thereof, and overcomes the defects of alkalinity consumption in the process of single sulfur autotrophic denitrification, alkalinity generation by single iron autotrophic denitrification and small quantity of microorganisms in the fixed bed filler.
In order to achieve the above purpose, the invention adopts a technical scheme that: the sulfur-iron autotrophic denitrification suspended filler is characterized by comprising: the core layer is a place for the sulfur-iron autotrophic denitrification reaction, and comprises the following raw materials in parts by weight: 5-10 parts of microbial inoculum, 30-80 parts of fixed carrier, 1-4 parts of elemental sulfur, 1-3 parts of iron powder, 0.1-0.5 part of carbon powder and 0.1-0.5 part of pH buffering agent; the cationic starch film layer increases the mechanical strength of the suspended filler and is coated on the outer surface of the core layer; and the sodium alginate film layer is used for enhancing the mechanical strength of the suspended filler and is coated on the outer surface of the cationic starch layer.
The invention adopts another technical scheme that: a preparation method of a sulfur-iron autotrophic denitrification suspended filler is characterized by comprising the following steps: weighing raw materials for preparing the core layer according to the weight part ratio; heating the fixed carrier to 60-80 ℃, stirring until the carrier is fully dissolved, and adding iron powder, sulfur powder, carbon powder and a pH buffering agent to prepare a first mixed solution; irradiating the first mixed solution under an ultraviolet lamp for sterilization, adding a microbial inoculum and fully stirring to prepare a second mixed solution; dripping the second mixed solution into a calcium chloride solution by using a burette, and fully stirring to carry out a gelation reaction to form a gel ball; putting the gel balls into a 2% cationic starch solution to form a film; washing the gel balls coated with the film, and then putting the gel balls into a sodium alginate solution to continuously coat the film for strengthening; and washing and storing the gel balls with strengthened coating films to obtain the suspended filler.
The invention has the beneficial effects that: by the sulfur-iron autotrophic denitrification suspended filler and the preparation method thereof, the concentration of autotrophic denitrification microorganisms in the suspended filler is improved by utilizing the advantages of sulfur-iron synergistic autotrophic denitrification, the mechanical strength and the mass transfer capacity of the suspended filler are improved by secondary film coating, and the adaptability of the suspended filler to different sewage environments is enhanced. When the invention is applied to a fluidized bed reactor, the autotrophic denitrification reaction can be quickly started, and the contact area between the filler and pollutants is increased, so that the wastewater treatment effect is improved.
Drawings
FIG. 1 is a schematic structural diagram of a sulfur-iron autotrophic denitrification suspended filler of the present invention;
the parts of the drawing are numbered as follows: 1-core layer, 2-cationic starch film layer and 3-sodium alginate film layer
FIG. 2 is a schematic view of the process for preparing the microbial gel beads according to the present invention;
FIG. 3 is the results of a comparative experiment using the present invention in a fluidized bed reactor;
note: in FIG. 3, reactivor 1 is reactor A and reactivor 2 is reactor B.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
It is noted that the terms first and second in the claims and the description of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
The invention fuses iron powder and sulfur powder which are needed by autotrophic denitrification bacteria agent and microbial inoculum for iron-sulfur denitrification reaction, adsorbent carbon powder for increasing microbial inoculum content and pH buffer agent for providing stable living environment for the microbial inoculum together through a fixed carrier to prepare the core layer of the suspended filler. In order to increase the mechanical strength of the suspended filler, a cationic starch layer and a sodium alginate layer are attached to the outer surface of the core layer. The strength of the suspended filler is enhanced while the autotrophic denitrification microorganisms are ensured to carry out denitrification reaction, and the service cycle and the sewage adaptability of the suspended filler are improved. The whole filler is spherical, so that the contact area of the filler and pollutants is increased, and the sewage treatment efficiency is improved.
Fig. 1 shows an embodiment of a sulfur-iron autotrophic denitrification suspension packing structure of the present invention, in which an iron-sulfur autotrophic denitrification suspension packing comprises: core layer 1, cationic starch rete 2, sodium alginate rete 3. In one embodiment of the present invention, the core layer 1 is used as a place for iron-sulfur autotrophic denitrification reaction, and comprises the following raw materials in parts by weight: 5-10 parts of microbial inoculum, 30-80 parts of fixed carrier, 1-4 parts of elemental sulfur, 1-3 parts of iron powder, 0.1-0.5 part of carbon powder and 0.1-0.5 part of pH buffering agent.
In another embodiment of the present invention, the core layer 1 comprises the following raw materials in parts by weight: 5 parts of microbial inoculum, 30 parts of fixed carrier, 1 part of elemental sulfur, 1 part of iron powder, 0.1 part of carbon powder and 0.1 part of pH buffering agent.
In another embodiment of the present invention, the core layer 1 comprises the following raw materials in parts by weight: 8 parts of microbial inoculum, 50 parts of fixed carrier, 2 parts of elemental sulfur, 2 parts of iron powder, 0.3 part of carbon powder and 0.3 part of pH buffering agent.
In another embodiment of the present invention, the core layer 1 comprises the following raw materials in parts by weight: 10 parts of microbial inoculum, 80 parts of fixed carrier, 4 parts of elemental sulfur, 3 parts of iron powder, 0.5 part of carbon powder and 0.5 part of pH buffering agent.
In one embodiment of the present invention, the outer surface of the core layer 1 is coated with a cationic starch layer 2 to increase the mechanical strength of the suspended filler, and in order to further increase the mechanical strength of the suspended filler, a sodium alginate layer 3 is coated on the cationic starch layer 2.
In a specific embodiment of the invention, the microbial inoculum in the sulfur-iron autotrophic denitrification suspended filler can be denitrifying bacterial inoculum or autotrophic denitrification inoculated sludge.
In a specific embodiment of the invention, the fixing carrier in the sulfur-iron autotrophic denitrification suspended filler is a gel, which contains 2-10% of polyvinyl alcohol and 1-4% of sodium alginate.
In one embodiment of the present invention, the buffer in the sulfur-iron autotrophic denitrification suspension filler can adopt one or a mixture of sodium bicarbonate and calcium carbonate.
Fig. 2 shows a specific embodiment of the preparation method of the sulfur-iron autotrophic denitrification suspended filler, and the method comprises the following steps:
weighing raw materials, namely weighing the raw materials for preparing the suspended filler core layer according to the weight part ratio, wherein the microbial inoculum can adopt denitrifying bacteria microbial inoculum or autotrophic denitrifying inoculated sludge, and the microbial inoculum can be in the form of liquid or suspension. The fixing carrier is gel containing 2-10% of polyvinyl alcohol and 1-4% of sodium alginate, and can be prepared by adding 2-10 parts by mass of polyvinyl alcohol and 1-4 parts by mass of sodium alginate into the gel, and adding the rest parts by mass of water and stirring the mixture in a heating state.
And a step of preparing a first mixed solution, namely taking the fixed carrier gel according to the calculated proportion, or taking raw materials for preparing the fixed carrier, heating to 60-80 ℃, and continuously stirring to fully dissolve the fixed carrier gel or the raw materials for preparing the fixed carrier gel (2-10 parts by mass of polyvinyl alcohol, 1-4 parts by mass of sodium alginate and the rest of water). And then adding the iron powder, the sulfur powder, the carbon powder and the pH buffering agent in the raw materials for preparing the suspended filler into the dissolved gel, and uniformly stirring to obtain a first mixed solution. Wherein the iron powder is 200-300 meshes, the sulfur powder is 100-300 meshes, and the powdered activated carbon is 200-300 meshes. In one embodiment of the present invention, the pH buffer may be one or a mixture of two of sodium bicarbonate and calcium carbonate.
And preparing a second mixed solution, namely, when the temperature of the prepared first mixed solution is reduced to 60 ℃, sterilizing by adopting ultraviolet irradiation, adding the weighed microbial inoculum into the first mixed solution after sterilization, and fully stirring to prepare the second mixed solution.
And (3) preparing gel spheres, namely sucking the second mixed solution by using a burette, and gradually dripping the second mixed solution into a calcium chloride solution, wherein the preferable temperature of the calcium chloride solution is 20-40 ℃, the concentration of the calcium chloride solution is 3-6%, and the titration speed is 30-60 drops/min. Fully stirring and reacting for 20-40 min. The reaction temperature is 20-40 ℃, and the second mixed solution is dripped into the calcium chloride solution and then undergoes a gelation reaction rapidly to form gel ball particles.
And (3) coating a film on the cationic starch, namely taking the prepared gel ball out of the calcium chloride solution, and putting the gel ball into a 2% cationic starch solution at the temperature of 20-40 ℃, wherein the cationic starch forms a cationic starch film on the surface of the gel ball. Thereby increasing the mechanical strength of the gel beads.
And a step of coating the film with sodium alginate, namely taking the gel balls coated with the cationic starch film out of the cationic starch solution, putting the gel balls into a 0.5-1.0% sodium alginate solution at the temperature of 20-40 ℃, and reacting for 10-20 min. So that the cationic starch film is covered with a sodium alginate film layer, thereby further enhancing the mechanical strength of the gel ball.
And a washing and storing step, namely taking out the gel balls covered with the sodium alginate film layer, washing and storing to obtain the prepared suspension seasoning.
The following is a test of the treatment effect of the prepared sulfur-iron autotrophic denitrification suspended filler on wastewater.
Example 1: the suspension filler prepared by the invention is used for treating the effluent of the secondary sedimentation tank of municipal sewage.
The daily sewage treatment capacity of a certain municipal sewage treatment plant is 8 million tons/day, the plant adopts a multi-stage treatment process of pretreatment + A2/O + three-stage treatment, and the effluent of a secondary sedimentation tank of the sewage treatment plant is used as a test object. 20g of prepared suspended filler is added into 100mL of water sample, shaking and shaking are carried out at room temperature for reaction for 24 hours, the total nitrogen value is changed from 19mg/L to 4.1mg/L, the degradation rate is 78.4%, the sulfate ion concentration is lower than 30mg/L, and the filler is not damaged.
Example 2: the suspension filler prepared by the invention can be used for carrying out deep denitrification treatment on the effluent of the secondary sedimentation tank of the printing and dyeing wastewater.
The daily sewage treatment capacity of a sewage treatment plant in a certain dyeing park is 3 million tons/day, the plant adopts a multi-stage treatment process of pretreatment, PACT and three-stage treatment, and the effluent of a secondary sedimentation tank of the sewage treatment plant is used as a test object. 20g of prepared suspended filler is added into 100mL of water sample, shaking and shaking are carried out at room temperature for reaction for 24 hours, the total nitrogen value is changed from 22mg/L to 3.5mg/L, the degradation rate is 84.1%, the sulfate ion concentration is lower than 40mg/L, and the filler is not damaged.
FIG. 3 shows an embodiment of the present invention in a fluidized bed reactor. In this embodiment, the wastewater treatment test was conducted according to the following steps:
and (3) sewage treatment test: two fluidized bed reactors with the volume of 100L are taken, wherein 4kg of suspended filler is added into the reactor A, 4L of activated sludge in a biological pool of a sewage plant is added into the reactor B, and sulfur powder and caustic soda flakes are periodically supplemented. The reactor control parameters were as follows: the water conservancy retention time HRT is 4h,the volume load of nitrate nitrogen is 0.2-0.4 kg/m3d, comparing and inspecting the starting time and the treatment effect of the two reactors when the dissolved oxygen is lower than 1.0mg/L and the concentration of the nitrate nitrogen of the water inlet of the reactors is 30-60 mg/L.
The test results of this embodiment are shown in fig. 3. The reactor A (reactor1) added with the suspended filler is started quickly, and the removal rate of 80-90% can be reached within 5 days; the reactor B (reactor2) inoculated with the sludge has longer start-up time, and the removal rate is still lower than 10 percent at 10 days. And the removal effect is less than that of reactor A (reactor 1). And the reactor A (reactor1) is continuously and stably operated for 1 month without supplementing carbon source, sulfur powder and flake alkali.
The application of the invention utilizes the advantages of sulfur and iron in cooperation with autotrophic denitrification, improves the concentration of autotrophic denitrification microorganisms in the suspended filler, improves the mechanical strength and mass transfer capacity of the suspended filler through secondary film coating, and enhances the adaptability of the suspended filler to different sewage environments. When the invention is applied to a fluidized bed reactor, the autotrophic denitrification reaction can be quickly started, and the contact area between the filler and pollutants is increased, so that the wastewater treatment effect is improved.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (14)
1. The sulfur-iron autotrophic denitrification suspended filler is characterized by comprising:
the core layer is a place for the sulfur-iron autotrophic denitrification reaction, and comprises the following raw materials in parts by weight: 5-10 parts of microbial inoculum, 30-80 parts of fixed carrier, 1-4 parts of elemental sulfur, 1-3 parts of iron powder, 0.1-0.5 part of carbon powder and 0.1-0.5 part of pH buffering agent;
a cationic starch film layer, which increases the mechanical strength of the suspended filler, coated on the outer surface of the core layer;
and the sodium alginate film layer is used for enhancing the mechanical strength of the suspended filler and is coated on the outer surface of the cationic starch layer.
2. The sulfur-iron autotrophic denitrification suspended filler according to claim 1, wherein the core layer comprises the following raw materials in parts by weight: 5 parts of microbial inoculum, 30 parts of fixed carrier, 1 part of elemental sulfur, 1 part of iron powder, 0.1 part of carbon powder and 0.1 part of pH buffering agent.
3. The sulfur-iron autotrophic denitrification suspended filler according to claim 1, wherein the core layer comprises the following raw materials in parts by weight: 8 parts of microbial inoculum, 50 parts of fixed carrier, 2 parts of elemental sulfur, 2 parts of iron powder, 0.3 part of carbon powder and 0.3 part of pH buffering agent.
4. The sulfur-iron autotrophic denitrification suspended filler according to claim 1, wherein the core layer comprises the following raw materials in parts by weight: 10 parts of microbial inoculum, 80 parts of fixed carrier, 4 parts of elemental sulfur, 3 parts of iron powder, 0.5 part of carbon powder and 0.5 part of pH buffering agent.
5. The pyrite autotrophic denitrification suspended filler according to any one of claims 1 to 4, wherein the microbial inoculum is a denitrifying bacterial inoculum or autotrophic denitrification seeded sludge.
6. The suspending filler for sulfur-iron autotrophic denitrification according to any one of claims 1 to 4, wherein the immobilization carrier is a gel containing 2-10% of polyvinyl alcohol and 1-4% of sodium alginate.
7. The ferrosulfur autotrophic denitrification suspending filler according to any one of claims 1 to 4, wherein the pH buffering agent is sodium bicarbonate and/or calcium carbonate.
8. A process for the preparation of a pyrite autotrophic denitrification suspending agent according to any one of claims 1 to 4, characterized by comprising the steps of:
weighing raw materials for preparing the core layer according to the weight part ratio;
heating the fixed carrier to 60-80 ℃, stirring until the carrier is fully dissolved, and then adding the iron powder, the sulfur powder, the carbon powder and the pH buffering agent to prepare a first mixed solution;
irradiating the first mixed solution under an ultraviolet lamp for sterilization, adding the microbial inoculum and fully stirring to prepare a second mixed solution;
dripping the second mixed solution into a calcium chloride solution by using a burette, and fully stirring to carry out a gelation reaction to form a gel ball;
putting the gel balls into a 2% cationic starch solution to form a film;
washing the gel balls coated with the film, and then putting the gel balls into a sodium alginate solution to continuously coat the film for reinforcement;
and washing and storing the gel balls with strengthened coating to obtain the suspended filler.
9. The method for preparing the sulfur-iron autotrophic denitrification suspended filler according to claim 8, wherein the microbial inoculum is denitrifying bacteria microbial inoculum or autotrophic denitrification inoculated sludge.
10. The method for preparing the sulfur-iron autotrophic denitrification suspending filler according to claim 8, wherein the fixed carrier is gel containing 2-10% of polyvinyl alcohol and 1-4% of sodium alginate.
11. The method for preparing a pyrite autotrophic denitrification suspending filler according to claim 8, wherein said pH buffering agent is sodium bicarbonate and/or calcium carbonate.
12. The method for preparing the sulfur-iron autotrophic denitrification suspension filler according to claim 8, wherein the titration conditions in the preparation of the gel beads are that the temperature is 20-40 ℃, the concentration of the calcium chloride solution is 3-6%, the titration speed is 30-60 drops/min, and the reaction time is 20-40 min.
13. The method for preparing the sulfur-iron autotrophic denitrification suspended filler according to claim 8, wherein the reaction conditions in the coating film are that the reaction time is 10-20 min at a water temperature of 20-40 ℃;
14. the method for preparing the sulfur-iron autotrophic denitrification suspended filler according to claim 8, wherein the reaction conditions for strengthening the coating are that the concentration of sodium alginate is 0.5-1.0%, the water temperature is 20-40 ℃, and the reaction time is 10-20 min.
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Application publication date: 20200428 |