CN114291896A - Carrier-solidified microbial sewage treatment agent and preparation method thereof - Google Patents
Carrier-solidified microbial sewage treatment agent and preparation method thereof Download PDFInfo
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- 239000010865 sewage Substances 0.000 title claims abstract description 45
- 230000000813 microbial effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 143
- 239000010439 graphite Substances 0.000 claims description 142
- 229910002804 graphite Inorganic materials 0.000 claims description 142
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 77
- 238000003756 stirring Methods 0.000 claims description 58
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- 238000005406 washing Methods 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 47
- 238000009830 intercalation Methods 0.000 claims description 37
- 230000002687 intercalation Effects 0.000 claims description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000012286 potassium permanganate Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 229910001510 metal chloride Inorganic materials 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 229960002089 ferrous chloride Drugs 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 19
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229920001661 Chitosan Polymers 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000010802 sludge Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 11
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 230000032770 biofilm formation Effects 0.000 claims description 11
- 239000004021 humic acid Substances 0.000 claims description 11
- 239000001632 sodium acetate Substances 0.000 claims description 11
- 235000017281 sodium acetate Nutrition 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 230000005495 cold plasma Effects 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004065 wastewater treatment Methods 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 28
- 244000005700 microbiome Species 0.000 abstract description 16
- 239000002351 wastewater Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000011068 loading method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 239000010949 copper Substances 0.000 description 7
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Abstract
Compared with the scheme that zero-valent iron and microorganisms are loaded on the same carrier in the prior art, the carrier A and the carrier B are arranged, the carrier A is used for loading the zero-valent iron, the carrier B is used for loading the microorganisms, the two are mutually cooperated when in use, but the arrangement of the carrier A and the carrier B reduces the joint contact of the microorganisms and the zero-valent iron, so that the influence of the zero-valent iron on the microorganisms is effectively avoided; the application discloses a carrier-solidified microbial sewage treating agent and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared sewage treating agent has an excellent treatment effect on hexavalent chromium wastewater, the cost is low, the efficiency is high, the carrier-solidified microbial sewage treating agent can be widely applied to sewage treatment of the hexavalent chromium wastewater, and the carrier-solidified microbial sewage treating agent has high practicability.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a carrier-solidified microbial sewage treatment agent and a preparation method thereof.
Background
Chromium and chemical substances thereof are widely applied in industry, and a large amount of chromium-containing wastewater is generated in a series of industries such as metallurgy, chemical engineering, mineral engineering, electroplating, chromium preparation, pigment, pharmacy, light textile, chromium salt and chromium compound production and the like, and chromium has serious harm to ecological environment and human health, so that the removal of the chromium-containing wastewater becomes one of hot topics which are currently concerned.
The zero-valent iron is a material widely applied to removing chromium in wastewater, and has the characteristics of low cost, strong reducing capability, good biocompatibility and the like, and under the anaerobic condition, the zero-valent iron can react with water to release hydrogen, can be utilized by microorganisms and is reduced cooperatively, so that the removing effect of chromium ions in the wastewater is improved; however, zero-valent iron is easy to agglomerate, so that research and development personnel can load zero-valent iron and microorganisms on the same carrier in the research and development process to avoid agglomeration of part iron and simultaneously realize the synergistic effect of zero-valent iron and microorganisms.
Based on the above situation, we disclose a carrier-immobilized microbial wastewater treatment agent and a preparation method thereof to solve the problem.
Disclosure of Invention
The invention aims to provide a carrier-solidified microbial sewage treatment agent and a preparation method 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 preparation method of a carrier-solidified microbial sewage treatment agent comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring, reacting for 0.5-1h in a water bath at 20-30 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at the temperature of 800-900 ℃, dissolving the graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring, adding an epoxy silane coupling agent, stirring in a constant-temperature water bath at the temperature of 75-80 ℃, washing, filtering, and vacuum drying to obtain a graphite carrier A;
(3) taking the graphite carrier A and the metal chloride, placing the graphite carrier A and the metal chloride in a ball mill, carrying out ball milling for 2-3h, transferring the ball milled for 2-3h to a vacuum tube furnace, vacuumizing, heating to 1000-plus-material 1100 ℃, carrying out heat preservation reaction, cooling, transferring to a cold plasma modification treatment instrument, and carrying out treatment for 10-15min in a hydrogen atmosphere to obtain a graphite intercalation compound;
(4) transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting in a water bath at 35-40 ℃, washing with deionized water, drying, transferring into a nitrogen environment, reacting at 840-850 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water, adding a graphite carrier B and calcium chloride, continuously stirring, washing with deionized water, drying, transferring to anaerobic activated sludge, and performing shaking culture and biofilm formation to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 20-25min to obtain material A;
taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting at 45-50 ℃, adding the biological carrier, continuing to react, centrifugally washing, and freeze-drying to obtain the sewage treatment agent.
The optimized scheme comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring for 20-30min, reacting for 0.5-1h in a water bath at 20-30 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at the temperature of 800-900 ℃ for 2-3min, dissolving the graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring for 2-2.5h, adding an epoxy silane coupling agent, stirring for 7-8h in a constant-temperature water bath at the temperature of 75-80 ℃, washing, filtering, and vacuum drying at the temperature of 80-85 ℃ to obtain a graphite carrier A;
(3) taking the graphite carrier A and the metal chloride, placing the graphite carrier A and the metal chloride in a ball mill, carrying out ball milling for 2-3h, transferring the ball milled for 2-3h to a vacuum tube furnace, vacuumizing, heating to 1000-1100 ℃, carrying out heat preservation for 2-3h under the condition that the vacuum degree is 3.5mPa, transferring the ball milled into a cold plasma modification treatment instrument after cooling, and carrying out treatment for 10-15min under the hydrogen atmosphere to obtain a graphite intercalation compound;
(4) transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting for 30-40min under the condition of 35-40 ℃ water bath, washing with deionized water, drying, transferring into a nitrogen environment, carrying out heat preservation reaction at 840 ℃ and 850 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water for 20-30min, adding a graphite carrier B and calcium chloride, continuously stirring for 1.5-2h, washing with deionized water, drying, transferring to anaerobic activated sludge, and performing oscillation culture and biofilm formation at 25-28 ℃ to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 20-25min to obtain material A;
taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting for 30-40min at 45-50 ℃, adding the biological carrier, continuing to react for 20-30min, centrifuging, washing, and freeze-drying to obtain the sewage treatment agent.
According to an optimized scheme, in the step (3), the metal chloride is ferrous chloride and copper chloride in a mass ratio of 2: 1 and mixing.
In the optimized scheme, in the step (2), the epoxy silane coupling agent is KH-560.
In the optimized scheme, in the step (4), the reaction time is kept for 2-3 h.
In an optimized scheme, in the step (4), the anaerobic activated sludge is acclimated in advance by an organic chromium solution.
According to an optimized scheme, in the step (1), the mass ratio of the crystalline flake graphite to the potassium permanganate is 1: 0.2.
according to an optimized scheme, in the step (4), the mass ratio of the pretreated graphite to the potassium permanganate is 1: 0.15.
according to an optimized scheme, the sewage treatment agent is prepared by the preparation method of the carrier solidified microorganism sewage treatment agent.
Compared with the prior art, the invention has the following beneficial effects:
compared with the scheme that zero-valent iron and microorganisms are loaded on the same carrier in the prior art, the carrier A and the carrier B are arranged, the carrier A is used for loading the zero-valent iron, the carrier B is used for loading the microorganisms, the two are mutually cooperated when in use, but the arrangement of the carrier A and the carrier B reduces the joint contact of the microorganisms and the zero-valent iron, so that the influence of the zero-valent iron on the microorganisms is effectively avoided;
meanwhile, zero-valent iron is easy to agglomerate and agglomerate in the solution, and the use of the zero-valent iron is influenced during actual use, so that the graphite carrier A is taken as a main body, the zero-valent iron is taken as an object, and the zero-valent iron is intercalated on the graphite carrier with the lamellar structure by a high-temperature molten salt method, so that the problem that the zero-valent iron is easy to agglomerate is solved; in the preparation process, firstly, the ferrous chloride high-temperature salt is inserted into the graphite layer, and then the graphite intercalation compound of the zero-valent iron intercalation graphite carrier A is formed by hydrogen reduction.
In order to improve the intercalation effect of the graphite intercalation compound, the graphite is pretreated, the graphite is firstly subjected to primary intercalation, the flake graphite is placed in a mixed solution of nitric acid and phosphoric acid, potassium permanganate is added for oxidation intercalation to obtain pretreated graphite, a sheet layer of the pretreated graphite is opened, preheating is performed at 900 ℃ through 800-doped silica gel, grafting modification is performed through an epoxy silane coupling agent after preheating, an epoxy group is introduced, a polar bonding effect exists between the epoxy group and ferrous chloride, and the ferrous chloride can be anchored so as to further improve the stability of subsequent intercalation.
Meanwhile, in order to further improve the chromium removal effect of the sewage treatment agent, a double-metal intercalation is selected during intercalation, metal chlorides are selected from ferrous chloride and copper chloride, zero-valent iron and zero-valent copper can be generated after subsequent hydrogen reduction, and the ferrous chloride and the zero-valent copper can mutually act in a synergistic manner to further improve the removal effect of chromium ions in the wastewater.
The graphite carrier B is also arranged, and is used for loading microorganisms, so that after graphite is pretreated to obtain pretreated graphite, the pretreated graphite is further subjected to secondary intercalation, graphite lamella is fully opened, the graphite lamella wall is thinner, the network-shaped pore system structure is richer, and more growth spaces can be provided when the microorganisms are loaded; meanwhile, humic acid and sodium acetate are introduced after loading, and can be used as organic matters to be used as carbon sources to be utilized by microorganisms, so that the activity of the microorganisms is enhanced, and the removal effect of chromium ions in the wastewater is improved.
The anaerobic activated sludge selected by the method is sludge in a secondary sedimentation tank of a certain sewage treatment plant in Guangzhou city, and the removal rate of the sludge can reach more than 95% at the Cr (VI) concentration of 10mg/L after acclimation for a period of time; the biological carrier is obtained by carrying out biofilm formation loading on the graphite carrier B through a graphite carrier B, and comprises the following components: by mass, 10-15 parts of chitosan, 2-3 parts of graphite intercalation compound, 6-8 parts of biological carrier and 2-3 parts of glutaraldehyde; and (5) coating and compounding the chitosan to obtain the sewage treatment agent.
The application discloses a carrier-solidified microbial sewage treating agent and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared sewage treating agent has an excellent treatment effect on hexavalent chromium wastewater, the cost is low, the efficiency is high, the carrier-solidified microbial sewage treating agent can be widely applied to sewage treatment of the hexavalent chromium wastewater, and the carrier-solidified microbial sewage treating agent has high practicability.
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:
a preparation method of a carrier-solidified microbial sewage treatment agent comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring for 20min, reacting for 1h in a water bath at 20 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at 800 ℃ for 3min, dissolving the pretreated graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring for 2h, adding an epoxy silane coupling agent, stirring for 8h in a 75 ℃ constant-temperature water bath, washing, filtering, and vacuum drying at 80 ℃ to obtain a graphite carrier A; the epoxy silane coupling agent is KH-560.
(3) Placing the graphite carrier A and the metal chloride in a ball mill for ball milling for 2h, transferring to a vacuum tube furnace, vacuumizing, heating to 1000 ℃, preserving heat for 3h under the condition that the vacuum degree is 3.5mPa, transferring to a cold plasma modification treatment instrument after cooling, and treating for 10min in a hydrogen atmosphere to obtain a graphite intercalation compound; the metal chloride is ferrous chloride and copper chloride, and the mass ratio of ferrous chloride to copper chloride is 2: 1 and mixing. Wherein the mol ratio of Fe to C is 0.05, and the mol ratio of Cu to C is 0.02.
(4) Transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting for 40min under the condition of 35 ℃ water bath, washing with deionized water, drying, transferring into a nitrogen environment, reacting for 3h under the condition of 840 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water for 20min, adding a graphite carrier B and calcium chloride, continuously stirring for 1.5h, washing with deionized water, drying, transferring to anaerobic activated sludge, and performing oscillation culture and biofilm formation at 25 ℃ to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 20min to obtain material A;
and (3) taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting for 40min at 45 ℃, adding the biological carrier, continuing to react for 20min, centrifuging, washing, and freeze-drying to obtain the sewage treatment agent.
The components comprise: by mass, 14 parts of chitosan, 3 parts of graphite intercalation compound, 8 parts of biological carrier and 3 parts of glutaraldehyde.
Example 2:
a preparation method of a carrier-solidified microbial sewage treatment agent comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring for 25min, reacting for 0.6h in a water bath at 25 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at 850 ℃ for 2min, dissolving the pretreated graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring for 2.2h, adding an epoxy silane coupling agent, stirring for 7.5h in a constant-temperature water bath at 78 ℃, washing, filtering, and vacuum drying at 83 ℃ to obtain a graphite carrier A; the epoxy silane coupling agent is KH-560.
(3) Placing the graphite carrier A and the metal chloride in a ball mill for ball milling for 2.5h, transferring to a vacuum tube furnace, vacuumizing, heating to 1050 ℃, preserving heat for 2.5h under the condition that the vacuum degree is 3.5mPa, cooling, transferring to a cold plasma modification treatment instrument, and treating for 13min in a hydrogen atmosphere to obtain a graphite intercalation compound; the metal chloride is ferrous chloride and copper chloride, and the mass ratio of ferrous chloride to copper chloride is 2: 1 and mixing. Wherein the mol ratio of Fe to C is 0.05, and the mol ratio of Cu to C is 0.02.
(4) Transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting for 35min under the condition of 38 ℃ water bath, washing with deionized water, drying, transferring into a nitrogen environment, reacting for 2.5h under the condition of 845 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water for 25min, adding a graphite carrier B and calcium chloride, continuously stirring for 1.8h, washing with deionized water, drying, transferring to anaerobic activated sludge, and carrying out oscillation culture and biofilm formation at 26 ℃ to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 23min to obtain material A;
and (3) taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting for 35min at 48 ℃, adding the biological carrier, continuing to react for 25min, centrifuging, washing, and freeze-drying to obtain the sewage treatment agent.
The components comprise: by mass, 14 parts of chitosan, 3 parts of graphite intercalation compound, 8 parts of biological carrier and 3 parts of glutaraldehyde.
Example 3:
a preparation method of a carrier-solidified microbial sewage treatment agent comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring for 30min, reacting for 1h in a water bath at 30 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at 900 ℃ for 3min, dissolving the pretreated graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring for 2.5h, adding an epoxy silane coupling agent, stirring for 8h in a 80 ℃ constant-temperature water bath, washing, filtering, and vacuum drying at 85 ℃ to obtain a graphite carrier A; the epoxy silane coupling agent is KH-560.
(3) Placing the graphite carrier A and the metal chloride in a ball mill for ball milling for 3h, transferring to a vacuum tube furnace, vacuumizing, heating to 1100 ℃, preserving heat for 3h under the condition that the vacuum degree is 3.5mPa, transferring to a cold plasma modification treatment instrument after cooling, and treating for 15min in a hydrogen atmosphere to obtain a graphite intercalation compound; the metal chloride is ferrous chloride and copper chloride, and the mass ratio of ferrous chloride to copper chloride is 2: 1 and mixing. Wherein the mol ratio of Fe to C is 0.05, and the mol ratio of Cu to C is 0.02.
(4) Transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting for 40min under the condition of water bath at 40 ℃, washing with deionized water, drying, transferring into a nitrogen environment, reacting for 3h under the condition of heat preservation at 850 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water for 30min, adding a graphite carrier B and calcium chloride, continuously stirring for 2h, washing with deionized water, drying, transferring to anaerobic activated sludge, and performing shake culture and biofilm formation at 28 ℃ to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 25min to obtain material A;
and (3) taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting for 40min at 50 ℃, adding the biological carrier, continuing to react for 30min, centrifuging, washing, and freeze-drying to obtain the sewage treatment agent.
The components comprise: by mass, 14 parts of chitosan, 3 parts of graphite intercalation compound, 8 parts of biological carrier and 3 parts of glutaraldehyde.
Comparative example 1:
a preparation method of a carrier-solidified microbial sewage treatment agent comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring for 25min, reacting for 0.6h in a water bath at 25 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at 850 ℃ for 2min, dissolving the pretreated graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring for 2.2h, adding an epoxy silane coupling agent, stirring for 7.5h in a constant-temperature water bath at 78 ℃, washing, filtering, and vacuum drying at 83 ℃ to obtain a graphite carrier A; the epoxy silane coupling agent is KH-560.
(3) Placing the graphite carrier A and the metal chloride in a ball mill for ball milling for 2.5h, transferring to a vacuum tube furnace, vacuumizing, heating to 1050 ℃, preserving heat for 2.5h under the condition that the vacuum degree is 3.5mPa, cooling, transferring to a cold plasma modification treatment instrument, and treating for 13min in a hydrogen atmosphere to obtain a graphite intercalation compound; the metal chloride is ferrous chloride and copper chloride, and the mass ratio of ferrous chloride to copper chloride is 2: 1 and mixing. Wherein the mol ratio of Fe to C is 0.05, and the mol ratio of Cu to C is 0.02.
(4) Mixing and stirring sodium acetate, humic acid and deionized water for 25min, adding a graphite carrier A and calcium chloride, continuously stirring for 1.8h, washing with deionized water, drying, transferring to anaerobic activated sludge, and performing oscillation culture and biofilm formation at 26 ℃ to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 23min to obtain material A;
and (3) taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting for 35min at 48 ℃, adding the biological carrier, continuing to react for 25min, centrifuging, washing, and freeze-drying to obtain the sewage treatment agent.
The components comprise: by mass, 14 parts of chitosan, 3 parts of graphite intercalation compound, 8 parts of biological carrier and 3 parts of glutaraldehyde.
Comparative example 1 parameter changes were made on the basis of example 2, and in comparative example 1, the preparation of the bio-carrier was performed by using the graphite carrier a, and the contents of the remaining components and the process parameters were the same as those of example 2.
Comparative example 2:
a preparation method of a carrier-solidified microbial sewage treatment agent comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring for 25min, reacting for 0.6h in a water bath at 25 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at 850 ℃ for 2min, dissolving the pretreated graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring for 2.2h, adding an epoxy silane coupling agent, stirring for 7.5h in a constant-temperature water bath at 78 ℃, washing, filtering, and vacuum drying at 83 ℃ to obtain a graphite carrier A; the epoxy silane coupling agent is KH-560.
(3) Placing the graphite carrier A and ferrous chloride in a ball mill for ball milling for 2.5h, transferring to a vacuum tube furnace, vacuumizing, heating to 1050 ℃, preserving heat for 2.5h under the condition that the vacuum degree is 3.5mPa, cooling, transferring to a cold plasma modification treatment instrument, and treating for 13min in a hydrogen atmosphere to obtain a graphite intercalation compound; wherein the molar ratio of Fe to C is 0.05.
(4) Transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting for 35min under the condition of 38 ℃ water bath, washing with deionized water, drying, transferring into a nitrogen environment, reacting for 2.5h under the condition of 845 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water for 25min, adding a graphite carrier B and calcium chloride, continuously stirring for 1.8h, washing with deionized water, drying, transferring to anaerobic activated sludge, and carrying out oscillation culture and biofilm formation at 26 ℃ to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 23min to obtain material A;
and (3) taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting for 35min at 48 ℃, adding the biological carrier, continuing to react for 25min, centrifuging, washing, and freeze-drying to obtain the sewage treatment agent.
The components comprise: by mass, 14 parts of chitosan, 3 parts of graphite intercalation compound, 8 parts of biological carrier and 3 parts of glutaraldehyde.
Comparative example 2 parameters were changed on the basis of example 2, in comparative example 2, the metal chloride was ferrous chloride, and the contents of the remaining components and the process parameters were the same as those of example 2.
Comparative example 3:
a preparation method of a carrier-solidified microbial sewage treatment agent comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring for 25min, reacting for 0.6h in a water bath at 25 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) taking the pretreated graphite, and preheating for 2min at 850 ℃ to obtain a graphite carrier A;
(3) placing the graphite carrier A and the metal chloride in a ball mill for ball milling for 2.5h, transferring to a vacuum tube furnace, vacuumizing, heating to 1050 ℃, preserving heat for 2.5h under the condition that the vacuum degree is 3.5mPa, cooling, transferring to a cold plasma modification treatment instrument, and treating for 13min in a hydrogen atmosphere to obtain a graphite intercalation compound; the metal chloride is ferrous chloride and copper chloride, and the mass ratio of ferrous chloride to copper chloride is 2: 1 and mixing. Wherein the mol ratio of Fe to C is 0.05, and the mol ratio of Cu to C is 0.02.
(4) Transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting for 35min under the condition of 38 ℃ water bath, washing with deionized water, drying, transferring into a nitrogen environment, reacting for 2.5h under the condition of 845 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water for 25min, adding a graphite carrier B and calcium chloride, continuously stirring for 1.8h, washing with deionized water, drying, transferring to anaerobic activated sludge, and carrying out oscillation culture and biofilm formation at 26 ℃ to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 23min to obtain material A;
and (3) taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting for 35min at 48 ℃, adding the biological carrier, continuing to react for 25min, centrifuging, washing, and freeze-drying to obtain the sewage treatment agent.
The components comprise: by mass, 14 parts of chitosan, 3 parts of graphite intercalation compound, 8 parts of biological carrier and 3 parts of glutaraldehyde.
Comparative example 3 the parameters were changed on the basis of example 2, and comparative example 3 was not treated with the epoxy silane coupling agent, and the contents of the remaining components and the process parameters were identical to those of example 2.
And (3) detection test:
the sewage treatment agents prepared in examples 1 to 3 and comparative examples 1 to 3 were used for the following tests:
and adding 2g of sewage treatment agent into 100mL of 10mg/L Cr (VI) solution, reacting at 30 ℃ for 6h, and detecting and calculating the Cr (VI) removal rate.
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Removal rate% | 99.2% | 99.5% | 99.1% | 98.9% | 99.3% | 99.1% |
And (4) conclusion: the application discloses a carrier-solidified microbial sewage treating agent and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared sewage treating agent has an excellent treatment effect on hexavalent chromium wastewater, the cost is low, the efficiency is high, the carrier-solidified microbial sewage treating agent can be widely applied to sewage treatment of the hexavalent chromium wastewater, and the carrier-solidified microbial sewage treating agent has high practicability.
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 (9)
1. A preparation method of a carrier-solidified microbial sewage treatment agent is characterized by comprising the following steps: the method comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring, reacting for 0.5-1h in a water bath at 20-30 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at the temperature of 800-900 ℃, dissolving the graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring, adding an epoxy silane coupling agent, stirring in a constant-temperature water bath at the temperature of 75-80 ℃, washing, filtering, and vacuum drying to obtain a graphite carrier A;
(3) taking the graphite carrier A and the metal chloride, placing the graphite carrier A and the metal chloride in a ball mill, carrying out ball milling for 2-3h, transferring the ball milled for 2-3h to a vacuum tube furnace, vacuumizing, heating to 1000-plus-material 1100 ℃, carrying out heat preservation reaction, cooling, transferring to a cold plasma modification treatment instrument, and carrying out treatment for 10-15min in a hydrogen atmosphere to obtain a graphite intercalation compound;
(4) transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting in a water bath at 35-40 ℃, washing with deionized water, drying, transferring into a nitrogen environment, reacting at 840-850 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water, adding a graphite carrier B and calcium chloride, continuously stirring, washing with deionized water, drying, transferring to anaerobic activated sludge, and performing shaking culture and biofilm formation to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 20-25min to obtain material A;
taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting at 45-50 ℃, adding the biological carrier, continuing to react, centrifugally washing, and freeze-drying to obtain the sewage treatment agent.
2. The method of claim 1, wherein the carrier-immobilized microbial wastewater treatment agent is prepared by: the method comprises the following steps:
(1) putting the flake graphite into a mixed solution of nitric acid and phosphoric acid, adding potassium permanganate, mixing and stirring for 20-30min, reacting for 0.5-1h in a water bath at 20-30 ℃, washing and filtering with deionized water, and drying in vacuum to obtain pretreated graphite;
(2) preheating pretreated graphite at the temperature of 800-900 ℃ for 2-3min, dissolving the graphite in a mixed solution of deionized water and absolute ethyl alcohol, ultrasonically stirring for 2-2.5h, adding an epoxy silane coupling agent, stirring for 7-8h in a constant-temperature water bath at the temperature of 75-80 ℃, washing, filtering, and vacuum drying at the temperature of 80-85 ℃ to obtain a graphite carrier A;
(3) taking the graphite carrier A and the metal chloride, placing the graphite carrier A and the metal chloride in a ball mill, carrying out ball milling for 2-3h, transferring the ball milled for 2-3h to a vacuum tube furnace, vacuumizing, heating to 1000-1100 ℃, carrying out heat preservation for 2-3h under the condition that the vacuum degree is 3.5mPa, transferring the ball milled into a cold plasma modification treatment instrument after cooling, and carrying out treatment for 10-15min under the hydrogen atmosphere to obtain a graphite intercalation compound;
(4) transferring the pretreated graphite into a mixed solution of nitric acid and formic acid, adding potassium permanganate, reacting for 30-40min under the condition of 35-40 ℃ water bath, washing with deionized water, drying, transferring into a nitrogen environment, carrying out heat preservation reaction at 840 ℃ and 850 ℃, and cooling to obtain a graphite carrier B;
mixing and stirring sodium acetate, humic acid and deionized water for 20-30min, adding a graphite carrier B and calcium chloride, continuously stirring for 1.5-2h, washing with deionized water, drying, transferring to anaerobic activated sludge, and performing oscillation culture and biofilm formation at 25-28 ℃ to obtain a biological carrier;
(5) mixing chitosan and acetic acid solution, and stirring for 20-25min to obtain material A;
taking absolute ethyl alcohol and glutaraldehyde, uniformly mixing, adding the material A and the graphite intercalation compound, reacting for 30-40min at 45-50 ℃, adding the biological carrier, continuing to react for 20-30min, centrifuging, washing, and freeze-drying to obtain the sewage treatment agent.
3. The method of claim 1, wherein the carrier-immobilized microbial wastewater treatment agent is prepared by: in the step (3), the metal chloride is ferrous chloride and copper chloride in a mass ratio of 2: 1 and mixing.
4. The method of claim 1, wherein the carrier-immobilized microbial wastewater treatment agent is prepared by: in the step (2), the epoxy silane coupling agent is KH-560.
5. The method of claim 1, wherein the carrier-immobilized microbial wastewater treatment agent is prepared by: in the step (4), the reaction time is kept for 2-3 h.
6. The method of claim 1, wherein the carrier-immobilized microbial wastewater treatment agent is prepared by: in the step (4), the anaerobic activated sludge is acclimated in advance by an organic chromium solution.
7. The method of claim 1, wherein the carrier-immobilized microbial wastewater treatment agent is prepared by: in the step (1), the mass ratio of the crystalline flake graphite to the potassium permanganate is 1: 0.2.
8. the method of claim 1, wherein the carrier-immobilized microbial wastewater treatment agent is prepared by: in the step (4), the mass ratio of the pretreated graphite to the potassium permanganate is 1: 0.15.
9. a wastewater treatment agent prepared by the method for preparing a carrier-immobilized microbial wastewater treatment agent according to any one of claims 1 to 8.
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| CN103304026A (en) * | 2013-07-08 | 2013-09-18 | 北京金科复合材料有限责任公司 | Preparation method and use of compound immobilized biological carrier |
| US20170175100A1 (en) * | 2015-12-17 | 2017-06-22 | Soochow University | Composite of Paracoccus denitrificans immobilized on modified graphene oxide and its preparation method and application |
| US20200222956A1 (en) * | 2016-08-22 | 2020-07-16 | Remediation Products, Inc. | Bioremediation composition with time-release materials for removing energetic compounds from contaminated environments |
| CN112897705A (en) * | 2021-01-13 | 2021-06-04 | 北京大学 | Preparation method and application of multilayer graphene oxide modified microbial carrier |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103304026A (en) * | 2013-07-08 | 2013-09-18 | 北京金科复合材料有限责任公司 | Preparation method and use of compound immobilized biological carrier |
| US20170175100A1 (en) * | 2015-12-17 | 2017-06-22 | Soochow University | Composite of Paracoccus denitrificans immobilized on modified graphene oxide and its preparation method and application |
| US20200222956A1 (en) * | 2016-08-22 | 2020-07-16 | Remediation Products, Inc. | Bioremediation composition with time-release materials for removing energetic compounds from contaminated environments |
| CN112897705A (en) * | 2021-01-13 | 2021-06-04 | 北京大学 | Preparation method and application of multilayer graphene oxide modified microbial carrier |
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