CN114832826A - Triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst and preparation method and application thereof - Google Patents
Triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst and preparation method and application thereof Download PDFInfo
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- CN114832826A CN114832826A CN202210301552.0A CN202210301552A CN114832826A CN 114832826 A CN114832826 A CN 114832826A CN 202210301552 A CN202210301552 A CN 202210301552A CN 114832826 A CN114832826 A CN 114832826A
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- triammonium citrate
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- magnesium
- doped magnesium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 239000002131 composite material Substances 0.000 title claims abstract description 118
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000001393 triammonium citrate Substances 0.000 title claims abstract description 102
- 235000011046 triammonium citrate Nutrition 0.000 title claims abstract description 102
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 35
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 34
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 15
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 15
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims description 42
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 40
- 230000015556 catabolic process Effects 0.000 claims description 29
- 230000003115 biocidal effect Effects 0.000 claims description 22
- 239000002351 wastewater Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical group [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012425 OXONE® Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical group CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 abstract description 19
- 238000004064 recycling Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 10
- 230000000593 degrading effect Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract 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 98
- 229960003405 ciprofloxacin Drugs 0.000 description 49
- 229910017052 cobalt Inorganic materials 0.000 description 20
- 239000010941 cobalt Substances 0.000 description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 15
- 230000003213 activating effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- -1 sulfate radicals Chemical class 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 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 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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Abstract
The invention discloses a triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound composite catalyst, a preparation method and application thereof, wherein the preparation method of the catalyst comprises the following steps: mixing cobalt salt, magnesium salt, aluminum salt, an alkali source and triammonium citrate to prepare a catalyst precursor solution, and carrying out hydrothermal reaction to obtain the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound catalyst. According to the preparation method, the triammonium citrate is used as a reducing agent to regulate and control the hydrothermal synthesis process, so that the prepared triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst has the advantages of low leaching risk, high catalytic activity, good recycling property and the like, is a novel hydrotalcite catalyst with excellent performance, can be widely used for degrading organic pollutants (such as antibiotics) in water, and has high use value and good application prospect. The preparation method has the advantages of simple preparation conditions, high yield, low cost, strong operability and the like, and is easy for batch production.
Description
Technical Field
The invention belongs to the field of preparation and application of hydrotalcite-like catalysts, and particularly relates to a triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst and a preparation method and application thereof.
Background
In recent years, Advanced Oxidation Processes (AOPs) have been considered as an effective means for treating various environmental pollutants, and among them, a process for generating active species by activating Persulfate (PS) is called persulfate Advanced Oxidation technology. This technology has received much attention because of its ability to generate sulfate radicals (SO 4-). Sulfate radicals have similar redox potentials (SO 4-: 1.8-2.7V,. OH: 1.5-2.8V) and higher lifetimes (SO 4-: about 30-40. mu.s,. OH: about 20ns) than hydroxyl radicals (. OH), and therefore have a higher potential in treating refractory pollutants. In addition, the pathway for degrading pollutants by persulfate-mediated non-free radical path, such as singlet oxygen, high-valence metal and electron transfer, also strengthens the selectivity and applicability of the process in the aspect of environmental pollution treatment.
Catalysts for activating persulfates are the core of the persulfate advanced oxidation technology, among which transition metal catalysts have been studied largely from the outset because of their high catalytic efficiency. Previous studies have confirmed that valence changes of transition metal elements are the main mechanism for driving persulfate activation, and cobalt is commonly used for potassium Peroxymonosulfate (PMS) activation, and iron is used for Peroxodisulfate (PDS) activation. In addition, the ability of transition metal elements such as copper, nickel, and zinc to activate persulfate has also been widely studied. Early persulfate advanced oxidation technologies used metal salts for homogeneous catalysis, which were difficult to control in terms of catalytic efficiency and environmental risk. Thus, in order to shift the catalytic pathway from homogeneous catalysis to heterogeneous catalysis, increase the number of metal active sites of the catalyst, speed up the metal redox cycling rate, and reduce the risk of leaching of metal ions, a variety of metal catalysts are sequentially introduced, including metal oxides, metal hydroxides, and metal-carbon composites, among others. Among many metal materials, Layered Double Hydroxides (LDHs) composed of metal Hydroxide layers and interlayer anions, also called Hydrotalcites (HT) or Hydrotalcite-Like Compounds (HTLCs, hereinafter also referred to as hydrotalcites), have received great attention for their abundant Layered structure, flexible structure-controlling ability and stable synthesis methods. At present, catalysts composed of metals such as cobalt, manganese, iron, nickel and the like are used for persulfate advanced oxidation, most of the hydrotalcite has a binary metal structure, and intercalation anions are generally inorganic acid radicals (such as nitrate and carbonate); the synthesis method of these hydrotalcites is represented by a coprecipitation method or an electrodeposition method, and is widely used. However, the cobalt-based hydrotalcite catalyst prepared by the existing preparation method has the problems of poor catalytic activity, poor recycling property, high leaching risk and the like, and the cobalt-based hydrotalcite catalyst doped with trace cobalt has poor catalytic efficiency although the environmental risk is relatively controllable. Therefore, a trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst modified by triammonium citrate and having low leaching risk, high catalytic activity, high degradation efficiency and good recycling property and a preparation method thereof need to be found, and the catalyst has important significance for efficiently removing antibiotics in water.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst with low leaching risk, high catalytic activity and good recycling property and a preparation method thereof, and also provides an application of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst in treating antibiotic wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme.
A preparation method of a triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst comprises the following steps:
s1, mixing cobalt salt, magnesium salt, aluminum salt, alkali source and triammonium citrate to prepare a catalyst precursor solution;
s2, carrying out hydrothermal reaction on the catalyst precursor solution obtained in the step S1 to obtain the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound catalyst.
In the preparation method, the mass ratio of the magnesium salt to the triammonium citrate is 7.649: 0.122-1.216.
The preparation method is further improved, and the mass ratio of the magnesium salt to the triammonium citrate is 7.649: 0.122-0.2091.
In step S1, the ratio of the cobalt salt, the magnesium salt, the aluminum salt and the solvent is 0.175-0.35 g: 7.692 g-15.384 g: 3.750 g-7.502 g: 0.1L, the mass ratio of the magnesium salt to the alkali source is 7.649: 10.5, the cobalt salt is cobalt nitrate hexahydrate, the magnesium salt is magnesium nitrate hexahydrate, the aluminum salt is aluminum nitrate nonahydrate, the alkali source is an organic amine, the organic amine includes one or more of urea, hexamethylenetetramine and ethylenediamine, and the solvent is water; the mixing is carried out under the condition of stirring, and the stirring time is 10 min-30 min.
In a further improvement of the above preparation method, in step S2, the temperature of the hydrothermal reaction is 90 ℃ to 150 ℃, and the time of the hydrothermal reaction is 12h to 24 h.
In a further improvement of the above preparation method, in step S2, the hydrothermal reaction further includes the following steps: cleaning and drying the reaction product; the drying temperature is 60-80 ℃, the drying time is 24-48 h, and the drying is vacuum drying.
As a general technical concept, the invention also provides a triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst prepared by the preparation method.
As a general technical concept, the invention also provides an application of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst in treatment of antibiotic wastewater.
The application is further improved, and comprises the following steps: mixing a trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst modified by triammonium citrate with antibiotic wastewater, and adding persulfate to perform a catalytic degradation reaction to complete the degradation of the antibiotic in the water body; the mass ratio of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst to the antibiotics in the antibiotic wastewater is 10-20: 1.
The application is further improved, the concentration of the antibiotics in the antibiotic wastewater is 10-20 mg/L, the initial pH value of the antibiotic wastewater is 3-11, the addition amount of the persulfate is 0.2-0.5 g of persulfate added to each liter of antibiotic wastewater, the antibiotics in the antibiotic wastewater are tetracycline, the persulfate is potassium peroxymonosulfate composite salt, the catalytic degradation reaction is carried out under the stirring condition, the stirring rotating speed is 300-500 r/min, and the stirring time is 30-90 min.
Compared with the prior art, the invention has the advantages that:
(1) aiming at the problems of poor catalytic activity, poor recycling property, high leaching risk and the like of the hydrotalcite catalyst prepared by the existing preparation method, the invention creatively provides a preparation method of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst. According to the method, on one hand, a uniform pH reaction system is formed through an alkali source in the raw materials, the hydrotalcite material with the advantages of high crystallinity, large grain size and the like can be synthesized, and necessary conditions are provided for the stability of the material modified by the triammonium citrate; on the other hand, the hydrotalcite is used as a carrier to load the cobalt element, so that the leaching of the cobalt ion can be effectively reduced, the agglomeration of the cobalt ion is reduced, the active site is increased, the cobalt element is easy to disperse in a material matrix, the utilization rate of the cobalt active site is higher, and the excellent recycling property and catalytic activity are further obtained; more importantly, the ammonium citrate tribasic is used as a reducing agent to regulate and control the hydrothermal synthesis process, so that the valence state of the transition metal element cobalt can be reduced, the active sites of the composite catalyst are increased, the crystallinity of the composite catalyst can be controllably reduced, the crystallinity of the composite catalyst is controlled within a reasonable range, an oxygen vacancy defect structure is selectively manufactured in the composite catalyst, excellent catalytic activity is further obtained, and the efficient and thorough degradation of organic pollutants (such as antibiotics) in a water body is finally facilitated. In the preparation method, the triammonium citrate is used as a reducing agent to regulate and control the hydrothermal synthesis process, so that the prepared triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst has the advantages of low leaching risk, high catalytic activity, good recycling property and the like, is a novel hydrotalcite catalyst with excellent performance, can be widely used for degrading organic pollutants (such as antibiotics) in water, and has high use value and good application prospect. Meanwhile, the preparation method has the advantages of simple preparation conditions, high yield, low cost, strong operability and the like, and is easy for batch production.
(2) In the preparation method, by optimizing the mass ratio of the magnesium salt to the triammonium citrate of 7.649: 0.122-0.2091, the composite catalyst with optimal leaching risk, catalytic activity and recycling performance can be obtained; when the dosage of the ammonium citrate is too low, the formation of oxygen vacancy defects is not facilitated, and the catalytic activity of the composite catalyst is further influenced; when the dosage of the triammonium citrate is too high, the content of magnesium carbonate in the composition of the composite catalyst is increased, the leaching amount of cobalt is increased, and meanwhile, the agglomeration of the composite catalyst is more serious, which can affect the recycling performance of the composite catalyst.
(3) The invention also provides a citric acid triammonium modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound catalyst, which has better cobalt dispersibility, rich oxygen vacancy defects and more active sites, is favorable for promoting the function of a non-free radical approach in a persulfate advanced oxidation system in degrading organic pollutants, and has the advantages of low leaching risk, high catalytic activity, good recycling property and the like, thereby having very high practicability.
(4) The invention also provides the application of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst in treating antibiotic wastewater, the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst is used for activating persulfate to degrade antibiotics in a water body, the antibiotics can be quickly removed, the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst has a good resistance effect on interfering ions in the water body, and the preparation method has the advantages of simplicity in operation, high treatment efficiency, controllable environmental secondary pollution risk, wide application range and the like, and has a good practical application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is an electron microscope scanning image of a trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH) modified by triammonium citrate prepared in example 1 of the present invention.
Fig. 2 is an electron microscope scanning image of the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) modified by triammonium citrate in example 1 of the present invention.
Fig. 3 is an electron microscope scanning image of the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA5-LDH) modified by triammonium citrate in example 1 of the present invention.
Fig. 4 is an electron microscope scanning image of the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA10-LDH) modified by triammonium citrate in example 1 of the present invention.
FIG. 5 is XRD patterns of the triammonium citrate-modified trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH, CA1-LDH, CA5-LDH, CA10-LDH) prepared in example 1 of the present invention and the trace cobalt-doped magnesium aluminum hydrotalcite-like composite catalyst (Co-LDH) prepared in comparative example 1.
FIG. 6 shows electron paramagnetic resonance spectra of a trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) modified by triammonium citrate in example 1 of the present invention and a trace cobalt-doped magnesium aluminum hydrotalcite-like composite catalyst (Co-LDH) prepared in comparative example 1.
FIG. 7 is a graph showing the degradation effect of ciprofloxacin degraded by using triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH, CA1-LDH, CA5-LDH, CA10-LDH) and trace cobalt-doped magnesium-aluminum hydrotalcite-like composite catalyst (Co-LDH) to activate persulfate.
FIG. 8 is a graph showing the degradation reaction rate of ciprofloxacin degraded by using triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH, CA5-LDH, CA1-LDH, CA10-LDH) and trace cobalt-doped magnesium-aluminum hydrotalcite-like composite catalyst (Co-LDH) to activate persulfate.
Fig. 9 is a graph of the degradation effect of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) in example 3 of the present invention on degradation of ciprofloxacin by activating persulfate under different pH conditions.
Fig. 10 is a cobalt leaching change diagram of the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) modified by triammonium citrate in example 3 of the present invention for activating persulfate to degrade ciprofloxacin under different pH conditions.
Fig. 11 is a graph of the degradation effect of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) in example 4 of the present invention on ciprofloxacin degradation by activating persulfate under different interferents.
Fig. 12 is a graph of cycle number-degradation effect corresponding to when the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound composite catalyst (CA1-LDH) modified by triammonium citrate activates persulfate to degrade ciprofloxacin in example 5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
Example 1:
the invention discloses a preparation method of a triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound catalyst, which comprises the following steps:
(1) 0.1750g of analytically pure cobalt nitrate hexahydrate, 7.6490g of magnesium nitrate hexahydrate and 3.7500g of aluminum nitrate nonahydrate are weighed as raw materials, placed in a 150ml beaker, and added with 50ml of a solution having a resistivity of 18.25 omega -1 The ultrapure water is placed on a magnetic stirrer and stirred until the ultrapure water is completely dissolved, so that a mixed solution is obtained.
(2) 10.5000g of urea is added into the mixed solution, 0.1046g of triammonium citrate is added continuously after the urea is fully dissolved, and the mixture is stirred for 15min until the mixed solution is clear pink, so that the catalyst precursor compound salt solution is obtained.
(3) And carrying out hydrothermal reaction on the catalyst precursor composite salt solution at 140 ℃ for 24h, carrying out centrifugal separation and washing on a product obtained by the reaction (the product is subjected to centrifugal separation for multiple times, keeping a precipitate each time, adding distilled water, uniformly mixing and centrifuging, then removing a supernatant, centrifuging again until the pH of the supernatant is neutral), and drying in vacuum at 80 ℃ for 48h to obtain the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst, which is recorded as CA 0.5-LDH.
In this embodiment, different triammonium citrate modified trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalysts are also prepared, and the preparation methods of the three are basically the same as the preparation method of the triammonium citrate modified trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH), and the differences are that: in the step (2), the dosage of the triammonium citrate is 0.2091g, 1.0456g and 2.0911g respectively, and the corresponding prepared triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst is named as CA1-LDH, CA5-LDH and CA10-LDH in sequence.
FIG. 1 is an electron microscope scanning image of a trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH) modified by triammonium citrate prepared in example 1 of the present invention. Fig. 2 is an electron microscope scanning image of the ferric ammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) prepared in example 1 of the present invention. Fig. 3 is an electron microscope scanning image of the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA5-LDH) modified by triammonium citrate in example 1 of the present invention. Fig. 4 is an electron microscope scanning image of the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA10-LDH) modified by triammonium citrate in example 1 of the present invention. As can be seen from fig. 1 to 4, the trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst modified by triammonium citrate prepared in embodiment 1 of the present invention has a smaller lamellar hydrotalcite structure, and as the addition amount of triammonium citrate increases, the lamellar structure of the catalyst is more finely divided, and the crystallinity of the catalyst decreases, so that the composite catalyst has a higher specific surface area, and is in favor of contact with an oxidant or a pollutant in actual use, so as to improve the treatment efficiency. Also, for CA5-LDH and CA10-LDH shown in fig. 3 and 4, the crystallinity was too low, and too small catalyst particles caused serious agglomeration or cobalt leaching problems.
Comparative example 1:
a preparation method of a trace cobalt-doped magnesium-aluminum hydrotalcite composite catalyst is basically the same as that in example 1, and the difference is only that: in step (2) of comparative example 1, no triammonium citrate was added.
The trace cobalt-doped magnesium aluminum hydrotalcite composite catalyst prepared in the comparative example 1 is marked as Co-LDH.
FIG. 5 is XRD patterns of the triammonium citrate-modified trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH, CA1-LDH, CA5-LDH, CA10-LDH) prepared in example 1 of the present invention and the trace cobalt-doped magnesium aluminum hydrotalcite-like composite catalyst (Co-LDH) prepared in comparative example 1. As can be seen from fig. 5, the trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalyst modified by triammonium citrate prepared by the invention is basically the same as the trace cobalt-doped magnesium aluminum hydrotalcite-like composite catalyst (Co-LDH) prepared by the comparative example 1 in composition components, and is a composite of magnesium aluminum hydrotalcite and magnesium carbonate (including hydromagnesite). The hydrotalcite phase of the ternary hydrotalcite-like catalyst with trace cobalt-doped magnesium and aluminum modified by the triammonium citrate takes a 003 peak at 11.7 degrees as an example, and after the triammonium citrate is modified, the peak height is obviously reduced and the peak width is obviously increased, which shows that the crystallinity of the material is reduced and a defect structure may exist.
FIG. 6 shows electron paramagnetic resonance spectra of a trace cobalt-doped magnesium aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) modified by triammonium citrate in example 1 of the present invention and a trace cobalt-doped magnesium aluminum hydrotalcite-like composite catalyst (Co-LDH) prepared in comparative example 1. As can be seen from fig. 6, the trace cobalt-doped magnesium aluminum ternary hydrotalcite composite catalyst (CA1-LDH) prepared by the present invention and the trace cobalt-doped magnesium aluminum hydrotalcite composite catalyst (Co-LDH) prepared by the comparative example 1 both have oxygen vacancies, but the trace cobalt-doped magnesium aluminum ternary hydrotalcite composite catalyst (CA1-LDH) modified by the present invention has higher abundance of oxygen vacancies, which indicates that the composite catalyst of the present invention has better ability of catalyzing and activating persulfate.
Example 2:
the application of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst in treating antibiotic wastewater specifically relates to the application of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst in activating persulfate to degrade ciprofloxacin in a water body, and comprises the following steps:
taking five 150mL beakers, adding 100mL and 20mg/L ciprofloxacin solution, then respectively adding the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalysts (CA0.5-LDH, CA1-LDH, CA5-LDH and CA10-LDH) prepared in the example 1 and the trace cobalt-doped magnesium-aluminum hydrotalcite-like composite catalysts (Co-LDH) prepared in the comparative example 1, respectively accounting for 20mg, then adding 50mg of potassium hydrogen peroxymonosulfate composite salt (Oxone) into each beaker, uniformly mixing, stirring at the rotating speed of 400r/min, carrying out catalytic degradation reaction, and finishing degradation of ciprofloxacin in the water body. In the catalytic degradation process, samples are taken for 0min, 5min, 10min, 20min, 30min, 45min and 60min, and the concentration of ciprofloxacin in each beaker is measured.
FIG. 7 is a graph showing the degradation effect of ciprofloxacin degraded by using triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH, CA1-LDH, CA5-LDH, CA10-LDH) and trace cobalt-doped magnesium-aluminum hydrotalcite-like composite catalyst (Co-LDH) to activate persulfate. As can be seen from FIG. 7, the removal rate of ciprofloxacin by CA0.5-LDH, CA1-LDH, CA5-LDH and CA10-LDH of the invention at 45min is over 90%, and especially the removal rate of ciprofloxacin by CA10-LDH at 30min is up to 90%; the removal rate of the ciprofloxacin by the CA0.5-LDH, the CA1-LDH, the CA5-LDH and the CA10-LDH can reach more than 97 percent at 60 min. In contrast, the Co-LDH of comparative example 1 has a ciprofloxacin removal rate of 45% at 30min, and the ciprofloxacin removal rate of only 75% at 60 min.
FIG. 8 is a graph showing the degradation reaction rate of ciprofloxacin degraded by using triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA0.5-LDH, CA5-LDH, CA1-LDH, CA10-LDH) and trace cobalt-doped magnesium-aluminum hydrotalcite-like composite catalyst (Co-LDH) to activate persulfate. As can be seen from FIG. 8, the reaction rates of CA0.5-LDH, CA1-LDH, CA5-LDH and CA10-LDH of the present invention were 0.071min in this order -1 、0.07min -1 、0.057min -1 、0.088min -1 Where the reaction rates of CA0.5-LDH and CA1-LDH were close, while the reaction rate of comparative example 1Co-LDH was only 0.022min -1 . Therefore, the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst can realize efficient and thorough degradation of antibiotics in water.
As can be seen from the combination of FIG. 7 and FIG. 8, compared with CA0.5-LDH, CA1-LDH and CA10-LDH, the removal rate and reaction rate of ciprofloxacin by CA5-LDH are relatively poor because: in the components of the CA5-LDH, the content of magnesium carbonate is increased, the agglomeration phenomenon of the catalyst is obvious, and the catalytic activity of the composite catalyst is further influenced. In addition, the removal rate and the reaction rate of the CA10-LDH on the ciprofloxacin are improved, and the reason is that: along with the increase of the content of the cobalt element in the composite catalyst, the leaching amount of cobalt ions is increased in the catalytic degradation reaction process, and the leaching of cobalt can further improve the catalytic activity of the composite catalyst.
Example 3:
the method is used for investigating the influence of the degradation effect of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst in the treatment of antibiotic wastewater under different pH conditions, and specifically comprises the following steps of activating persulfate to degrade ciprofloxacin in a water body by adopting the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst:
ciprofloxacin solutions with pH values of 3, 5, 7, 9 and 11 are prepared respectively (the initial concentration of the solution is 20mg/L and the volume of the solution is 100mL), 20mg of the triammonium citrate modified trace cobalt-doped magnalium ternary hydrotalcite-like composite catalyst (CA1-LDH) prepared in the example 1 is added, 50mg of potassium peroxymonosulfate composite salt (Oxone) is added, stirring is carried out at the rotating speed of 400r/min, catalytic degradation reaction is carried out, and degradation of ciprofloxacin in the water body is completed. Sampling and measuring the ciprofloxacin concentration in each sample at 10min and 60min to finally obtain the catalytic performance of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst under different pH conditions.
Fig. 9 is a graph of the degradation effect of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) in example 3 of the present invention on degradation of ciprofloxacin by activating persulfate under different pH conditions. As can be seen from FIG. 9, when the initial pH is 11, the removal rate of ciprofloxacin by CA1-LDH at 10min can reach 55%, and when the initial pH is 3, the removal rate of ciprofloxacin by CA1-LDH at 10min can reach 65%; meanwhile, when the pH value is within the range of 3-11, the removal rate of the CA1-LDH to ciprofloxacin is more than 98% in 60min, which shows that the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound catalyst has an excellent removal effect on ciprofloxacin. Therefore, the trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst modified by the triammonium citrate has a very good catalytic degradation effect in a wider pH range.
Sampling and measuring at 60min, and calculating to obtain the leaching amount of cobalt.
Fig. 10 is a cobalt leaching change diagram of the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) modified by triammonium citrate in example 3 of the present invention for activating persulfate to degrade ciprofloxacin under different pH conditions. From fig. 10, under different pH conditions, when the trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst modified by triammonium citrate activates persulfate to degrade ciprofloxacin, the leaching of cobalt is at a lower level, and the concentration of cobalt does not reach the standard influencing ecological environment, i.e., no significant ecological risk exists. Therefore, the trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst modified by the triammonium citrate is safe and environment-friendly, and has small potential environmental risk.
Example 4:
the method is used for investigating the influence of the degradation effect of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst in the treatment of antibiotic wastewater under the condition of a complex water body, and specifically comprises the following steps of activating persulfate to degrade ciprofloxacin in the water body by adopting the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst, wherein the persulfate is activated by adopting the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst:
respectively preparing the mixture containing 50mmol/LH 2 PO 4 - 、50mmol/L HCO 3 - 、50mmol/L Cl - 、50mmol/L NO 3 - The method comprises the following steps of preparing a ciprofloxacin solution containing 200mg/L of Humic Acid (HA) interferent and a ciprofloxacin solution containing no interferent, wherein the ciprofloxacin concentration is 20mg/L, the volume is 100mL, taking six 150mL beakers, respectively adding 20mg of the triammonium citrate modified trace cobalt-doped magnalium ternary hydrotalcite-like composite catalyst (CA1-LDH) prepared in the example 1 and the ciprofloxacin solution, then adding 50mg of potassium hydrogen peroxymonosulfate composite salt (Oxone) into each beaker, stirring at the rotating speed of 400r/min, carrying out catalytic degradation reaction for 60min, completing degradation of ciprofloxacin in a water body, and sampling and determining.
Fig. 11 is a graph of the degradation effect of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst (CA1-LDH) in example 4 of the present invention on ciprofloxacin degradation by activating persulfate under different interferents. As can be seen from FIG. 11, in H 2 PO 4 - 、HCO 3 - 、Cl - 、NO 3 - When HA exists, the removal rate of ciprofloxacin by CA1-LDH within 60min is 93.2%, 100%, 97.1% and 97.3% respectively; for comparison, when no interferent is contained, the removal rate of the CA1-LDH to ciprofloxacin within 60min is 98.2%, which shows that the performance of the prepared triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst for degrading ciprofloxacin is still stable in the presence of various common high-concentration interfering ions. Furthermore, HCO 3 - And Cl - The presence of (A) can significantly accelerate degradation of ciprofloxacin, and H 2 PO 4 - Has negative effects on the degradation capability and the degradation rate of ciprofloxacin.
Therefore, the trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst modified by the triammonium citrate still shows stable degradation capability under complex interference conditions, can be widely applied to various water bodies, and particularly has good application prospect for removing antibiotics in high-salinity wastewater.
Example 5:
examining the reusability of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst in treating antibiotic wastewater, in particular to a method for activating persulfate to degrade ciprofloxacin in a water body by adopting the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst, which comprises the following steps:
(1) taking a 150mL beaker, adding 100mL of 20mg/L ciprofloxacin solution, then adding 20mg of the triammonium citrate modified trace cobalt-doped magnalium ternary hydrotalcite-like composite catalyst (CA1-LDH) prepared in the example 1, then adding 20mg of potassium peroxymonosulfate composite salt (Oxone), stirring at the rotating speed of 400r/min, and carrying out catalytic degradation reaction for 60min, so as to realize degradation of ciprofloxacin in the water body and complete one cycle.
(2) And (2) after one cycle is completed, washing the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst reacted in the step (1) with 300ml of distilled water, 200ml of absolute ethyl alcohol and 300ml of distilled water in sequence, and drying at 80 ℃ for 12 hours to obtain the regenerated triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst.
(3) And (3) repeating the step (1) and the step (2) for three times to complete the degradation cycle experiment.
Fig. 12 is a graph of the degradation effect and the cycle number corresponding to when the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound catalyst (CA1-LDH) activates persulfate to degrade ciprofloxacin in example 5 of the present invention. From figure 12, the trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst modified by triammonium citrate has good recycling performance, ciprofloxacin is almost completely removed in the first cycle, the removal rate of the second cycle to the ciprofloxacin is reduced to 99.5%, and the removal rate of the third cycle to the ciprofloxacin is reduced to 84.0%, so that the composite catalyst has recycling value and is beneficial to reducing the cost of the catalyst in actual use.
In conclusion, the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst has better cobalt dispersibility, abundant oxygen vacancy defects and more active sites, is favorable for promoting the effect of a non-free radical approach in a persulfate advanced oxidation system in degrading organic pollutants, has the advantages of low leaching risk, high catalytic activity, high degradation efficiency, good recycling property and the like, can realize the rapid and safe removal of antibiotics in water, and has high practicability and good application prospect.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. A preparation method of a triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound catalyst is characterized by comprising the following steps:
s1, mixing cobalt salt, magnesium salt, aluminum salt, alkali source and triammonium citrate to prepare a catalyst precursor solution;
s2, carrying out hydrothermal reaction on the catalyst precursor solution obtained in the step S1 to obtain the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like compound catalyst.
2. The preparation method of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst according to claim 1, wherein the mass ratio of the magnesium salt to the triammonium citrate is 7.649: 0.122-1.216.
3. The preparation method of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst according to claim 2, wherein the mass ratio of the magnesium salt to the triammonium citrate is 7.649: 0.122-0.2091.
4. The preparation method of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst according to claim 3, wherein in step S1, the ratio of the cobalt salt, the magnesium salt, the aluminum salt and the solvent is 0.175-0.35 g: 7.692-15.384 g: 3.750-7.502 g: 0.1L, the mass ratio of the magnesium salt to the alkali source is 7.649: 10.5, the cobalt salt is cobalt nitrate hexahydrate, the magnesium salt is magnesium nitrate hexahydrate, the aluminum salt is aluminum nitrate nonahydrate, the alkali source is organic amine, the organic amine comprises one or more of urea, hexamethylenetetramine and ethylenediamine, and the solvent is water; the mixing is carried out under the condition of stirring, and the stirring time is 10 min-30 min.
5. The method for preparing the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst according to claim 1, wherein in step S2, the temperature of the hydrothermal reaction is 90-150 ℃, and the time of the hydrothermal reaction is 12-24 h.
6. The method for preparing the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst according to any one of claims 1 to 5, wherein in step S2, the method further comprises the following steps after the hydrothermal reaction: cleaning and drying the reaction product; the drying temperature is 60-80 ℃, the drying time is 24-48 h, and the drying is vacuum drying.
7. The preparation method of any one of claims 1 to 6, wherein the trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst is modified by triammonium citrate.
8. The application of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst in treating antibiotic wastewater according to claim 7.
9. Use according to claim 8, characterized in that it comprises the following steps: mixing a trace cobalt-doped magnesium-aluminum ternary hydrotalcite composite catalyst modified by triammonium citrate with antibiotic wastewater, and adding persulfate to perform a catalytic degradation reaction to complete the degradation of the antibiotic in the water body; the mass ratio of the triammonium citrate modified trace cobalt-doped magnesium-aluminum ternary hydrotalcite-like composite catalyst to the antibiotics in the antibiotic wastewater is 10-20: 1.
10. The application of claim 9, wherein the concentration of antibiotics in the antibiotic wastewater is 10mg/L to 20mg/L, the initial pH of the antibiotic wastewater is 3 to 11, the addition amount of persulfate is 0.2g to 0.5g of persulfate added to each liter of antibiotic wastewater, the antibiotics in the antibiotic wastewater is tetracycline, the persulfate is potassium peroxymonosulfate composite salt, the catalytic degradation reaction is performed under stirring conditions, the stirring rotation speed is 300r/min to 500r/min, and the stirring time is 30min to 90 min.
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