CN109092329A - A kind of method that hollow rich cobalt dual-metal sulfide activation persulfate quickly removes hardly degraded organic substance in waste water - Google Patents
A kind of method that hollow rich cobalt dual-metal sulfide activation persulfate quickly removes hardly degraded organic substance in waste water Download PDFInfo
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- CN109092329A CN109092329A CN201811049163.3A CN201811049163A CN109092329A CN 109092329 A CN109092329 A CN 109092329A CN 201811049163 A CN201811049163 A CN 201811049163A CN 109092329 A CN109092329 A CN 109092329A
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- metal sulfide
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- waste water
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 40
- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 38
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000002351 wastewater Substances 0.000 title claims abstract description 15
- 230000004913 activation Effects 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000004073 vulcanization Methods 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 2
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000003918 potentiometric titration Methods 0.000 abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 229960005404 sulfamethoxazole Drugs 0.000 description 30
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 30
- 230000015556 catabolic process Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 20
- 239000011572 manganese Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 239000012621 metal-organic framework Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052725 zinc 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to field of environment pollution control, more particularly to a kind of method that hollow rich cobalt dual-metal sulfide activation persulfate quickly removes hardly degraded organic substance in waste water, the MOF formed using methylimidazole and bimetallic nitrate is as presoma, then bimetallic sulfide is prepared using solvent heat vulcanization reaction, most forms stable hollow crystal structure through calcining afterwards；Under the conditions of extensive pH, to the waste water containing hardly degraded organic substance in add hollow rich cobalt dual-metal sulfide prepared by the present invention, persulfate can be activated and generate potentiometric titrations rapidly, hardly degraded organic substance is efficiently removed in 10min.Compared with prior art, hollow rich cobalt dual-metal sulfide preparation simplicity, stable structure, the dosage involved by the present invention are few, high-efficient, and applicable pH range is wide, has superior economic technique superiority.
Description
Technical field
The invention belongs to field of environment pollution control, are related to the technology of hardly degraded organic substance in advanced oxidation processing waste water,
More particularly to a kind of preparation method and applications of hollow rich cobalt dual-metal sulfide.
Background technique
Hardly degraded organic substance is difficult under field conditions (factors) to be fallen progressively decomposition by biological effect, they are often through food chain
It is gradually concentrated, to easily cause very big harm to environment and ecology.Therefore, using in the method control water environment of high-efficiency and economic
Hardly degraded organic substance pollution have great importance.
In recent years, the high-level oxidation technology based on potentiometric titrations has been widely used for hardly degraded organic substance processing.
Due to the very high oxidation-reduction potential (E of potentiometric titrations0=2.5~3.1V), and have more relative to hydroxyl radical free radical
Long half-life period and higher stability.Persulfate high-level oxidation technology has oxidant stability good, the sulfate radical of generation
Free radical ability is strong, is influenced the advantages that small, oxidant utilization is high and nontoxic by pH.The side of conventional persulfate activation
Method includes physical methods and the transition metal ions such as heating, ultraviolet, microwave, such as Co (II), Mn (II), Fe (II) chemical method
Activation.The technology that persulfate is activated based on transitional metal ion Co (II) is that one kind can carry out, at room temperature without additional
The method of energy.It is disclosed in the patent document of the patent No. 201710371696.2 a kind of using the absorption of MOFs containing In-Co and living
Change the method that Antibiotics of Low Concentration in water removal is removed in persulfate collaboration, but long action time, treatment effeciency are low.The patent No.
201510487197.0 patent document in disclose a kind of manganese cobalt composite oxide activation persulfate degradation of organic waste water
Method, but catalyst and oxidizer are big, processing cost is high.
Currently, hollow rich cobalt dual-metal sulfide material there is no to activate hardly degraded organic substance in persulfate removal waste water
Report.
Summary of the invention
The present invention solves the above-mentioned technical problems in the prior art, provides the hollow rich cobalt dual-metal sulfide of one kind
Preparation method, and it is applied to activation persulfate, quickly remove hardly degraded organic substance in waste water.
To solve the above problems, technical scheme is as follows:
A kind of preparation method of hollow rich cobalt dual-metal sulfide, comprising the following steps:
Step 1, M (NO is taken3)2With Co (NO3)2It is dissolved in organic solvent, methylimidazole is added and is sufficiently mixed, at room temperature
Stand 6~48h；MOF presoma is made in taking precipitate；Wherein M be Mn (II), it is Zn (II), Cu (II), any one in Ni (II)
Kind；
Step 2, MOF presoma made from step 1 is dissolved in organic solvent, thioacetamide is added, 60~180
Solvent heat vulcanization reaction is carried out at DEG C, reaction time control is dried under the conditions of 50~100 DEG C in 1~15h, sediment obtained
It is drying to obtain black crystals；
Step 3, black crystals made from step 2 are calcined in 200~500 DEG C and nitrogen atmosphere, hollow rich cobalt is made
Bimetallic sulfide.
Preferably, the organic solvent is the organic matter of alcoholic hydroxy；Such as methanol, ethyl alcohol.
Preferably, in the step 1, M (NO3)2Addition final concentration of 0.1~0.5mol/L, Co (NO3)2Addition it is whole
Concentration is 0.1~0.5mol/L, the final concentration of 0.2~1.0mol/L of the addition of methylimidazole.
Preferably, in the step 2, the addition of the final concentration of 1~5g/L of the addition of MOF presoma, thioacetamide are whole
Concentration is 0.1~0.5mol/L.
Preferably, in the hollow rich cobalt dual-metal sulfide, the ratio between amount of substance of M and Co is 1:(20~1), wherein
M is Mn (II), Zn (II), Cu (II), any one in Ni (II).
Application of the above-mentioned hollow rich cobalt dual-metal sulfide in removal waste water in hardly degraded organic substance.
Preferably, concrete application method are as follows:
It is connect to waste water and adds persulfate and hollow rich cobalt dual-metal sulfide, hybrid reaction 1min or more.Preferably 10-
20min。
Preferably, the hollow rich cobalt dual-metal sulfide, persulfate, in waste water hardly degraded organic substance mass concentration
The ratio between be (0.5~3): (1.8~18): 1.
Preferably, the persulfate is any one in peroxy-monosulfate and peroxydisulfate；The permonosulphuric acid
Salt is KHSO5And NaHSO5In any one；The peroxydisulfate is K2S2O8And Na2S2O8In any one.
Preferably, the pH range of the waste water is 2~14.
Compared with the existing technology, advantages of the present invention is as follows,
(1) preparation method through the invention can prepare uniform bimetallic sulfide, be different from surface doping and different
Matter junction structure can manipulate the electronic property and surface nature of material of main part, be allowed to more active.Hollow structure specific surface area
Greatly, more active sites can be exposed, the process of chemical reaction is accelerated；It is more that compatibility can be prepared using MOF as presoma
Metal ion, inner hollow, uniform metal sulfide.
(2) the hollow rich cobalt dual-metal sulfide material in the present invention can effectively activate persulfate and generate sulfate radical
Free radical, and free radical utilization rate is high, reaction speed is fast, and it is good to the removal effect of hardly degraded organic substance, it is difficult in reaction 10 minutes
The removal rate of degradation of organic substances is up to 99%.
(3) advantage of hollow structure, a large amount of active sites of exposure are given full play in the present invention, bimetallic ion is uniformly mixed
Miscellaneous and hollow structure synergistic effect has been obviously improved catalytic performance, can efficiently remove hardly degraded organic substance under room temperature, simultaneously
The dosage of catalyst and oxidant is few；Compared with prior art, 7~12 times of chemical kinetics effect promoting of the present invention, over cure
The dosage of hydrochlorate reduces 8~14 times, and the dosage of catalyst reduces 3~10 times.
(4) material structure is stablized, repeatable to recycle, and activity is held essentially constant in multiple circulation.
Detailed description of the invention
Fig. 1 is sulfamethoxazole degradation figure under different proportion doping metals
Fig. 2 is the degradation figure of sulfamethoxazole under variety classes doping metals
Fig. 3 is the degradation figure of sulfamethoxazole under different persulfate dosages.
Fig. 4 is the degradation figure of sulfamethoxazole under different catalysts dosage.
Fig. 5 is the degradation figure of sulfamethoxazole under different pH value.
Fig. 6 is hollow bimetallic sulphide cycle lab diagram.
Specific embodiment
Hollow richness cobalt dual-metal sulfide used in embodiment and comparative example is prepared using following methods:
(1) M (NO is taken3)2(M is doping metals, can be selected from Mn (II), Zn (II), Cu (II), any one in Ni (II)
Kind) (C=0.1~0.5mol/L) and Co (NO3)2(C=0.1~0.5mol/L) is dissolved in organic solvent, and methylimidazole is added
(C=0.2~1.0mol/L) is sufficiently stirred, and is stood 6~48h at room temperature and is carried out self assembly.Sediment is after being centrifuged with having
Solvent washing, 50~100 DEG C of vacuum drying obtain MOF presoma.
(2) MOF presoma (ω=1~5g/L) is taken to be dissolved in organic solvent, addition thioacetamide (C=0.1~
Solvent heat vulcanization reaction 0.5mol/L) is carried out at 60~180 DEG C, the reaction time controls the sediment warp obtained in 1~15h
Organic solvent washing is used after centrifugation, 50~100 DEG C of drying obtain black crystals.
(3) hollow rich cobalt dual-metal sulfide is calcined in 200~500 DEG C and nitrogen atmosphere, and it is more stable to obtain crystal form
Hollow rich cobalt dual-metal sulfide.
Hollow richness cobalt dual-metal sulfide is to adulterate Mn (II), Zn (II), Cu (II), Ni (II) based on Co (II)
In any one.
In hollow richness cobalt dual-metal sulfide, the ratio between amount of substance of doping metals and cobalt metal is (1:20)~(1:1).
The organic solvent that above-mentioned reaction and washing use is the organic matter of the alcoholic hydroxies such as methanol, ethyl alcohol.
Embodiment 1
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
(Mn:Co=1:20) hollow rich cobalt dual-metal sulfide, is sufficiently stirred.
(2) 25mg KHSO is added into reaction system5, sample at interval of a period of time, be quenched with methanol, utilized
Instrument is measured remaining sulfamethoxazole concentration.Experimental result is shown in Fig. 1.Wherein, C0For initial concentration, C is final concentration,
C/C0Indicate degradation rate.Similarly hereinafter.
Embodiment 2
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
(Mn:Co=1:1) hollow rich cobalt dual-metal sulfide, is sufficiently stirred.
(2) 25mg KHSO is added into reaction system5, sample at interval of a period of time, be quenched with methanol, utilized
Instrument is measured remaining sulfamethoxazole concentration.Experimental result is shown in Fig. 1.
Embodiment 3:
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
(Mn:Co=1:9) hollow rich cobalt dual-metal sulfide, is sufficiently stirred.
(2) 25mg KHSO is added into reaction system5, sample at interval of a period of time, be quenched with methanol, utilized
Instrument is measured remaining sulfamethoxazole concentration.Experimental result is shown in Fig. 1.
Embodiment 4
Change doping metals Mn and replace with Ni, Cu, Zn respectively, ratio remains unchanged, and repeats to obtain in embodiment 3 (1) (2)
The degradation figure of sulfamethoxazole is as shown in Figure 2 under to different doping metals.
Embodiment 5:
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
(Mn:Co=1:9) hollow rich cobalt dual-metal sulfide material, is sufficiently stirred.
(2) 5mg KHS is added into reaction system2O8, sampled at interval of a period of time, be quenched with methanol, utilize instrument
Device is measured remaining sulfamethoxazole concentration.
(3) change KHS2O8The dosage of (oxidant) is respectively 15mg, 25mg, 50mg, repeats (1) (2), obtains in difference
The degradation of sulfamethoxazole is as shown in Figure 3 under persulfate dosage.
Embodiment 6:
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, is added
The hollow rich cobalt dual-metal sulfide material of 1.35mg (Mn:Co=1:9), is sufficiently stirred.
(2) 25mg KHS is added into reaction system2O8, sample at interval of a period of time, be quenched with methanol, utilized
Instrument is measured remaining sulfamethoxazole concentration.
(3) dosage for changing catalyst (hollow richness cobalt dual-metal sulfide) is respectively 4mg, 5mg, 8.25mg, is repeated (1)
(2), the degradation for obtaining the sulfamethoxazole under different catalysts dosage is as shown in Figure 4.
Embodiment 7:
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, molten with HCI
Liquid (C=1mol/L) and NaOH solution (C=1mol/L) adjust pH=2.61, and the hollow richness of 2.5mg (Mn:Co=1:9) is added
Cobalt dual-metal sulfide material, is sufficiently stirred.
(2) 25mg KHS is added into reaction system2O8, sample at interval of a period of time, be quenched with methanol, utilized
Instrument is measured remaining sulfamethoxazole concentration.
(3) changing pH value is respectively 5.58,8.38,10.98, repeats (1) (2), obtains in different pH value sulfamethoxazoles
Degradation it is as shown in Figure 5.
Embodiment 8:
(1) methyl orange solution for preparing 20mg/L at room temperature, takes 50mL solution in 100mL conical flask, addition 5mg (Mn:
Co=1:9 hollow rich cobalt dual-metal sulfide material), is sufficiently stirred.
(2) 25mg KHS is added into reaction system2O8, sample at interval of a period of time, be quenched with methanol, utilized
Instrument is measured remaining methyl orange concentration.The result shows that the degradation of methyl orange reaches 99% or more within 6min.
Embodiment 9:
(1) the bisphenol-A solution for preparing 20mg/L at room temperature, takes 50mL solution in 100mL conical flask, addition 5mg (Mn:
Co=1:9 hollow rich cobalt dual-metal sulfide material), is sufficiently stirred.
(2) 25mg KHS is added into reaction system2O8, sample at interval of a period of time, be quenched with methanol, utilized
Instrument is measured remaining bisphenol A concentration.The result shows that the degradation of 7min etc bisphenol-A reaches 99% or more.
Embodiment 10:
(1) the sodium butylnaphthalenesulfonate solution for preparing 100mg/L at room temperature, takes 50mL solution in 100mL conical flask, is added
The hollow rich cobalt dual-metal sulfide material of 5mg (Mn:Co=1:9), is sufficiently stirred.
(2) 25mg KHS is added into reaction system2O8, sample at interval of a period of time, be quenched with methanol, utilized
Instrument is measured remaining sodium butylnaphthalenesulfonate concentration.The result shows that the degradation of sodium butylnaphthalenesulfonate reaches within 9min
99% or more.
Embodiment 11
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
(Mn:Co=1:9) hollow rich cobalt dual-metal sulfide material, is sufficiently stirred.
(2) 5mg KHS is added into reaction system2O8, sampled at interval of a period of time, be quenched with methanol, utilize instrument
Device is measured remaining sulfamethoxazole concentration.
(3) solution after reaction is centrifuged, washed, filtered, catalyst is recycled, then repeat (1) (2).
Circuit sequentially obtain three times material circulation experiment figure it is as shown in Figure 6.
Comparative example 1
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
The material of MOFs containing In-Co disclosed in the patent document of the patent No. 201710371696.2, is sufficiently stirred.
(2) 5mg KHS is added into reaction system2O8, sampled at interval of a period of time, be quenched with methanol, utilize instrument
Device is measured remaining sulfamethoxazole concentration.The result shows that reaction 60min or more degradation rate can be only achieved 95% or more.
Comparative example 2
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
The pure cobalt sulfide of monometallic, is sufficiently stirred.
(2) 5mg KHS is added into reaction system2O8, sampled at interval of a period of time, be quenched with methanol, utilize instrument
Device is measured remaining sulfamethoxazole concentration.The result shows that reaction 20min or more degradation rate can be only achieved 99% or more.
Comparative example 3
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
The hollow rich cobalt dual-metal sulfide material (Mn:Co=1:9) calcined at 800 DEG C, is sufficiently stirred.
(2) 5mg KHS is added into reaction system2O8, sampled at interval of a period of time, be quenched with methanol, utilize instrument
Device is measured remaining sulfamethoxazole concentration.The result shows that reaction 30min or more degradation rate can be only achieved 95% or more.
Comparative example 4
(1) the sulfamethoxazole solution for preparing 55mg/L at room temperature, takes 50mL solution in 100mL conical flask, and 5mg is added
The hollow rich cobalt dual-metal sulfide material (Mn:Co=1:9) calcined at 100 DEG C, is sufficiently stirred.
(2) 5mg KHS is added into reaction system2O8, sampled at interval of a period of time, be quenched with methanol, utilize instrument
Device is measured remaining sulfamethoxazole concentration.The result shows that reaction 60min or more degradation rate can be only achieved 90% or more.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of hollow rich cobalt dual-metal sulfide, which comprises the following steps:
Step 1, M (NO is taken3)2With Co (NO3)2It is dissolved in organic solvent, methylimidazole is added and is sufficiently mixed, stands 6 at room temperature
~48h；MOF presoma is made in taking precipitate；Wherein M be Mn (II), Zn (II), Cu (II), any one in Ni (II)；
Step 2, MOF presoma made from step 1 is dissolved in organic solvent, thioacetamide is added, at 60~180 DEG C
Solvent heat vulcanization reaction is carried out, in 1~15h, sediment obtained is passed through dries system under the conditions of 50~100 DEG C for reaction time control
Obtain black crystals；
Step 3, black crystals made from step 2 are calcined in 200~500 DEG C and nitrogen atmosphere, the hollow double gold of rich cobalt is made
Belong to sulfide.
2. preparation method as described in claim 1, which is characterized in that the organic solvent is the organic matter of alcoholic hydroxy.
3. preparation method as described in claim 1, which is characterized in that in the step 1, M (NO3)2Addition it is final concentration of
0.1~0.5mol/L, Co (NO3)2The final concentration of 0.1~0.5mol/L of addition, the addition of methylimidazole final concentration of 0.2
~1.0mol/L.
4. preparation method as described in claim 1, which is characterized in that in the step 2, the addition final concentration of MOF presoma
For 1~5g/L, the final concentration of 0.1~0.5mol/L of the addition of thioacetamide.
5. preparation method as described in claim 1, which is characterized in that in the hollow rich cobalt dual-metal sulfide, M and Co's
The ratio between amount of substance is 1:(20~1), wherein M be Mn (II), Zn (II), Cu (II), any one in Ni (II)
6. hollow rich cobalt dual-metal sulfide answering in hardly degraded organic substance in removal waste water as claimed in claims 1-5
With.
7. application as claimed in claim 6, which is characterized in that concrete application method are as follows: connect to waste water add persulfate and
Hollow richness cobalt dual-metal sulfide, hybrid reaction 1min or more.
8. the use as claimed in claim 7, which is characterized in that the hollow rich cobalt dual-metal sulfide, persulfate, waste water
The ratio between mass concentration of middle hardly degraded organic substance is (0.5~3): (1.8~18): 1.
9. the use as claimed in claim 7, which is characterized in that the persulfate is in peroxy-monosulfate and peroxydisulfate
Any one；The peroxy-monosulfate is KHSO5And NaHSO5In any one；The peroxydisulfate is K2S2O8With
Na2S2O8In any one.
10. the use as claimed in claim 7, which is characterized in that the pH range of the waste water is 2~14.
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| CN110581268A (en) * | 2019-09-26 | 2019-12-17 | 安徽师范大学 | Self-supporting binary metal sulfide composite material and preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN110773197A (en) * | 2019-10-29 | 2020-02-11 | 李平 | Two-dimensional bimetallic sulfide nanosheet photocatalyst and preparation method thereof |
| CN111302476A (en) * | 2020-02-27 | 2020-06-19 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN112642433A (en) * | 2020-12-29 | 2021-04-13 | 西安交通大学 | Preparation method of two-dimensional flaky porous composite oxide and application of two-dimensional flaky porous composite oxide in control of chlorine-containing volatile organic pollutants |
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| CN113181933A (en) * | 2021-04-23 | 2021-07-30 | 重庆大学 | Iron-copper bimetallic sulfide microsphere, preparation method thereof and application thereof in water treatment |
| CN113751074A (en) * | 2021-09-02 | 2021-12-07 | 北京建筑大学 | Immobilized catalyst and preparation method and application thereof |
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| CN110581268A (en) * | 2019-09-26 | 2019-12-17 | 安徽师范大学 | Self-supporting binary metal sulfide composite material and preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN110773197A (en) * | 2019-10-29 | 2020-02-11 | 李平 | Two-dimensional bimetallic sulfide nanosheet photocatalyst and preparation method thereof |
| CN111302476A (en) * | 2020-02-27 | 2020-06-19 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN111302476B (en) * | 2020-02-27 | 2021-12-17 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN112642433A (en) * | 2020-12-29 | 2021-04-13 | 西安交通大学 | Preparation method of two-dimensional flaky porous composite oxide and application of two-dimensional flaky porous composite oxide in control of chlorine-containing volatile organic pollutants |
| CN112978811A (en) * | 2021-02-04 | 2021-06-18 | 北京理工大学 | Hollow sulfide microsphere with rich sulfur vacancy and preparation method and application thereof |
| CN113181933A (en) * | 2021-04-23 | 2021-07-30 | 重庆大学 | Iron-copper bimetallic sulfide microsphere, preparation method thereof and application thereof in water treatment |
| CN113751074A (en) * | 2021-09-02 | 2021-12-07 | 北京建筑大学 | Immobilized catalyst and preparation method and application thereof |
| CN113751074B (en) * | 2021-09-02 | 2023-04-25 | 北京建筑大学 | Immobilized catalyst and preparation method and application thereof |
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