CN115414911B - Is rich in Fe x N-structure pharmaceutical sludge biochar, preparation method and application - Google Patents
Is rich in Fe x N-structure pharmaceutical sludge biochar, preparation method and application Download PDFInfo
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- CN115414911B CN115414911B CN202210996097.0A CN202210996097A CN115414911B CN 115414911 B CN115414911 B CN 115414911B CN 202210996097 A CN202210996097 A CN 202210996097A CN 115414911 B CN115414911 B CN 115414911B
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- 239000010802 sludge Substances 0.000 title claims abstract description 167
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 176
- 239000002351 wastewater Substances 0.000 claims abstract description 62
- 229910052742 iron Inorganic materials 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000003242 anti bacterial agent Substances 0.000 claims description 18
- 229940088710 antibiotic agent Drugs 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229940124307 fluoroquinolone Drugs 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 24
- 238000000197 pyrolysis Methods 0.000 abstract description 20
- 230000001105 regulatory effect Effects 0.000 abstract description 9
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 3
- 239000010826 pharmaceutical waste Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 description 19
- 229960003376 levofloxacin Drugs 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 16
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 13
- 238000004065 wastewater treatment Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000643 oven drying Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RXZBMPWDPOLZGW-XMRMVWPWSA-N (E)-roxithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=N/OCOCCOC)/[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 RXZBMPWDPOLZGW-XMRMVWPWSA-N 0.000 description 1
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 description 1
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 description 1
- 229910002552 Fe K Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 102100031180 Hereditary hemochromatosis protein Human genes 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- PNNCWTXUWKENPE-UHFFFAOYSA-N [N].NC(N)=O Chemical compound [N].NC(N)=O PNNCWTXUWKENPE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000002599 biostatic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- -1 difluorofloxacin Chemical compound 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229960000740 enrofloxacin Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960003276 erythromycin Drugs 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
- 229960001699 ofloxacin Drugs 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229960005224 roxithromycin Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000003805 vibration mixing Methods 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/026—Treating water for medical or cosmetic purposes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Is rich in Fe x N-structure pharmaceutical sludge biochar, a preparation method and application thereof, and belongs to the technical field of pharmaceutical waste treatment. The method comprises the steps of taking pharmaceutical sludge containing Fenton iron mud, carrying out filter pressing dehydration, drying and crushing, and adding ZnCl 2 Carrying out activation pretreatment and drying to obtain pretreated pharmaceutical sludge; uniformly mixing the pretreated pharmaceutical sludge with 3 times of urea solid in the mass ratio of N 2 Pyrolyzing for 1-2 h under the protection of 750-850 ℃, cooling, washing with hydrochloric acid, and regulating pH to 7 with deionized water to obtain pharmaceutical sludge biochar; and degrading antibiotic pharmaceutical wastewater by activating peroxymonosulfate with pharmaceutical sludge biochar. According to the invention, the pharmaceutical sludge is subjected to iron-nitrogen co-doping modification pyrolysis treatment, so that the pharmaceutical sludge biochar with excellent catalytic performance is obtained, and is reasonably applied to the antibiotic pharmaceutical wastewater, so that the treatment of the antibiotic pharmaceutical wastewater is effectively realized.
Description
Technical Field
The invention relates to the technical field of pharmaceutical waste treatment, in particular to a method for treating pharmaceutical wasteAnd a method for utilizing Fe-enriched material x A method for treating pharmaceutical wastewater by using pharmaceutical sludge biochar with an N structure.
Background
The scale of treating high-concentration pharmaceutical wastewater is huge due to the rapid development of the pharmaceutical industry. At present, biological treatment units are still an important way for removing antibiotics in pharmaceutical wastewater; but the biostatic nature of antibiotics can greatly limit the removal capacity of this technique. Because the traditional wastewater treatment system is difficult to effectively remove antibiotics in water, advanced oxidation technology is added to deeply treat pharmaceutical wastewater.
In addition to the deep removal of antibiotics, the disposal of pharmaceutical sludge is another problem that plagues pharmaceutical wastewater treatment. A large amount of pharmaceutical sludge is generated in the pharmaceutical wastewater treatment process, and compared with other types of sludge, the pharmaceutical sludge has complex composition, contains high-concentration salts, antibiotics, pharmaceutical active components and the like, has a plurality of toxic and harmful substances, has high concentration and is huge in potential hazard. Therefore, the pharmaceutical sludge must be safely treated to avoid environmental hazards.
The pyrolysis charcoal making technology is a process that biomass raw materials absorb heat energy under the condition of isolating oxygen, and a biomass structure is destroyed to form pores, so that the biomass raw materials are converted into charcoal. The pharmaceutical sludge contains a large amount of organic matters, so that the pharmaceutical sludge can be utilized by a pyrolysis charcoal making technology. During pyrolysis, high temperatures of hundreds of degrees can destroy high risk contaminants such as antibiotics adsorbed on pharmaceutical sludge. In addition, in order to improve biodegradability of pharmaceutical wastewater, wastewater treatment systems generally pretreat pharmaceutical wastewater using a Fenton method. Iron sludge produced by Fenton pretreatment, namely Fenton iron sludge, is used by many pharmaceutical factories to replace commercial conditioner to promote dehydration of pharmaceutical sludge, so that the dehydrated pharmaceutical sludge contains rich Fe (mainly Fe (OH)) 3 )。
However, it is shown in the related art that Fe 2 O 3 And Fe (Fe) 3 O 4 Municipal sludge, which is the primary iron source, is difficult to form Fe during nitrogen doping x N structure, even with commercially available FeCl 3 Fe is also difficult to form as an iron source x N structure, but often forms FeN x Structure of FeN x The catalytic performance of the structure is obviously reduced. Therefore, a need exists to find a method for preparing Fe-rich sludge that can effectively utilize pharmaceutical sludge x The catalyst with the structure N can deeply treat pharmaceutical wastewater.
Disclosure of Invention
To solve the problems in the prior art, the invention provides a method for preparing a high-Fe alloy by using Fe x Method for treating pharmaceutical wastewater by using N-structured pharmaceutical sludge biochar, and attempts are made to contain Fe (OH) 3 The pharmaceutical sludge of (2) is mixed with an external nitrogen source to perform anaerobic pyrolysis to prepare the Fe-containing material x The biochar with the N structure is used as a catalyst to efficiently activate persulfate to degrade organic pollutants remained in the pharmaceutical wastewater conventionally treated effluent. The method can realize safe treatment of pharmaceutical sludge and advanced treatment of pharmaceutical wastewater, can synchronously solve the problems that the prior pharmaceutical wastewater of pharmaceutical enterprises has poor antibiotic removal effect and the pharmaceutical sludge is difficult to safely treat, and is a new idea of treating waste with waste and cleaning production.
The specific technical scheme of the invention is as follows:
in one aspect, a Fe-enriched composition is provided x The preparation method of the pharmaceutical sludge biochar with the N structure comprises the following steps:
(1) Adding Fenton iron-containing mud into pharmaceutical sludge, press-filtering, dewatering, drying, pulverizing, adding ZnCl whose mole concentration is 5mol/L 2 Carrying out modification pretreatment in an aqueous solution, and drying to obtain pretreated pharmaceutical sludge;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid, and then adding the mixture into N 2 Under the protection of 750-850 ℃ for co-pyrolysis for 1-2 h, cooling, washing with hydrochloric acid and deionized water, and adjusting pH to 7 to obtain Fe-enriched alloy x N structure pharmaceutical sludge biochar.
Optionally, in the step (1), the addition amount of the Fenton iron mud is 5-20% of the total pharmaceutical sludge.
Further, in the step (1), the addition amount of the Fenton iron mud is 10% of the total pharmaceutical sludge.
Optionally, in the step (2), the mass ratio of the pretreated pharmaceutical sludge to urea is 1:1-1:4.
Further, in the step (2), the mass ratio of the pretreated pharmaceutical sludge to urea is 1:3.
In another aspect, a pharmaceutical sludge biochar prepared by the method is provided.
In a further aspect, there is provided a Fe-enriched product obtained by the above process x Application of N-structure pharmaceutical sludge biochar in treating pharmaceutical wastewater to enrich Fe x The pharmaceutical sludge biochar with the N structure is added into fluoroquinolone antibiotics pharmaceutical wastewater containing peroxymonosulfate, and the reaction of activating the peroxymonosulfate to degrade the antibiotics is carried out at the temperature of 25-45 ℃ to obtain treated effluent.
Optionally, the Fe-rich material x The adding amount of the pharmaceutical sludge biochar with the N structure is 0.05-0.15 g/L.
Optionally, the adding amount of the peroxymonosulfate is 1-10 mM.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the Fe-N co-doping modification pyrolysis treatment to the pharmaceutical sludge to obtain the Fe-enriched material x The pharmaceutical sludge biochar with the N structure and excellent catalytic performance is reasonably applied to fluoroquinolone antibiotic pharmaceutical wastewater, so that the fluoroquinolone antibiotic pharmaceutical wastewater is effectively treated.
2. The raw material of the pharmaceutical sludge biochar prepared by the invention is pharmaceutical sludge generated by a pharmaceutical wastewater treatment system, so that the purchase is not needed, and the transportation, storage and other costs generated by alternative raw materials are saved.
3. The iron source for carrying out iron doping modification on the sludge comes from Fe (OH) generated by a Fenton pretreatment system of pharmaceutical wastewater 3 Can effectively form Fe with the doped nitrogen element x The N structure does not need to additionally purchase iron-based chemical agents, so that the preparation cost is greatly saved.
4. The pharmaceutical sludge biochar has excellent performance of activating the peroxymonosulfate, and can activate 5mM of peroxymonosulfate to completely degrade 80mg/L levofloxacin under the addition amount of 0.1g/L within 90 min.
5. The invention uses the pharmaceutical sludge biochar to activate the peroxymonosulfate to treat pharmaceutical wastewater, has simple operation and low cost, and can effectively solve the problem of unsatisfactory biological treatment process effect.
6. The invention utilizes the pharmaceutical wastewater treatment system to prepare the iron-nitrogen co-doped biochar from the waste pharmaceutical sludge and Fenton iron sludge for carrying out catalytic degradation treatment on pharmaceutical wastewater, thereby realizing the treatment of waste with waste and clean production in pharmaceutical enterprises.
Fe x N and FeN x Is characterized by the following and catalytic principle:
Fe x n and FeN x Are all substances having Fe-N structure. Wherein Fe is x N is formed by the gradual diffusion of N atoms into interstitial sites of the metal Fe lattice, during which process the metal Fe creates two distinct layers. The outermost layer of iron (the composite layer or "white" layer) contains iron nitride, and the diffusion layer underneath the composite layer contains a lattice of Fe. Fe (Fe) x N has very high hardness and corrosion resistance, and the composite layer can effectively protect the metal of the inner layer from being dissolved by etching, avoid poisoning of adsorption species and improve the durability of the catalyst. Meanwhile, the metal of the inner layer can provide free electrons, promote electron transfer and help to enhance catalytic performance. Thus Fe x N has strong reactivity and is very stable, insensitive to the pH change of the solution and wide in pH range of the pharmaceutical wastewater suitable for degradation. And FeN x In contrast thereto, it is often the Fe atom that is loaded between 4 coordinated N atoms. In an acidic medium, feN x The active sites are susceptible to protonation, which reduces their intrinsic catalytic activity, and demetallization of the central Fe atom may reduce the number of active sites, which in turn leads to activity decay.
Drawings
Fig. 1 is a transmission electron micrograph of a pharmaceutical sludge biochar catalyst according to example 1 of the present invention.
Fig. 2 is an XRD pattern of the biochar catalyst in exemplary example 1, example 5 and comparative examples 1 to 2 of the present invention.
FIG. 3 is a high resolution N1s spectrum of the biochar catalyst of example 1, example 5 and comparative examples 1-2 according to the present invention.
Fig. 4 is an XRD pattern of the biochar catalyst in exemplary embodiments 1 to 4 of the present invention.
FIG. 5 is a high resolution N1s spectrum of the biochar catalyst of exemplary embodiments 1-4 of the present invention.
FIG. 6 is a Fe-enriched alloy of exemplary embodiment 1 of the present invention x The effect of the N-structure pharmaceutical sludge biochar on the removal rate of the levofloxacin under different pH conditions is shown.
FIG. 7 is an exemplary comparative example 3 of the present invention to illustrate pyrolysis temperature, pyrolysis time versus Fe-rich formation x Influence of pharmaceutical sludge biochar of N structure.
Detailed Description
The use of embodiments of the invention is rich in Fe x The method for treating pharmaceutical wastewater by using the pharmaceutical sludge biochar with the N structure comprises the following steps of:
(1) Adding Fenton iron mud into pharmaceutical sludge, press-filtering, dewatering, drying, pulverizing, mixing with 5mol/L ZnCl 2 Mixing the aqueous solutions, carrying out modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in some specific embodiments, the mixing mode can be known mixing modes such as mechanical stirring, vibration mixing and the like, the drying is generally carried out by adopting an oven, the drying temperature is generally 100-200 ℃, and the Fenton iron mud is easily decomposed into Fe due to the overhigh temperature 2 O 3 Or Fe 3 O 4 The temperature is too low, which is unfavorable for quick drying.
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid, and then adding the mixture into N 2 Under the protection, heating to 750-850 ℃, pyrolyzing for 1-2 h, cooling, cleaning by hydrochloric acid and deionized water, and adjusting pH to 7 to obtain the Fe-enriched material x Pharmaceutical sludge biochar with an N structure; pyrolysis temperatures above 850 ℃ or below 750 ℃ are detrimental to Fe formation x And an N structure.
(3) The Fe-enriched material obtained in the step (2) x The pharmaceutical sludge biochar with the N structure is added into fluoroquinolone antibiotics pharmaceutical wastewater containing peroxymonosulfate, and the reaction of activating the peroxymonosulfate to degrade the antibiotics is carried out at the temperature of 25-45 ℃ to obtain treated effluent.
The invention adopts a method for preparing the Fe (OH) containing alloy 3 Urea nitrogen doping modification is carried out on pharmaceutical sludge of (2) to obtain Fe with the following properties x The pharmaceutical sludge biochar catalyst with the N structure is reasonably used in the advanced oxidation process of fluoroquinolone antibiotic pharmaceutical wastewater, and the advanced treatment of the fluoroquinolone antibiotic pharmaceutical wastewater is effectively realized. By the specific embodiment of the invention, the use of pure Fe (OH) can be reasonably speculated 3 Instead of containing Fe (OH) 3 The pharmaceutical sludge of (2) can also obtain Fe x N, but it will be appreciated that this increases the cost and does not achieve the environmental protection of "waste with waste".
In addition, the Fe-enriched alloy obtained by the invention x The pharmaceutical sludge biochar with the N structure can also be applied to the field of other organic wastewater treatment except fluoroquinolone antibiotic wastewater.
Fluoroquinolone antibiotics according to the present invention include, but are not limited to, ofloxacin, enrofloxacin, ciprofloxacin, norfloxacin, difluorofloxacin, erythromycin, roxithromycin, and the like.
The invention will be further described with reference to the following examples, which are given by way of illustration only, but the scope of the invention is not limited thereto.
The pharmaceutical sludge used in the following examples was a fluoroquinolone antibiotic pharmaceutical company A 2 And (3) discharging sludge from a secondary sedimentation tank after the O wastewater treatment system, adding Fenton iron sludge as a sludge dewatering conditioner, wherein the water content of the sludge after press filtration is 52.3%, the iron content is 244.69 +/-3.15 mg/g, the total solid is 476.9g/L, the volatile solid is 316.3g/L, and the VS/TS is 66.3%.
It will be appreciated that the pharmaceutical sludge according to embodiments of the present invention may also be derived from municipal sludge or other high organic waste.
Example 1
The present embodiment provides a method for producing a high-purity Fe-rich alloy x The method for deeply treating fluoroquinolone antibiotic pharmaceutical wastewater by using the pharmaceutical sludge biochar with an N structure comprises the following specific steps:
(1) Mixing Fenton iron mud with pharmaceutical sludge with weight of 10%, press-filtering and dewatering to obtain sludge cake, oven drying to constant weight, grinding, sieving with 60 mesh sieve, and mixing with 5mol/L ZnCl 2 Mixing the aqueous solutions, carrying out modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge and ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1:1, the aqueous solution is vibrated for 24 hours to be uniformly mixed, and the drying conditions are as follows: oven drying at 105deg.C to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with 3 times of urea solid by weight, and adding the mixture into N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is increased to 800 ℃, the pyrolysis is carried out for 1h, after cooling, the mixture is washed by hydrochloric acid with the volume fraction of 5%, the pH is regulated to 7 by deionized water, and the Fe-enriched product is obtained x Pharmaceutical sludge biochar with an N structure (labeled as PZBC 800U);
(3) 10mg of the Fe-enriched material obtained in the step (2) is taken x Adding pharmaceutical sludge biochar (PZBC 800U) with an N structure into 100mL of pharmaceutical wastewater containing levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater of the levofloxacin is 80mg/L, the pH value is 6.5, and the adding amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, and the shaking is carried out in a dark place under the condition of 25 ℃ and 220r/min, so that treated effluent is obtained after the catalytic degradation reaction.
Example 2
This comparative example provides a method of using a Fe-rich alloy x The method for deeply treating fluoroquinolone antibiotic pharmaceutical wastewater by using the pharmaceutical sludge biochar with an N structure comprises the following specific steps:
(1) Mixing Fenton iron mud with the pharmaceutical sludge with the mass of 5%, press-filtering and dehydrating to obtain pharmaceutical sludge cake, drying to constant weight,grinding, sieving with 60 mesh sieve, mixing with 5mol/L ZnCl 2 Mixing the aqueous solutions, carrying out modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge and ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1:1, the aqueous solution is vibrated for 24 hours to be uniformly mixed, and the drying conditions are as follows: oven drying at 105deg.C to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid with the same weight, and adding the mixture into N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is increased to 850 ℃, the pyrolysis is carried out for 2 hours, after cooling, the mixture is washed by hydrochloric acid with the volume fraction of 5%, the pH is regulated to 7 by deionized water, and the Fe-enriched product is obtained x Pharmaceutical sludge biochar with an N structure (labeled as PZBC 800U-1);
(3) 10mg of the Fe-enriched material obtained in the step (2) is taken x Adding pharmaceutical sludge biochar (PZBC 800U-1) with an N structure into 100mL of pharmaceutical wastewater containing levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater of the levofloxacin is 80mg/L, the pH value is 6.5, and the adding amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, and the shaking is carried out in a dark place under the condition of 25 ℃ and 220r/min, so that treated effluent is obtained after the catalytic degradation reaction.
Example 3
This comparative example provides a method of using a Fe-rich alloy x The method for deeply treating fluoroquinolone antibiotic pharmaceutical wastewater by using the pharmaceutical sludge biochar with an N structure comprises the following specific steps:
(1) Mixing Fenton iron mud with pharmaceutical sludge with weight of 10%, press-filtering and dewatering to obtain pharmaceutical sludge cake, oven drying to constant weight, grinding, sieving with 60 mesh sieve, and mixing with 5mol/L ZnCl 2 Mixing the aqueous solutions, carrying out modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge and ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1:1, the aqueous solution is vibrated for 24 hours to be uniformly mixed, and the drying conditions are as follows: oven drying at 105deg.C to constant weight;
(2) The pretreated pharmacy obtained in the step (1)Uniformly mixing the sludge and urea solid with the weight being 2 times that of the sludge, and adding the urea solid into the mixture in the presence of N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is raised to 750 ℃, the pyrolysis is carried out for 1.5 hours, the cooling is carried out, the washing is carried out with hydrochloric acid with the volume fraction of 5%, the pH is regulated to 7 by deionized water, and the Fe-enriched product is obtained x Pharmaceutical sludge biochar with an N structure (labeled as PZBC 800U-2);
(3) 10mg of the Fe-enriched material obtained in the step (2) is taken x Adding pharmaceutical sludge biochar (PZBC 800U-2) with an N structure into 100mL of pharmaceutical wastewater containing levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater of the levofloxacin is 80mg/L, the pH value is 6.5, and the adding amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, and the shaking is carried out in a dark place under the condition of 25 ℃ and 220r/min, so that treated effluent is obtained after the catalytic degradation reaction.
Example 4
This comparative example provides a method of using a Fe-rich alloy x The method for deeply treating fluoroquinolone antibiotic pharmaceutical wastewater by using the pharmaceutical sludge biochar with an N structure comprises the following specific steps:
(1) Mixing Fenton iron mud with the weight of 15% of that of pharmaceutical sludge, press-filtering and dewatering to obtain pharmaceutical sludge cake, oven drying to constant weight, grinding, sieving with 60 mesh sieve, and mixing with 5mol/L ZnCl 2 Mixing the aqueous solutions, carrying out modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge and ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1:1, the aqueous solution is vibrated for 24 hours to be uniformly mixed, and the drying conditions are as follows: oven drying at 105deg.C to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with 4 times of urea solid by weight, and adding the mixture into N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is increased to 800 ℃, the pyrolysis is carried out for 1.5 hours, the cooling is carried out, the washing is carried out with hydrochloric acid with the volume fraction of 5%, the pH is regulated to 7 by deionized water, and the Fe-enriched product is obtained x Pharmaceutical sludge biochar with an N structure (labeled as PZBC 800U-4);
(3) Step 10mg is taken(2) The obtained Fe-enriched alloy is rich in Fe x Adding pharmaceutical sludge biochar (PZBC 800U-4) with an N structure into 100mL of pharmaceutical wastewater containing levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater of the levofloxacin is 80mg/L, the pH value is 6.5, and the adding amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, and the shaking is carried out in a dark place under the condition of 25 ℃ and 220r/min, so that treated effluent is obtained after the catalytic degradation reaction.
Example 5
The comparative example provides a method for deeply treating fluoroquinolone antibiotics pharmaceutical wastewater by using pharmaceutical sludge biochar, which comprises the following specific steps:
(1) According to the quality of Fenton iron mud being 20% of the quality of pharmaceutical sludge, mixing the two, performing filter pressing and dehydration to obtain pharmaceutical sludge cake, drying to constant weight, grinding, sieving with a 60-mesh sieve, adding 35g of pharmaceutical sludge cake into 500ml of ultrapure water, adjusting pH=2.0, adding 15g of ferrous sulfate and 60ml of hydrogen peroxide into sludge suspension, reacting for 1h, adjusting pH to about 7.0, dehydrating and drying to obtain pharmaceutical sludge with increased endogenous iron content of 381.70 +/-6.82 mg/g;
(2) Adding the pharmaceutical sludge with the increased endogenous iron obtained in the step (1) into ZnCl with the molar concentration of 5mol/L 2 Carrying out modification pretreatment in aqueous solution; pharmaceutical sludge and ZnCl 2 Oscillating for 24 hours at the water solution impregnation ratio (w/v) of 1:1, and drying in a baking oven at 105 ℃ to obtain pretreated pharmaceutical sludge;
(3) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (2) with 3 times of urea solid by weight under the protection of N2, wherein N is 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, pyrolysis is carried out for 1.5 hours at 800 ℃, after cooling, hydrochloric acid with the volume fraction of 5% is used for cleaning, the pH value is regulated to 7 by deionized water, and the pharmaceutical sludge biochar (PZBC 800 U+Fe) for increasing endogenous iron is obtained.
(4) Adding 10mg of the charcoal (PZBC 800 U+Fe) catalyst prepared in the step (3) into 100mL of pharmaceutical wastewater containing levofloxacin, wherein the initial concentration C0 of the pharmaceutical wastewater of the levofloxacin is 80mg/L, the pH value is 6.5, and the adding amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, and the shaking is carried out in a dark place under the condition of 25 ℃ and 220r/min, so that treated effluent is obtained after the catalytic degradation reaction.
The invention characterizes the iron-nitrogen co-doped pharmaceutical sludge biochar (PZBC 800U) prepared in the embodiment 1, and the obtained transmission electron microscope photograph is shown in figure 1; as can be seen from FIG. 1, the morphology and lattice fringe spacing of the pharmaceutical sludge biochar in example 1 are as follows and Fe reported in the literature x N is consistent, which indicates that Fe is formed in the biochar during the preparation process x N structure.
Example 6
Wastewater treatment at different pH conditions:
five pH gradients of 3.0, 5.0, 6.5, 8.0 and 10.0 were set for single variable experiments of pH. The Fe is rich x The pharmaceutical sludge biochar with the N structure is PZBC800U in example 1, and the other conditions are the same as those in example 1 except that the pH value of the levofloxacin pharmaceutical wastewater is different. The results of levofloxacin removal are shown in fig. 6:
EXAMPLE 7 Effect of wastewater treatment with various fluoroquinolone antibiotics
The treatment effect of various antibiotic wastewater is as follows:
the charcoal is PZBC800U in example 1, the wastewater is treated by secondary charcoal of a wastewater treatment system of a fluoroquinolone antibiotic production enterprise, and the water quality is pH 7.1, COD 410.1 + -82.9 mg/L and ammonia nitrogen 2.8mg/L.
Table 2 7 antibiotic removal effects
It can be seen that the Fe-rich alloy is utilized x Pharmaceutical sludge generator with N structureThe method for deeply treating the fluoroquinolone antibiotic pharmaceutical wastewater by using the charcoal has good treatment effect on common fluoroquinolone antibiotic pharmaceutical wastewater.
Comparative example 1
The comparative example provides a method for deeply treating fluoroquinolone antibiotics pharmaceutical wastewater by using pharmaceutical sludge biochar, which comprises the following specific steps:
(1) Mixing Fenton iron mud with pharmaceutical sludge with weight of 10%, press-filtering and dewatering to obtain pharmaceutical sludge cake, oven drying to constant weight, grinding, sieving with 60 mesh sieve, and mixing with 5mol/L ZnCl 2 Mixing the aqueous solutions, carrying out modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; then put it in N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is raised to 800 ℃ for pyrolysis for 1.5 hours, the mixture is washed by 5% hydrochloric acid by volume fraction after cooling, the pH is regulated to 7 by deionized water, and the pharmaceutical sludge biochar (labeled as PZBC 800) which is not doped with nitrogen is obtained.
(2) Adding 10mg of the biochar (PZBC 800) prepared in the step (1) into 100mL of pharmaceutical wastewater containing levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater containing levofloxacin is 80mg/L, the pH value is 6.5, and the adding amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask is placed in a constant temperature oscillator, the shaking is carried out in a dark place under the condition of 25 ℃ and 220r/min, and the treated effluent is obtained after the catalytic degradation reaction.
Comparative example 2
The comparative example provides a method for deeply treating fluoroquinolone antibiotics pharmaceutical wastewater by using pharmaceutical sludge biochar, which comprises the following specific steps:
(1) Taking pharmaceutical sludge, performing filter pressing and dehydration to obtain pharmaceutical sludge cake, drying to constant weight, grinding, sieving with a 60-mesh sieve, then putting into a mixed solution of 1M HCl and 10% (v/v) HF for soaking treatment for 24 hours, cleaning, and drying to obtain pharmaceutical sludge with reduced endogenous iron, wherein the iron content of the sludge is 82.53 +/-1.34 mg/g;
(2) Adding the pharmaceutical sludge obtained in the step (1) with the endogenous iron removed into the sludge with the molar concentration of5mol/LZnCl 2 Carrying out modification pretreatment in aqueous solution; pharmaceutical sludge and ZnCl 2 Oscillating for 24 hours at the water solution impregnation ratio (w/v) of 1:1, and drying in a baking oven at 105 ℃ to obtain pretreated pharmaceutical sludge;
(3) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (2) with 3 times of urea solid in weight in N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, pyrolysis is carried out for 1.5 hours at 800 ℃, after cooling, the mixture is washed by hydrochloric acid with volume fraction of 5%, the pH is regulated to 7 by deionized water, and the pharmaceutical sludge biochar (PZBC 800U-Fe) for reducing iron sources is obtained.
(4) Adding 10mg of the biochar catalyst prepared in the step (3) into 100mL of pharmaceutical wastewater containing levofloxacin, wherein the initial concentration C0 of the pharmaceutical wastewater of the levofloxacin is 80mg/L, the pH value is 6.5, and the adding amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, and the shaking is carried out in a dark place under the condition of 25 ℃ and 220r/min, so that treated effluent is obtained after the catalytic degradation reaction.
XRD and characterization of high-resolution N1s spectrograms are carried out on the pharmaceutical sludge biochar prepared in the examples 1-5 and the comparative examples 1-2, and the obtained results are shown in the figures 2-5 respectively; FIG. 2 compares the crystal structures of several biochars, and XRD patterns show that the main crystal structure of the Fe-N co-doped biochar is Fe x N (x=2, 3, 4), which is consistent with the result of transmission electron microscopy. Fe with the increase of the iron content in the sludge x The peak intensity of the N characteristic peak is also increasing. Meanwhile, because the iron content in the sludge is low, fe does not appear in the PZBC800U-Fe x And an N structure. Furthermore, as can be seen from fig. 3, the biochar which is not nitrogen-doped does not exhibit Fe x N peak and PZBC800U-Fe may be Fe due to low iron content in the sludge x The N signal is also very weak, indicating that co-doping of iron and nitrogen is Fe formation x Important conditions for the N structure. Fe with the increase of the iron content in the sludge x The intensity of the N peak increases. The results of FIGS. 4 and 5 show that a mass ratio of 1:3 of sludge to urea is the optimum doping ratio to form a further improvementFe at a large amount x N. Fe in biochar x The higher the content of the N structure, the more active sites of the catalyst, i.e. the higher the catalytic performance of the catalyst. The results of XRD and XPS demonstrate that Fe in sludge forms Fe in biochar x N structure, the key role in improving catalytic performance.
In addition, 2mL of water samples in the conical flasks of examples 1 to 5 and comparative examples 1 to 2 were sampled at intervals for filtration to obtain a filtrate; taking 1mL of filtrate, measuring the concentration of the treated levofloxacin by liquid chromatography, drawing a degradation curve and calculating the reaction rate constant of the catalytic reaction. The results are shown in Table 1.
Table 1 properties of the biochar catalysts prepared in examples and comparative examples to activate peroxymonosulfate degradation antibiotics
| Case (B) | Catalyst | Removal rate (60 min) (%) | Reaction Rate K obs (min -1 ) |
| Example 1 | PZBC800U | 92.03 | 0.034 |
| Example 2 | PZBC800U-1 | 66.94 | 0.009 |
| Example 3 | PZBC800U-2 | 68.24 | 0.010 |
| Example 4 | PZBC800U-4 | 73.43 | 0.015 |
| Example 5 | PZBC800U+Fe | 100 | 0.118 |
| Comparative example 1 | PZBC800 | 84.98 | 0.025 |
| Comparative example 2 | PZBC800U-Fe | 80.58 | 0.016 |
Note that: the steps and parameters are the same except that the parameter indexes are different in the cases.
As can be seen from Table 1, example 5 has higher catalytic performance of PZBC800U+Fe after increasing the iron content in the sludge, and can achieve 100% LEV removal within 60min, K obs Reaching 0.118min -1 . As a comparison, PZBC800 and PZBC800U-Fe K obs Respectively 0.025min -1 And 0.016min -1 This indicates that Fe is co-doped with endogenous Fe and exogenous N x N is the key catalytically active site of the catalyst.
Comparative example 3
The comparative example provides a preparation method of pharmaceutical sludge biochar, which comprises the following specific steps:
(1) Mixing Fenton iron mud with pharmaceutical sludge with weight of 10%, press-filtering and dewatering to obtain sludge cake, oven drying to constant weight, grinding, sieving with 60 mesh sieve, and mixing with 5mol/L ZnCl 2 Mixing the aqueous solutions, carrying out modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge and ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1:1, the aqueous solution is vibrated for 24 hours to be uniformly mixed, and the drying conditions are as follows: oven drying at 105deg.C to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with 3 times of urea solid by weight, and adding the mixture into N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is raised to 500 ℃, the pyrolysis is carried out for 2.5 hours, after cooling, the mixture is washed by hydrochloric acid with the volume fraction of 5%, the pH is regulated to 7 by deionized water, and the pharmaceutical sludge biochar (PZBC 500U) is obtained. XRD patterns of PZBC500U are shown in FIG. 7, it can be seen that Fe is not formed x N structure, indicating that Fe-rich products cannot be obtained even with prolonged pyrolysis times at pyrolysis temperatures below 750deg.C x N structure pharmaceutical sludge biochar.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (7)
1. Is rich in Fe x The preparation method of the pharmaceutical sludge biochar with the N structure is characterized by comprising the following steps of:
(1) Adding Fenton iron mud into pharmaceutical sludge, press-filtering, dehydrating, drying, pulverizing, and adding ZnCl with molar concentration of 5mol/L 2 Carrying out modification pretreatment in an aqueous solution, and drying to obtain pretreated pharmaceutical sludge;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid, and then adding the mixture into N 2 Co-pyrolyzing under protection at 750-850 ℃ for 1-2 h, cooling, washing with hydrochloric acid and deionized water, and adjusting pH to 7 to obtain Fe-enriched alloy x Pharmaceutical sludge biochar of N structure, wherein x = 2,3,4;
in the step (1), the addition amount of Fenton iron sludge is 5-20% of the pharmaceutical sludge;
in the step (2), the mass ratio of the pretreated pharmaceutical sludge to urea is 1:1-1:4.
2. The method according to claim 1, wherein in the step (1), the Fenton iron sludge is added in an amount of 10% of the pharmaceutical sludge.
3. The method according to claim 1, wherein in the step (2), the mass ratio of the pretreated pharmaceutical sludge to urea is 1:3.
4. Is rich in Fe x The pharmaceutical sludge biochar with the N structure is characterized by being prepared by the method of any one of claims 1-3.
5. A Fe-rich product obtained by the process according to any one of claims 1 to 3 x The application of the N-structured pharmaceutical sludge biochar in treating pharmaceutical wastewater is characterized in that the Fe-enriched biochar is prepared by x The pharmaceutical sludge biochar with the N structure is added into fluoroquinolone antibiotics pharmaceutical wastewater containing peroxymonosulfate, and the reaction of activating the peroxymonosulfate to degrade antibiotics is carried out at the temperature of 25-45 ℃ to obtain treated effluent.
6. The use according to claim 5, wherein the Fe-enriched material x The adding amount of the pharmaceutical sludge biochar with the N structure is 0.05-0.15 g/L.
7. The use according to claim 6, wherein the amount of the peroxymonosulfate added is 1 to 10mM.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110171876A (en) * | 2019-05-16 | 2019-08-27 | 浙江科技学院 | A kind of N doping sludge carbon carries the preparation method and applications of nano ferriferrous oxide |
| CN110171830A (en) * | 2019-05-16 | 2019-08-27 | 浙江科技学院 | A kind of preparation method and applications of N doping magnetic bio charcoal |
| CN110227534A (en) * | 2019-07-16 | 2019-09-13 | 河南省科学院化学研究所有限公司 | A kind of magnetic N doping biology Pd/carbon catalyst and preparation method thereof based on sludge |
| CN113620368A (en) * | 2021-09-07 | 2021-11-09 | 浙江清华长三角研究院 | Method for advanced treatment of fluoroquinolone antibiotic pharmaceutical wastewater by using pharmaceutical sludge biochar |
| CN114229983A (en) * | 2021-11-29 | 2022-03-25 | 哈尔滨工业大学（深圳） | Method for preparing catalytic activated biochar from iron-containing excess sludge and removing antibiotics |
| CN114349296A (en) * | 2022-01-17 | 2022-04-15 | 江西颖南原环能有限公司 | Comprehensive recycling treatment method for Fenton iron mud |
| CN114768779A (en) * | 2022-04-18 | 2022-07-22 | 武汉理工大学 | Preparation method of nitrogen-doped magnetic iron sludge biochar applied to tetracycline removal in water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459237B (en) * | 2017-09-18 | 2018-09-25 | 华中科技大学 | Based on the sludge composite conditioner of iron containing sludge pyrolysis residue and its preparation and application |
-
2022
- 2022-08-18 CN CN202210996097.0A patent/CN115414911B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110171876A (en) * | 2019-05-16 | 2019-08-27 | 浙江科技学院 | A kind of N doping sludge carbon carries the preparation method and applications of nano ferriferrous oxide |
| CN110171830A (en) * | 2019-05-16 | 2019-08-27 | 浙江科技学院 | A kind of preparation method and applications of N doping magnetic bio charcoal |
| CN110227534A (en) * | 2019-07-16 | 2019-09-13 | 河南省科学院化学研究所有限公司 | A kind of magnetic N doping biology Pd/carbon catalyst and preparation method thereof based on sludge |
| CN113620368A (en) * | 2021-09-07 | 2021-11-09 | 浙江清华长三角研究院 | Method for advanced treatment of fluoroquinolone antibiotic pharmaceutical wastewater by using pharmaceutical sludge biochar |
| CN114229983A (en) * | 2021-11-29 | 2022-03-25 | 哈尔滨工业大学（深圳） | Method for preparing catalytic activated biochar from iron-containing excess sludge and removing antibiotics |
| CN114349296A (en) * | 2022-01-17 | 2022-04-15 | 江西颖南原环能有限公司 | Comprehensive recycling treatment method for Fenton iron mud |
| CN114768779A (en) * | 2022-04-18 | 2022-07-22 | 武汉理工大学 | Preparation method of nitrogen-doped magnetic iron sludge biochar applied to tetracycline removal in water |
Non-Patent Citations (1)
| Title |
|---|
| 氮自掺杂污泥炭催化过一硫酸盐氧化去除水中苯酚;孙洪伟;蒋福春;;中国给水排水(05);全文 * |
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