CN111097399A - Magnetic charcoal catalyst prepared from PTA residues and advanced oxidation water treatment method thereof - Google Patents
Magnetic charcoal catalyst prepared from PTA residues and advanced oxidation water treatment method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 14
- 230000003647 oxidation Effects 0.000 title abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title abstract description 11
- 239000003610 charcoal Substances 0.000 title description 2
- 239000002351 wastewater Substances 0.000 claims abstract description 21
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 238000001994 activation Methods 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 15
- 239000002028 Biomass Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 235000013980 iron oxide Nutrition 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000007885 magnetic separation Methods 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 2
- 241001330002 Bambuseae Species 0.000 claims 1
- 239000011425 bamboo Substances 0.000 claims 1
- 238000010525 oxidative degradation reaction Methods 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 239000002910 solid waste Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 13
- 239000000126 substance Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000010815 organic waste Substances 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010840 domestic wastewater Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000209128 Bambusa Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/345—Phenols
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a magnetic biochar catalyst prepared from PTA residues (solid wastes generated in the production process of purified terephthalic acid) and a high-grade oxidation water treatment method thereof, belonging to the fields of comprehensive utilization of wastes and wastewater treatment. The invention provides a magnetic biochar catalyst prepared by converting PTA residues containing organic solid wastes and heavy metal ions, which is used in the advanced oxidation water treatment process to achieve the purpose of treating wastes with processes of wastes against one another. The magnetic biochar catalyst is added into wastewater, persulfate is added, electron transmission is carried out through catalyst surface groups, a carbon skeleton and loaded metal oxide, persulfate is activated, sulfate radicals are generated, advanced redox reaction is carried out, and organic pollutants in the wastewater are efficiently degraded. The method comprehensively utilizes the organic solid waste to carry out efficient wastewater treatment, has good effect, no residue and low cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to a magnetic activated carbon catalyst prepared from PTA residues, which is used for treating organic pollutants in wastewater by advanced oxidation and belongs to the technical field of comprehensive utilization of wastes and advanced oxidation water treatment.
Background
The PTA residue is solid waste produced in the production process of pure terephthalic acid and is earthy yellow. The PTA residue contains high contents of benzoic acid and phthalic acid (phthalic acid, isophthalic acid and terephthalic acid) as main components, and small amounts of methylbenzoic acid and p-carboxybenzaldehyde, and further contains small amounts of catalysts such as cobalt and manganese. Because the system is complicated, the existing disposal method directly disposes the waste as solid waste or concentrates on the recovery of some chemicals such as terephthalic acid, cobalt and manganese catalysts. The disposal of solid waste is mainly carried out by methods such as landfill, incineration and water treatment, which waste useful substances (chemicals or carbon-based materials) in the residue, especially loss of noble metal cobalt, and cause secondary pollution to the environment. The method for recovering chemicals has the defects of difficult separation and purification of all components, long process path, poor broad spectrum property due to the adjustment and treatment method of specific raw material components, or low economic benefit due to the small proportion of the recovered substances in the total components, and still needs to be further treated.
With the development of economic society, a large amount of industrial and domestic wastewater is generated, wherein the wastewater often contains toxic and nondegradable organic pollutants, and the migration in the environment, the influence on the environment and the treatment process also become research hotspots in the field of environmental science and engineering. Advanced Oxidation technologies AOPs (advanced Oxidation processes) can completely remove harmful pollutants in organic wastewater and mineralize the harmful pollutants into CO2And H2And O, the application prospect is wide. The high-oxidation-reduction-potential sulfate radical advanced oxidation water treatment technology has the advantages of wide pH adaptation range, stronger oxidizability under neutral conditions and longer radical half-life period, and becomes a research hotspot, but the traditional activation medium can form metal ion residues to cause secondary pollution. The carbon-based material can avoid the leaching problem of the metal catalyst, does not introduce new substances and secondary pollution, and has great potential in a heterogeneous system combined with peroxide. However, the existing carbon-based materials are concentrated on graphene, carbon nanotubes and nanodiamonds, and are high in price and low in practicability. Thermalization of organic wastesThe chemical conversion process can generate carbon-rich solid residue (biochar), has rich pore canals and pore structures, can be modified to be used as an adsorbent or a catalyst carrier, and lacks a utilization way with high added value at present.
The binary composite material taking two transition metal elements as catalytic cores can reduce the manufacturing cost of the catalyst and simultaneously realize the dual improvement of the efficiency and the stability of the catalyst. The invention patent with the publication number of CN105084511A adopts heterogeneous manganese cobalt oxide as a catalyst, and can efficiently and continuously activate persulfate to generate sulfate radicals and hydroxyl radicals, thereby achieving the purpose of degrading organic pollutants; meanwhile, the manganese oxide is used as an environment-friendly material, so that cobalt ion leakage can be effectively reduced, and secondary pollution and biotoxicity are reduced.
Disclosure of Invention
Aiming at the limitation of the prior art, the invention provides a magnetic biochar catalyst prepared by converting PTA residues, which is used in the advanced oxidation water treatment process and aims at the effects of treating wastes with processes of wastes against one another, by surrounding the characteristics that the PTA residues simultaneously contain organic solid wastes and heavy metal ions and combining the problem of secondary pollution in the advanced oxidation process.
A method for preparing a magnetic biochar catalyst from PTA residues is characterized by comprising the following steps:
(1) preparing a precursor: mixing PTA residues, biomass and ferric oxide, wherein the biomass content in the mixture is not higher than 30wt%, and the ferric oxide content in the mixture is not higher than 5 wt%;
(2) and (3) drying: drying the obtained precursor at 100-120 ℃ for 10-12 h;
(3) carbonizing: heating the dried precursor to 300-600 ℃ in a carbonization atmosphere, carbonizing at a constant temperature for 2-6 h, and using generated pyrolysis gas for combustion to supply heat for the activation and drying processes;
(4) and (3) activation: the superheated steam with the temperature of 700-1100 ℃ is used for activation for 30-50 min, and the amount of the superheated steam is not higher than 0.2Nm3The overflowed superheated steam tail gas is used as a carbonization atmosphere; then ammonia acts for 20-40 min at 300-500 ℃, and the amount of ammonia is not more than 0.1Nm3/kg；
(5) Washing and drying: and washing and drying the product to obtain the magnetic biochar catalyst.
Further, the biomass is one or more of branches, bamboos and straws.
In the activation process, the temperature of the effluent steam tail gas is higher, the effluent steam tail gas does not contain oxygen, and the effluent steam tail gas can be used as a carbonization atmosphere to directly heat the raw materials, so that the heat utilization rate is improved.
The nitrogen-containing functional groups on the surface of the biochar, such as pyridine and aromatic amine, can be enriched by ammonia activation, and can cooperate with metal elements in the catalyst to carry out electron transmission and activate persulfate to generate sulfate radicals, so that the catalytic oxidation degradation performance of organic pollutants is improved.
The biochar catalyst is characterized in that the specific surface area is 20-500 m2The magnetic separation material is loaded with manganese, cobalt and iron oxides, has a magnetic separation characteristic, and has an iodine value of 500-700 mg/g and a methylene blue value of 50-150 mg/g.
The method for treating the wastewater by using the biochar catalyst comprises the following steps: 2-5 g/L of a biochar catalyst, 2-5 g/L of persulfate, 25-60 ℃ and 100-200 s of wastewater retention time are added into the wastewater.
The wastewater contains organic wastes such as phenol, methylene blue and the like, and the concentration of the organic wastes is lower than 250 mg/L.
The magnetic biochar catalyst has the following wastewater treatment principle:
the magnetic biochar catalyst carries out electron transmission through surface groups, a carbon skeleton and loaded metal oxide, and activates persulfate so as to generate sulfate radicals for carrying out advanced redox reaction.
After the waste water containing the organic wastes is treated, the concentration of the wastes is reduced to 1 mg/L.
The invention has the beneficial effects that:
(1) the PTA residues are comprehensively utilized to carry out high-efficiency treatment on the wastewater, so that the waste is treated by the waste, and two purposes are achieved at one stroke;
(2) when the PTA residues are used for preparing the active carbon, appropriate biomass is prepared, the heat value of the residues is adjusted, and the self-heating balance in the preparation process is realized;
(3) the defects in the traditional PTA residue disposal process are avoided, the impact on the environment is reduced, and the economy is improved;
(4) proper ferric oxide is prepared, and the cobalt and manganese in the residue are combined, so that the prepared active carbon has magnetism, is convenient for magnetic separation, and avoids the generation of metal ion residues after the wastewater is treated by the traditional advanced oxidation method;
(5) compared with the traditional catalyst taking the carbon nano tube and the graphene as the base materials, the catalyst has more active sites, good catalytic activity and obviously reduced cost;
(6) the treatment efficiency is high, and the reaction speed is high;
(7) can be used for drinking water disinfection and industrial and domestic wastewater treatment;
(8) not only can degrade organic pollutants in water, but also can kill harmful microorganisms.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of applicability of the invention.
Example 1
65wt% of PTA residue, 30wt% of biomass and 5wt% of iron oxide were mixed and the mixture was dried at 100 ℃ for 10 h. And (3) placing the dried precursor in the atmosphere of water vapor activation tail gas, heating to 300 ℃, keeping the temperature constant for 6h, and using the generated pyrolysis gas for combustion supply activation and drying processes. Activating with 700 deg.C superheated steam for 50min, the amount of superheated steam is 0.2Nm3In terms of/kg. Then ammonia gas is acted for 40min at 300 ℃, and the ammonia gas amount is 0.1Nm3And/kg, washing the product, and drying to obtain the magnetic biochar catalyst.
The specific surface area of the biochar catalyst is 500m2Iodine value of 700mg/g and methylene blue value of 120 mg/g. 2g/L of biochar catalyst, 5g/L of persulfate, 25 ℃ and 180s of action time are added into the wastewater containing 250mg/L of phenol. After the treatment, the phenol concentration is reduced to less than 1 mg/L.
Example 2
Mixing 76wt% PTA residue, 20wt% biomass and 4wt% iron oxide, and mixing the mixtureDrying at 120 ℃ for 12 h. And (3) placing the dried precursor in the atmosphere of water vapor activation tail gas, heating to 500 ℃, keeping the temperature constant for 4 hours, and using the generated pyrolysis gas for combustion supply activation and drying processes. Activating with 900 deg.C superheated steam for 45min, wherein the superheated steam amount is 0.15Nm3In terms of/kg. Then reacting with ammonia gas at 350 deg.C for 35min, wherein the ammonia gas amount is 0.05Nm3And/kg, washing the product, and drying to obtain the magnetic biochar catalyst.
The specific surface area of the biochar catalyst is 400m2Iodine value of 650mg/g and methylene blue value of 150 mg/g. Adding 3g/L of biochar catalyst, 3g/L of persulfate, 35 ℃ and 120s of action time into the wastewater containing 200mg/L of phenol. After the treatment, the phenol concentration is reduced to be less than 0.5 mg/L.
Example 3
84wt% of PTA residue, 15wt% of biomass and 1wt% of iron oxide were mixed and the mixture was dried at 105 ℃ for 11 h. And (3) placing the dried precursor in the atmosphere of water vapor activation tail gas, heating to 500 ℃, keeping the temperature for 2h, and using the generated pyrolysis gas for combustion supply activation and drying processes. Activating with 800 deg.C superheated steam for 50min, wherein the superheated steam amount is 0.1Nm3In terms of/kg. Then ammonia gas is acted for 30min at 400 ℃, and the ammonia gas amount is 0.03Nm3And/kg, washing the product, and drying to obtain the magnetic biochar catalyst.
The specific surface area of the biochar catalyst is 100m2Iodine value of 500mg/g and methylene blue value of 50 mg/g. 4g/L of biochar catalyst, 2.5g/L of persulfate, 45 ℃ and 100s of action time are added into the wastewater with the methylene blue concentration of 100 mg/L. After the treatment, the concentration of methylene blue is reduced to be less than 0.4 mg/L.
Example 4
93wt% of PTA residue, 5wt% of biomass and 2wt% of iron oxide were mixed and the mixture was dried at 110 ℃ for 10 h. And (3) placing the dried precursor in the atmosphere of water vapor activation tail gas, heating to 600 ℃, keeping the temperature constant for 3h, and using the generated pyrolysis gas for combustion supply activation and drying processes. Activating with 1000 deg.C superheated steam for 35min, the amount of superheated steam is 0.05Nm3In terms of/kg. Then theThe ammonia gas acts for 25min at 440 ℃, and the ammonia gas amount is 0.07Nm3And/kg, washing the product, and drying to obtain the magnetic biochar catalyst.
The specific surface area of the biochar catalyst is 200m2The iodine value is 630mg/g, and the methylene blue value is 100 mg/g. Adding 4.5g/L of biochar catalyst, 4g/L of persulfate, 55 ℃ and 80s of action time into the wastewater with the methylene blue concentration of 100 mg/L. After the treatment, the concentration of methylene blue is reduced to be less than 0.1 mg/L.
Example 5
89wt% of PTA residue, 10wt% of biomass and 1wt% of iron oxide were mixed and the mixture was dried at 105 ℃ for 12 h. And (3) placing the dried precursor in the atmosphere of water vapor activation tail gas, heating to 400 ℃, keeping the temperature for 5 hours, and using the generated pyrolysis gas for combustion supply activation and drying processes. Activating with superheated steam of 1100 deg.C for 30min, wherein the superheated steam amount is 0.1Nm3In terms of/kg. Then ammonia gas is acted for 20min at 500 ℃, and the ammonia gas amount is 0.04Nm3And/kg, washing the product, and drying to obtain the magnetic biochar catalyst.
The specific surface area of the biochar catalyst is 20m2Iodine value of 600mg/g and methylene blue value of 130 mg/g. 5g/L of biochar catalyst, 2g/L of persulfate, 60 ℃ and 200s of action time are added into the wastewater with the methylene blue concentration of 50 mg/L. After the treatment, the concentration of methylene blue is reduced to be less than 0.2 mg/L.
Claims (5)
1. A method for preparing a magnetic biochar catalyst from PTA residues is characterized by comprising the following steps:
(1) preparing a precursor: mixing PTA residues, biomass and ferric oxide, wherein the biomass content in the mixture is not higher than 30wt%, and the ferric oxide content in the mixture is not higher than 5 wt%;
(2) and (3) drying: drying the obtained precursor at 100-120 ℃ for 10-12 h;
(3) carbonizing: heating the dried precursor to 300-600 ℃ in a carbonization atmosphere, carbonizing at a constant temperature for 2-6 h, and using generated pyrolysis gas for combustion to supply heat for the activation and drying processes;
(4) and (3) activation: the superheated steam with the temperature of 700-1100 ℃ is used for activation for 30-50 min, and the amount of the superheated steam is not higher than 0.2Nm3Per kg; then ammonia acts for 20-40 min at 300-500 ℃, and the amount of ammonia is not more than 0.1Nm3/kg；
(5) Washing and drying: and washing and drying the product to obtain the magnetic biochar catalyst.
2. The method of claim 1, wherein the biomass is one or more of branches, bamboo, and straw.
3. The method according to claim 1, wherein the specific surface area of the magnetic biochar catalyst is 20-500 m2The magnetic separation material is loaded with manganese, cobalt and iron oxides, has a magnetic separation characteristic, and has an iodine value of 500-700 mg/g and a methylene blue value of 50-150 mg/g.
4. The application of the magnetic biochar catalyst prepared by the method according to any one of claims 1 to 3 in wastewater treatment is characterized in that the biochar catalyst is used for advanced oxidative degradation of organic pollutants in wastewater, and the specific method is as follows: adding 2-5 g/L of the biochar catalyst and 2-5 g/L of persulfate into the wastewater, adjusting the temperature to be 25-60 ℃, and keeping the wastewater for 100-200 s.
5. The use of claim 4, wherein the wastewater contains phenol and methylene blue at a concentration of less than 250 mg/L.
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