CN108675430A - Generate potentiometric titrations and the catalysis process of active oxygen species and the advanced oxidization method of difficult for biological degradation organic pollution - Google Patents

Generate potentiometric titrations and the catalysis process of active oxygen species and the advanced oxidization method of difficult for biological degradation organic pollution Download PDF

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CN108675430A
CN108675430A CN201810460979.9A CN201810460979A CN108675430A CN 108675430 A CN108675430 A CN 108675430A CN 201810460979 A CN201810460979 A CN 201810460979A CN 108675430 A CN108675430 A CN 108675430A
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solution
transition metal
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water
hydroxyl
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CN108675430B (en
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吕聪
贺丹
李易丞
张其慧
杨雪娇
冯威
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Jilin University
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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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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

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Abstract

The present invention provides a kind of generation potentiometric titrations and the catalysis process of active oxygen species and the advanced oxidization method of difficult for biological degradation organic pollution, to solve the problems, such as that organic pollutant degradation efficiency is relatively low, of high cost in the prior art.The catalysis process for generating potentiometric titrations and active oxygen species is using transition metal oxyhydroxide sill as catalyst, generate potentiometric titrations, hydroxyl radical free radical, superoxide radical and singlet oxygen non-free radical, and then efficient oxidation difficult for biological degradation organic pollution.The present invention improves the activation efficiency of persulfate using transition metal oxyhydroxide sill as catalyst, produces a variety of free radicals and active oxygen species, to improve the rates of oxidative degradation of organic pollution；Catalyst structure is stablized, and heavy metal dissolution rate is low in catalytic process, and non-secondary pollution can be widely applied to the improvement of the purified treatment, contaminated soil of industrial production wastewater processing, sanitary sewage disposal, polluted underground water and surface water.

Description

The catalysis process and difficult for biological degradation for generating potentiometric titrations and active oxygen species have The advanced oxidization method of machine pollutant
Technical field
The invention belongs to environmental protections and pollutant Prevention Technique field, and in particular to a kind of to generate sulfate radical freedom simultaneously The advanced oxidization method of the catalysis process and difficult for biological degradation organic pollution of base and active oxygen species.
Background technology
With the progress of society, while the economic life level of people is improved rapidly, environmental problem becomes It is increasingly severe, for example, ball warms, depletion of the ozone layer, acid rain, freshwater resources crisis, energy shortage, desertification of land rubbish at Calamity, toxic chemical pollution etc., some have threatened human survival.
The pollution of difficult for biological degradation organic pollution is one kind of toxic chemical pollution.With the production development of industrial or agricultural, Difficult for biological degradation organic pollution becomes a kind of essential industry and life material；And difficult for biological degradation organic pollution exists More difficult in water to be biodegradable, they can be polluted into water body by all means, and be gradually concentrated by food chain And it causes damages.The persistence of difficult for biological degradation organic pollution in the environment, and dispersion wide regional coverage, to environment with ecology It affects greatly, is all the important link of environmental pollution, ecological environment vicious circle all the time.
Currently, by the effort of environmental worker, studying and having developed advanced oxidation technology can reach efficient Mineralising aoxidizes to handle difficult for biological degradation organic pollution, reduces pollution, has good application prospect.
Traditional high-level oxidation technology (Advanced Oxidation Process, AOP) is the hydroxyl using high activity Free radical realizes Oxidative Degradation Process, includes mainly Fenton methods, Fenton-like method, photochemical oxidation, catalytic wet oxidation, sound Chemical oxidation, ozone oxidation, electrochemical oxidation etc..Compared with traditional water technology, high-level oxidation technology AOP, which has, to be applicable in The advantages of range is wide, reaction rate is fast, oxidability is strong, pollution-free or of low pollution.But the oxidability of hydroxyl radical free radical according to So there is certain bottleneck, applicable pH is limited in scope.
Novel high-level oxidation technology AOP is based on potentiometric titrations (SO4 -·,E0=2.5-3.1V), it is demonstrate,proved It is bright than traditional based on hydroxyl radical free radical (OH, E0=1.8-2.7V) oxidability it is strong, have higher half-life period, can fit The pH ranges answered are relatively wide (pH=2-10), do not have volatility, and to more environment-friendly, selective oxidizing is stronger, can be for a long time Keep character.But, however it remains factor of the potentiometric titrations in high-level oxidation technology is restricted, such as：Sulfate radical is free The mechanism of action of base and gas chromatography also needs further to explore；Producing method high energy consumption is activated, utilization rate is low；There is side reaction hair Raw, potentiometric titrations yield is low；It still can remaining oxidizing agent and metal ion after reaction；Can in underground water or in waste water A variety of interfering ion reactions, treatment effeciency susceptible.
In the prior art, the process that potentiometric titrations are generated in advanced oxidation processes, is urged by homogeneous catalyst Change, still, as the catalyst of generation potentiometric titrations, homogeneous catalyst has difficult recycling, hardly possible detaches, consumption is big, Refractory reason, secondary pollution problems are remained, while the additive amount of catalyst influences greatly reaction system, there are inorganic matter competition is anti- The distinct disadvantage answered.
Invention content
The technical problem to be solved in the present invention is to provide a kind of catalysis sides generating potentiometric titrations and active oxygen species The advanced oxidization method of method and difficult for biological degradation organic pollution, it is dirty to solve difficult for biological degradation organic pollution in the prior art The problem of dye.
In order to solve the above technical problems, the embodiment of the present invention provides a kind of generation potentiometric titrations and active oxygen species Catalysis process, the catalysis process is using transition metal oxyhydroxide as catalyst.
Further, the transition metal oxyhydroxide includes：Hydroxy cobalt oxide, hydroxyl manganese oxide, FeOOH, Hydroxy nickel oxide；
The active oxygen species include：Hydroxyl radical free radical, superoxide radical and singlet oxygen non-free radical.
Further, described method includes following steps：
The solid material of transition metal oxyhydroxide is ground, obtains catalyst fines by step S11；
Persulfate or single persulfate are added to the water by step S12, and be configured to 0.15~0.3mol/L first is molten Liquid；
Step S13 the catalyst fines is added in first solution, with 100r/min~400r/min speed It is stirred, activation persulfate generates potentiometric titrations and active oxygen species.
Further, the building-up process of the hydroxy cobalt oxide is as follows：
Step S211, by Co (NO3)2·6H2O is soluble in water, obtains the second solution of a concentration of 0.15~0.2mol/L；
Step S212 takes NaOH soluble in water, is configured to the NaOH solution of 0.5~2mol/L；
Step S213, by volume 1:NaOH solution is added dropwise in the second solution by 1 ratio, and supernatant is by rhodo Discoloration is transparent, and the reaction was complete, obtains third solution；
The third solution is placed in 60 DEG C of heating of constant temperature in water-bath, pours out supernatant, it is molten to obtain the 4th by step S214 Liquid；
Step S215, the 4th solution are placed on water-bath, and total solution quality 30% is added dropwise in heating stirring H2O2, then 60 DEG C of water-bath 3h of constant temperature, obtain the 5th solution；
Step S216 after centrifuging the 5th solution, washs solid, and solid is dry for 24 hours to get to hydroxyl in an oven Base cobalt oxide.
Further, the hydroxy nickel oxide building-up process is as follows：
Step S220, by NiSO4Solid is added to the water the NiSO of 0.15~0.3mol/L of preparation4Solution；
Step S221, by volume 1:1 ratio, by a concentration of 0.15~0.3mol/LK2S2O8Solution is added dropwise to described NiSO4In solution, the 6th solution is obtained；
Ammonium hydroxide is added in the 6th solution and adjusts acid-base value to pH=7~9 by step S222；
Step S223 stands 72 hours, obtains the 7th solution by the 6th solution under conditions of 35 DEG C；
Step S224 centrifuges the 7th solution, dry after obtained solid is washed；
Step S225, NaOH solids are added to a concentration of 0.15 by the concentration for being 1%~3% by mass fraction~ The 8th solution is obtained in the NaClO solution of 0.3mol/L, the solid in step S224 after drying is placed in the 8th solution It is uniformly mixed, obtains the 9th solution；
Step S226 centrifuges the 9th solution, and obtained solid washing after centrifugation, which is placed on baking oven, to be done It is dry for 24 hours to get to hydroxy nickel oxide.
Further, the building-up process of the hydroxyl manganese oxide is as follows：
Step S231, the concentration for being 1%~3% by mass fraction, by MnSO4·H2The NaOH that O is added to 0.1mol/L is molten In liquid；
30%~50%H of total solution quality is added in the solution obtained by step S231 by step S2322O2And it mixes equal It is even；
Step S232 acquired solutions are added in reaction kettle by step S233, are heated to 150 DEG C and are kept 15h；
Product in reaction kettle is naturally cooled to room temperature, washes with water to surface of solids pH and be in neutrality by step S234；
Obtained solid is placed in vacuum drying chamber by step S235, and 50 DEG C of vacuum drying 4h are to get to hydroxyl manganese oxide.
Further, the building-up process of the FeOOH is as follows：
Step S241, under stirring conditions, by volume 3:1 ratio, by the NaOH solution of a concentration of 1mol/L by It is added dropwise to the Fe (NO of a concentration of 1.2mol/L3)3In solution, vermilion precipitation is obtained；
PH of mixed is adjusted to 8~12, after standing 1~4h, is put into heat preservation by step S242 after vermilion precipitation is complete 30 DEG C of constant temperature of case activate 2h；
Step S243 cleans sediment repeatedly with water, until pH value 7~9；
Step S244, by 30 DEG C of the sediment constant temperature drying after cleaning to get to FeOOH.
Further, load has metal oxide or the transition metal hydroxyl on the transition metal oxyhydroxide It is oxide carried in non-metal carrier or the transition metal oxyhydroxide doped with transition metal ions.
Further, the transition metal oxyhydroxide includes：Hydroxy cobalt oxide, hydroxyl manganese oxide, FeOOH, Hydroxy nickel oxide；The metal oxide loaded on the transition metal oxyhydroxide includes： TiO2、ZnO、CuO、Al2O3、 Fe3O4、MnO2、Bi2O3、CeO2、NiO、Co3O4And V2O5；The non-metal carrier includes：Three-dimensional grapheme, redox graphite Alkene, carbon nanotube, molecular sieve；Molecular formula doped with the transition metal oxyhydroxide of transition metal ions is MxN1-xOOH, Wherein 0<x<1, M Ni, Mn, Co, Zn, Fe element, N Ni, Mn, Co, Zn, Fe, Mg, Cu element, and M and N are different member Element.
According to another aspect of the present invention, a kind of advanced oxidation side of difficult for biological degradation organic pollution is additionally provided Method, the advanced oxidization method using transition metal oxyhydroxide substance be used as catalyst, generate potentiometric titrations with Active oxygen species, and then oxidative degradation is carried out to the difficult for biological degradation organic pollution.
Above-mentioned technical proposal of the present invention has the beneficial effect that：
Catalysis process and the difficult for biological degradation organic contamination of the generation potentiometric titrations and active oxygen species of the present embodiment The advanced oxidization method of object is catalyzed using transition metal oxyhydroxide as catalyst by transition metal oxyhydroxide Persulfate or single persulfate generate potentiometric titrations and active oxygen species include hydroxyl radical free radical, superoxide radical and Singlet oxygen non-free radical carries out oxidative degradation to difficult for biological degradation organic pollution.By by transition metal oxyhydroxide The fine particle of class catalyst is put into reactor, oxidant of the persulfate as reaction system is added, then put into organic dirt Dye object is degraded.The present invention improves activation persulfate using transition metal oxyhydroxide sill as catalyst Efficiency, improves the rates of oxidative degradation of organic pollution, and transition metal oxyhydroxide class catalyst structure is stablized, cannot be by S2O8 2-Oxygenolysis, heavy metal dissolution rate is low in catalytic process, the heavy metal Gao Rong of the current homogeneous catalyst of effective solution Go out, the problem of degradation condition harshness, catalytic process will not bring the secondary pollution of heavy metal ion, two are hardly brought to environment Secondary pollution, can be used for sanitary sewage disposal, industrial and agricultural production wastewater treatment, underground water and surface water purified treatment, repair by The soil of organic pollution.It is greatly improved the removal efficiency to difficult for biological degradation organic pollution, the removal rate of organic matter can Up to 88%~100%.
Description of the drawings
For the elaboration the embodiment of the present invention being more clear and existing technical solution, below by the technical side of the present invention Case illustrates that attached drawing does simple introduction, it is clear that, without creative efforts, ordinary skill people Member can obtain other attached drawings by this attached drawing.
Fig. 1 is to carry out treated design sketch to the solution containing dyestuff contaminant using the embodiment of the present invention 8；
Fig. 2 is to carry out treated design sketch to the solution containing chlorophenol pollutants using the embodiment of the present invention 8；
Fig. 3 is to carry out treated design sketch to the solution containing antibiotic pollutant using the embodiment of the present invention 8；
Fig. 4 is to carry out treated design sketch to the solution containing chlorophenol pollutants using the embodiment of the present invention 8；
Fig. 5 is to carry out treated design sketch to the solution containing dyestuff contaminant using the embodiment of the present invention 8.
Specific implementation mode
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool Technical solution of the present invention is described in body embodiment.
The problem of present invention is handled for difficult for biological degradation organic pollution in the prior art is based on high-level oxidation technology (Advanced Oxidation Process, AOP), it is proposed that a kind of generation potentiometric titrations, hydroxyl radical free radical, super oxygen from By the catalysis process of base and singlet oxygen non-free radical and to the advanced oxidization method of difficult for biological degradation organic pollution, this hair The catalyst for generating potentiometric titrations and active oxygen in bright embodiment is using transition metal oxyhydroxide.Transition metal hydroxyl Base oxide class catalyst includes hydroxy cobalt oxide CoOOH, hydroxyl manganese oxide MnOOH, FeOOH FeOOH, hydroxyl oxidation Nickel OOH etc..This kind of catalyst all has efficient electron transfer rate, has multiple surface-active points, is to have high surface The strongly hydrophilic compound of hydroxyl group sites, while supporting heterogeneous reaction may be used as various forms of catalyst and (such as disperse , it is load and colloid), transition metal dissolution rate is relatively low, has high stability, has efficiently activation persulfate, degradation The ability of organic pollution in water or in soil.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
The present embodiment propose it is a kind of generate potentiometric titrations and active oxygen species catalysis process, use CoOOH for Catalyst includes the following steps：
Synthesize CoOOH：
Step S211 takes Co (NO3)2·6H2O is soluble in water, obtains the second solution of a concentration of 0.15~0.2mol/L；
Step S212 takes NaOH soluble in water, prepares the NaOH solution of 1mol/L；
Step S213, by volume 1:NaOH solution is added dropwise in the second solution by 1 ratio, and supernatant is by rhodo Discoloration is transparent, and the reaction was complete, obtains third solution；
The third solution is placed in 60 DEG C of heating of constant temperature in water-bath, pours out supernatant, it is molten to obtain the 4th by step S214 Liquid；
Step S215, the 4th solution are placed on water-bath, and it is 30% that molar concentration is added dropwise in heating stirring H2O2, then 60 DEG C of water-bath 3h of constant temperature, obtain the 5th solution；
Step S216 after centrifuging the 5th solution, washs solid, and solid is dry for 24 hours to get to hydroxyl in an oven Base cobalt oxide.
Complete catalysis：
The solid material of hydroxy cobalt oxide is ground to fine particle and obtains hydroxy cobalt oxide powder by step S111；It is described Grain diameter is 1um~30um；
Single persulfate (peroxymonosulfate, PMS) is added to the water, is configured to single persulfate by step S112 Aqueous solution；
Hydroxy cobalt oxide powder is added in single persulfate aqueous solution, is stirred with 400r/min speed by step S113 It mixes, generates potentiometric titrations and active oxygen species.Preferably, the active oxygen species include：Hydroxyl radical free radical, super oxygen are free Base and singlet oxygen non-free radical.
Embodiment 2
The present embodiment proposes a kind of catalysis process generating potentiometric titrations and active oxygen species, the catalysis process It uses NiOOH for catalyst, includes the following steps：
Synthesize NiOOH：
Step S220, by NiSO4Solid is added to the water the NiSO of 0.15~0.3mol/L of preparation4Solution；
Step S221, by volume 1:1 ratio, by a concentration of 0.15~0.3mol/LK2S2O8Solution is added dropwise to described NiSO4In solution, the 6th solution is obtained；
Step S222 is slowly added to ammonium hydroxide in the 6th solution and adjusts acid-base value to pH=7~9；
Step S223 stands 72 hours, obtains the 7th solution by the 6th solution under conditions of 35 DEG C；
Step S224 centrifuges the 7th solution after standing, the solid that will be obtained, dry after washing；
Step S225, NaOH solids are added to a concentration of 0.15 by the concentration for being 1%~3% by mass fraction~ The 8th solution is obtained in the NaClO solution of 0.3mol/L, the solid in step S224 after drying is placed in the 8th solution It is uniformly mixed, obtains the 9th solution；Step S226 centrifuges the 9th solution, and obtained solid after centrifugation is washed It washs and is placed on oven drying for 24 hours to get to hydroxy nickel oxide.Complete catalysis：
The solid material of hydroxy nickel oxide is ground to fine particle and obtains nickel oxyhydroxide powder by step S121；It is described Grain diameter is 1um~30um；
Step S122, persulfate is added to the water, and is configured to persulfate aqueous solution；
Nickel oxyhydroxide powder is added in persulfate aqueous solution, is stirred with 100r/min speed by step S123, Generate potentiometric titrations and active oxygen species.Preferably, the active oxygen species include：Hydroxyl radical free radical, superoxide radical, With singlet oxygen non-free radical.
Embodiment 3
The present embodiment propose it is a kind of generate potentiometric titrations and active oxygen species catalysis process, use MnOOH for Catalyst includes the following steps：
Synthesize MnOOH：
Step S231, the concentration for being 1%~3% by mass fraction, by MnSO4·H2O is added to the NaOH of 0.1mol/L In solution；
30%~50%H of total solution quality is added in the solution obtained by step S231 by step S2322O2And it mixes equal It is even；
Step S232 acquired solutions are added in reaction kettle by step S233, are heated to 150 DEG C and are kept 15h；
Product in reaction kettle is naturally cooled to room temperature, washes with water to surface of solids pH and be in neutrality by step S234；
Obtained solid is placed in vacuum drying chamber by step S235, and 50 DEG C of vacuum drying 4h are to get to hydroxyl manganese oxide.
Complete catalysis：
The solid material of hydroxyl manganese oxide is ground to fine particle and obtains hydroxyl manganese oxide powder by step S131；It is described Grain diameter is 1um~30um；
Persulfate and single persulfate are added to the water, are configured to compound saline solution by step S132 according to a certain ratio；
Hydroxyl manganese oxide powder is added in compound saline solution, is stirred with 300r/min speed by step S133, is produced Raw potentiometric titrations and active oxygen species.Preferably, the active oxygen species include：Hydroxyl radical free radical, superoxide radical and Singlet oxygen non-free radical.
Embodiment 4
This example implement propose it is a kind of generate potentiometric titrations and active oxygen species catalysis process, use FeOOH for Catalyst includes the following steps：
Synthesize FeOOH：
Step S241, under stirring conditions, by volume 3:1 ratio, by the NaOH solution of a concentration of 1mol/L by It is added dropwise to the Fe (NO of a concentration of 1.2mol/L3)3In solution, vermilion precipitation is obtained；
PH of mixed is adjusted to 8~12, after standing 1~4h, is put into heat preservation by step S242 after vermilion precipitation is complete 30 DEG C of constant temperature of case activate 2h；
Step S243 cleans sediment repeatedly with water, until pH value 7~9；
Step S244, by 30 DEG C of the sediment constant temperature drying after cleaning to get to FeOOH.
Complete catalysis：
The solid material of FeOOH is ground to fine particle and obtains FeOOH powder by step S141；It is described Grain diameter is 1um~30um；
Step S142, persulfate is added to the water, and is configured to persulfate aqueous solution；
FeOOH powder is added in persulfate aqueous solution, is stirred with 200r/min speed by step S143, Generate potentiometric titrations and active oxygen species.Preferably, the active oxygen species include：Hydroxyl radical free radical, superoxide radical, With singlet oxygen non-free radical.
Embodiment 5
This example is implemented to propose a kind of catalysis process generating potentiometric titrations and active oxygen species, using on CoOOH Metal oxide-loaded Bi2O3For catalyst, include the following steps：
Load is had Bi by step S1512O3The solid material of CoOOH be ground to fine particle, the grain diameter is 1um~30um；
Step S152, persulfate is added to the water, and is configured to persulfate aqueous solution；
Load is had Bi by step S1532O3CoOOH powder be added persulfate aqueous solution in, with 200r/min speed It is stirred, generates potentiometric titrations and active oxygen species.Preferably, the active oxygen species include：Hydroxyl radical free radical surpasses Oxygen radical and singlet oxygen non-free radical.
The load in the present embodiment has Bi2O3CoOOH solid material preparation process and embodiment 1 in CoOOH building-up processes are essentially identical, the difference is that step S211 is：By 2.91gCo (NO3)2·6H2After O is dissolved in ultrasound Bi2O3200ml is added water in solution, makes the Co (NO of 0.05mol/L3)2Solution.
Particularly, the metal oxide Bi in the present embodiment2O3It could alternatively be one kind of multiple in following oxides： TiO2、ZnO、CuO、Al2O3、Fe3O4、MnO2、CeO2、NiO、Co3O4And V2O5；Transition metal oxyhydroxide in the present embodiment Hydroxy cobalt oxide could alternatively be hydroxyl manganese oxide, FeOOH, hydroxy nickel oxide.
Embodiment 6
This example is implemented to propose a kind of catalysis process generating potentiometric titrations and active oxygen species, using in CoOOH Doping Ni ions are catalyst, are included the following steps：
Step S161 will be ground to fine particle doped with the solid material of the CoOOH of Ni ions, and the grain diameter is 1um~30um；
Step S162, persulfate is added to the water, and is configured to persulfate aqueous solution；
Step S163 will be added in persulfate aqueous solution doped with the CoOOH powder of Ni ions, with 200r/min speed Degree is stirred, and generates potentiometric titrations and active oxygen species.Preferably, the active oxygen species include：Hydroxyl radical free radical, Superoxide radical and singlet oxygen non-free radical.
The building-up process of the CoOOH solid materials of the doping Ni ions in the present embodiment and CoOOH in embodiment 1 Building-up process it is essentially identical, the difference is that step S211 is：It will be according to Ni：Co=0.05：095, weigh 2.7645g's Co(NO3)2·6H2O is dissolved in 200ml water, then weighs the Ni (NO of 0.1455g3)2·6H2O is dissolved in above-mentioned solution, and is stirred Uniformly.
Particularly, CoOOH, that is, NiCoOOH of the doping Ni ions in the present embodiment, could alternatively be general formula is MxN1- xThe transition metal oxyhydroxide containing transition metal ions of OOH, wherein 0<x<1, M Ni, Mn, Co, Zn, Fe element, N For Ni, Mn, Co, Zn, Fe, Mg, Cu element, and M and N is different element；Transition metal oxyhydroxide in the present embodiment Hydroxy cobalt oxide could alternatively be hydroxyl manganese oxide, FeOOH, hydroxy nickel oxide.
Embodiment 7
This example is implemented to propose a kind of catalysis process generating potentiometric titrations and active oxygen species, negative using CoOOH It is catalyst to be loaded in graphene oxide, is included the following steps：
The solid material for the CoOOH being carried on graphene oxide is ground to fine particle, the particle by step S171 Grain size is 1um~30um；
Step S172, persulfate is added to the water, and is configured to persulfate aqueous solution；
Step S173 the CoOOH powder being carried on graphene oxide is added in persulfate aqueous solution, with 200r/ Min speed is stirred, and generates potentiometric titrations and active oxygen species.Preferably, the active oxygen species include：Hydroxyl is certainly By base, superoxide radical and singlet oxygen non-free radical.
The preparation process and embodiment of the solid material of the CoOOH being carried on graphene oxide in the present embodiment The building-up process of CoOOH is essentially identical in 1, the difference is that step S211 is：1mg/mL concentration is configured in 500mL beakers Graphene oxide, ultrasonic 12h, ultrasound uniformly after with 0.5mol/LCo (NO3)2·6H2O solution equal proportions mix.
Particularly, the graphene oxide as carrier in the present embodiment, could alternatively be carbon nanotube, three-dimensional graphite Alkene, redox graphene, molecular sieve；Transition metal oxyhydroxide hydroxy cobalt oxide in the present embodiment could alternatively be hydroxyl Base manganese oxide, FeOOH, hydroxy nickel oxide.
The catalysis process generated free radicals described in embodiment 1 to 7, using transition metal oxyhydroxide as catalysis There is larger specific surface area, efficient electron transfer rate to improve activation persulfate for agent, transition metal oxyhydroxide With the efficiency of single persulfate；Transition metal oxyhydroxide class catalyst structure is stablized, cannot be by S2O8 2-Oxygenolysis, weight Digestion of metallic ion rate is low, and catalytic process will not bring the secondary pollution of heavy metal ion, and secondary dirt is hardly brought to environment Dye, potential hazard are small；Meanwhile technical solution of the embodiment of the present invention can be used for sanitary sewage disposal, industrial and agricultural production wastewater treatment, The purified treatment of underground water and surface water repairs soil polluted by organic matter, greatly improves to the difficult biology drop of difficult for biological degradation The removal efficiency of organic pollution is solved, the removal rate of organic matter is up to 88%~100%.The generation potentiometric titrations of the present invention And the catalysis process of active oxygen species has certain repeatable usability, economic cost is low relative to other treatment technologies, tool Have broad application prospects.
Embodiment 8
This example applies the advanced oxidization method for providing a kind of difficult for biological degradation organic pollution, the advanced oxidization method It is catalyzed persulfate by transition metal oxyhydroxide or single persulfate generates potentiometric titrations and active oxygen to hardly possible life Object degradable organic pollutant carries out oxidative degradation.Specifically, the described method comprises the following steps：
Persulfate or single persulfate are added to the water by step S32, are configured to degradation aqueous solution；
The degradation aqueous solution is added in the solution containing difficult for biological degradation organic pollution step S33；
Catalyst is added in the solution containing difficult for biological degradation organic pollution of the step S33 in step S34, then The persulfate solution stirring prepared is added, is stirred, is completed in pending solution with 100r/min~400r/min speed The degradation of difficult for biological degradation organic pollution.Wherein, S in the aqueous solution of the step S322O8 2-With the organic dirt of difficult for biological degradation The molar ratio for contaminating object is 20:1；The solid water ratio for the transition metal oxyhydroxide aqueous solution being added in the step S32 is 0.1~ 0.4g/L。
Further, the catalyst is transition metal oxyhydroxide.Preferably, on the transition metal oxyhydroxide Load has metal oxide or the transition metal oxyhydroxide to be carried on non-metal carrier or the transition metal hydroxyl Doped with transition metal ions in oxide.
Further, the transition metal oxyhydroxide includes：Hydroxy cobalt oxide, hydroxyl manganese oxide, FeOOH, Hydroxy nickel oxide；The metal oxide loaded on the transition metal oxyhydroxide includes： TiO2、ZnO、CuO、Al2O3、 Fe3O4、MnO2、Bi2O3、CeO2、NiO、Co3O4And V2O5；The non-metal carrier includes：Three-dimensional grapheme, redox graphite Alkene, carbon nanotube, molecular sieve；The molecular formula of the transition metal oxyhydroxide of containing transition metal ion is MxN1-xOOH, In 0<x<1, M Ni, Mn, Co, Zn, Fe element, N Ni, Mn, Co, Zn, Fe, Mg, Cu element, and M and N are different element.
Using the advanced oxidization method of the present embodiment, at the solution containing different difficult for biological degradation organic pollutions Reason, wherein different difficult for biological degradation organic pollutions is respectively：Dyestuff, chlorophenol, antibiotic.
Fig. 1 is shown carries out treated design sketch using the present embodiment to the solution containing dyestuff contaminant, is used Catalyst be hydroxy cobalt oxide, hydroxyl manganese oxide, FeOOH, hydroxy nickel oxide；Processing parameter is：Degradation of dye pollutes Object AO7Pollutant concentration=150mg/L；[PMS]/[pollutant]=20:1；Solid water ratio=0.2g/L；Fig. 2 is shown using this Embodiment carries out treated design sketch to the solution containing chlorophenol pollutants, and used catalyst is hydroxy cobalt oxide, hydroxyl Base manganese oxide, FeOOH, hydroxy nickel oxide；Processing parameter is：Degrading chlorophenol pollutant 2,4-DCP, pollutant concentration =100mg/L；[PMS]/[pollutant]=20:1；Solid water ratio=0.2g/L；Fig. 3 show anti-to containing using the present embodiment The solution of raw element pollutant carries out that treated design sketch, used catalyst is hydroxy cobalt oxide, hydroxyl manganese oxide, hydroxyl Iron oxide, hydroxy nickel oxide；Processing parameter is：Degradation antibiotic contamination tetracycline, pollutant concentration=100mg/L； [PMS]/[pollutant]=20:1；Solid water ratio=0.2g/L；Fig. 4 is shown using the present embodiment to containing chlorophenol pollutant Solution carries out treated design sketch, and used catalyst, which is load, Bi3O2Hydroxy cobalt oxide；Processing parameter is：Degradation Chlorophenol pollutant 2,4-DCP pollutant concentrations=150mg/L；[PMS]/[pollutant]=20:1；Solid water ratio=0.1g/L；Figure 5 show and carry out treated design sketch to the solution containing dyestuff contaminant using the present embodiment, and used catalyst is mixed The miscellaneous CoOOH for having NiCoOOH；Processing parameter is：Degradation of dye AO7Pollutant, pollutant concentration=100mg/L；[PMS]/ [pollutant]=20:1；Solid water ratio=0.4g/L.
It will be seen from figure 1 that the persulfate solution that heterogeneous transition metal oxyhydroxide class catalyst is catalyzed, Can effective degradation of dye pollutant, wherein four kinds of transition metal oxyhydroxides persulfate is catalyzed after to dye discoloration The degradation effect sequence of object is CoOOH>NiOOH>MnOOH>FeOOH；From figure 2 it can be seen that heterogeneous transition metal hydroxyl The persulfate solution that oxide-based catalyst is catalyzed, can effective degrading chlorophenol pollutant, wherein four kinds of transition The degradation effect sequence of parachlorphenol pollutant is CoOOH after metal oxyhydroxides are catalyzed persulfate>MnOOH> NiOOH>FeOOH；From figure 3, it can be seen that the persulfate that heterogeneous transition metal oxyhydroxide class catalyst is catalyzed Solution, can effectively degrade antibiotic contamination, wherein after four kinds of transition metal oxyhydroxides are catalyzed persulfate Degradation effect sequence to antibiotic contamination is CoOOH>NiOOH>MnOOH>FeOOH；From fig. 4, it can be seen that load has The persulfate solution that the transition metal oxyhydroxide class catalyst of metal oxide is catalyzed, can effective degrading chlorophenol Pollutant；From fig. 5, it can be seen that being M doped with general formulaxN1-xThe transition metal hydroxyl such as CoOOH of the transition metal ions of OOH The persulfate solution that base oxide class catalyst is catalyzed, can effective degradation of dye pollutant.It can be seen that using non- Homogeneous transition metal oxyhydroxide class catalyst is catalyzed one salt of persulfuric acid, can efficiently generate for advanced oxidation The potentiometric titrations and active oxygen of reaction, to which efficiently degradation carries the pollutant of phenyl ring.
It can be seen that the advanced oxidation of the difficult for biological degradation organic pollution difficult for biological degradation organic pollution of the present embodiment The fine particle of transition metal oxyhydroxide class catalyst is put into reactor by method, and persulfate is added as reaction The oxidant of system, then put into organic pollution and degrade, transition metal oxyhydroxide class catalyst, which improves, to be activated The efficiency of sulfate, transition metal oxyhydroxide class catalyst structure are stablized, cannot be by S2O8 2-Oxygenolysis, it is effective to solve The heavy metal height of certainly current homogeneous catalyst dissolves out, and the problem of degradation condition harshness, catalytic process will not bring heavy metal ion Secondary pollution, secondary pollution is hardly brought to environment, can be used for sanitary sewage disposal, industrial and agricultural production wastewater treatment, The purified treatment of lower water and surface water repairs soil polluted by organic matter.It is greatly improved to difficult for biological degradation organic contamination The removal efficiency of object, the removal rate of organic matter is up to 88%~100%.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims (10)

1. a kind of catalysis process generating potentiometric titrations and active oxygen species, which is characterized in that the catalysis process uses Transition metal oxyhydroxide is as catalyst.
2. catalysis process according to claim 1, which is characterized in that the transition metal oxyhydroxide includes：Hydroxyl Cobalt oxide, hydroxyl manganese oxide, FeOOH, hydroxy nickel oxide；
The active oxygen species include：Hydroxyl radical free radical, superoxide radical and singlet oxygen non-free radical.
3. catalysis process according to claim 1 or 2, which is characterized in that described method includes following steps：
The solid material of transition metal oxyhydroxide is ground, obtains catalyst fines by step S11；
Persulfate or single persulfate are added to the water, are configured to the first solution of 0.15~0.3mol/L by step S12；
The catalyst fines are added in first solution, are stirred with 100r/min~400r/min speed by step S13 It mixes, activation persulfate generates potentiometric titrations and active oxygen species.
4. catalysis process according to claim 2, which is characterized in that the building-up process of the hydroxy cobalt oxide is as follows：
Step S211, by Co (NO3)2·6H2O is soluble in water, obtains the second solution of a concentration of 0.15~0.2mol/L；
Step S212 takes NaOH soluble in water, is configured to the NaOH solution of 0.5~2mol/L；
Step S213, by volume 1:NaOH solution is added dropwise in the second solution by 1 ratio, and supernatant is by rhodo discoloration To be transparent, the reaction was complete, obtains third solution；
The third solution is placed in 60 DEG C of heating of constant temperature in water-bath, pours out supernatant, obtain the 4th solution by step S214；
Step S215, the 4th solution are placed on water-bath, and the H of total solution quality 30% is added dropwise in heating stirring2O2, then 60 DEG C of water-bath 3h of constant temperature, obtain the 5th solution；
Step S216 after centrifuging the 5th solution, washs solid, and solid is dry for 24 hours to get to hydroxyl oxygen in an oven Change cobalt.
5. catalysis process according to claim 2, which is characterized in that the hydroxy nickel oxide building-up process is as follows：
Step S220, by NiSO4Solid is added to the water the NiSO of 0.15~0.3mol/L of preparation4Solution；
Step S221, by volume 1:1 ratio, by a concentration of 0.15~0.3mol/LK2S2O8Solution is added dropwise to the NiSO4It is molten In liquid, the 6th solution is obtained；
Ammonium hydroxide is added in the 6th solution and adjusts acid-base value to pH=7~9 by step S222；
Step S223 stands 72 hours, obtains the 7th solution by the 6th solution under conditions of 35 DEG C；
Step S224 centrifuges the 7th solution, dry after obtained solid is washed；
NaOH solids are added to a concentration of 0.15~0.3mol/L's by step S225, the concentration for being 1%~3% by mass fraction The 8th solution is obtained in NaClO solution, and the solid in step S224 after drying is placed in the 8th solution and is uniformly mixed, is obtained To the 9th solution；
Step S226 centrifuges the 9th solution, and obtained solid washing after centrifugation is placed on oven drying For 24 hours to get to hydroxy nickel oxide.
6. catalysis process according to claim 2, which is characterized in that the building-up process of the hydroxyl manganese oxide is as follows：
Step S231, the concentration for being 1%~3% by mass fraction, by MnSO4·H2O is added to the NaOH solution of 0.1mol/L In；
30%~50%H of total solution quality is added in the solution obtained by step S231 by step S2322O2And it is uniformly mixed；
Step S232 acquired solutions are added in reaction kettle by step S233, are heated to 150 DEG C and are kept 15h；
Product in reaction kettle is naturally cooled to room temperature, washes with water to surface of solids pH and be in neutrality by step S234；
Obtained solid is placed in vacuum drying chamber by step S235, and 50 DEG C of vacuum drying 4h are to get to hydroxyl manganese oxide.
7. catalysis process according to claim 2, which is characterized in that the building-up process of the FeOOH is as follows：
Step S241, under stirring conditions, by volume 3:1 ratio adds the NaOH solution of a concentration of 1mol/L dropwise Enter the Fe (NO to a concentration of 1.2mol/L3)3In solution, vermilion precipitation is obtained；
PH of mixed is adjusted to 8~12, after standing 1~4h, is put into incubator 30 by step S242 after vermilion precipitation is complete DEG C constant temperature activates 2h；
Step S243 cleans sediment repeatedly with water, until pH value 7~9；
Step S244, by 30 DEG C of the sediment constant temperature drying after cleaning to get to FeOOH.
8. catalysis process according to claim 1, which is characterized in that load has gold on the transition metal oxyhydroxide Belong to oxide or the transition metal oxyhydroxide is carried in non-metal carrier or the transition metal oxyhydroxide Doped with transition metal ions.
9. catalysis process according to claim 8, which is characterized in that the transition metal oxyhydroxide includes：Hydroxyl Cobalt oxide, hydroxyl manganese oxide, FeOOH, hydroxy nickel oxide；The metal oxygen loaded on the transition metal oxyhydroxide Compound includes：TiO2、ZnO、CuO、Al2O3、Fe3O4、MnO2、Bi2O3、CeO2、NiO、Co3O4And V2O5；The non-metal carrier Including：Three-dimensional grapheme, redox graphene, carbon nanotube, molecular sieve；Doped with the transition metal hydroxyl of transition metal ions The molecular formula of base oxide is MxN1-xOOH, wherein 0<x<1, M Ni, Mn, Co, Zn, Fe element, N Ni, Mn, Co, Zn, Fe, Mg, Cu element, and M and N is different element.
10. a kind of advanced oxidization method of difficult for biological degradation organic pollution, which is characterized in that the advanced oxidization method uses Transition metal oxyhydroxide substance generates potentiometric titrations and active oxygen species, and then to the difficulty as catalyst Biodegradable organic pollution carries out oxidative degradation.
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