CN103304092A - Method for removing antibiotics in swine wastewater by use of metal oxide loaded active carbon - Google Patents
Method for removing antibiotics in swine wastewater by use of metal oxide loaded active carbon Download PDFInfo
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- CN103304092A CN103304092A CN2013101797172A CN201310179717A CN103304092A CN 103304092 A CN103304092 A CN 103304092A CN 2013101797172 A CN2013101797172 A CN 2013101797172A CN 201310179717 A CN201310179717 A CN 201310179717A CN 103304092 A CN103304092 A CN 103304092A
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Abstract
The invention provides a method for removing antibiotics in swine wastewater by use of metal oxide loaded active carbon. By combining metal oxide loaded active carbon with an ozone oxidation technology and adopting active carbon as an adsorbent, trace antibiotics in the water body can be adsorbed and are enriched on the surface of the active carbon so that the ozone contacts and reacts with antibiotics more easily; and meanwhile, the active carbon also can be used as a catalyst to catalyze ozonolysis to generate free radicals with strong oxidbillity. The metal oxide loaded on the surface of the active carbon also can catalyze ozonolysis to generate free radicals, and the antibiotic molecules are quickly oxidized and decomposed into smaller molecules and are further mineralized into carbon dioxide, water and inorganic salt so as to achieve the aims of degradation and antibiotic removal. The method provided by the invention realizes an obvious effect on removing antibiotics of the output swine wastewater treated by a biological treatment process, and has the advantages of economy, convenience, strong operability, good comprehensive treatment effect and the like.
Description
Technical field
The present invention relates to the method that a kind of metal oxide-loaded activated carbon catalysis ozone oxidation is removed for the waste water microbiotic of raising pigs.
Background technology
Large scale of pig farm waste water is mainly derived from pig farm to the cleaning of pig house, pig urine and pig manure partly etc., so its waste water has characteristics such as organic concentration height, suspension content height, concentration of nitrogen and phosphorus height; And in order to improve the upgrowth situation of pig; large scale of pig farm factory can use some to contain fodder additives and the antibiotics material of heavy metals such as Cu usually; wherein have only 10～20% Cu and microbiotic to digest in the pig body, most heavy metal and antibiotic substance can directly excrete by the Digestive tract of pig.There are some researches show that in the pig manure of drying, antibiotic average content is up to 121.78mg/kg, the content of Cu is also up to 135～471mg/kg.
The main treatment scheme of livestock breeding wastewater is both at home and abroad at present: solid-liquid separation-anaerobic digestion-aerobic treatment, its main purpose are organism, nitrogen, phosphorus and the heavy metals of removing in the waste water.The waste water of raising pigs is through after solid-liquid separation-anaerobic digestion-aerobic treatment flow process, wastewater pH reaches 7.0-9.0, COD, ammonia nitrogen and total phosphorus all can be up to standard, and removal rate of heavy metal such as Cu can reach 80-90%, and the antibiotics material can not effectively be removed in the biological treatment flow process.Effectively just remove as non-confrontational living element and to discharge, the antibiotics material will be in the medium-term and long-term existence of environment, and enter human body by migration and the enrichment of food chain, even bring out pathogenic bacterium and produce resistance, not only become the very big hidden danger of ecological safety, and can cause human health and seriously influence.Studies show that, raising pigs, antibiotic main component is terramycin, tsiklomitsin, duomycin, norfloxicin, Ciprofloxacin, Enrofloxacin, erythromycin, Roxithromycin, Sulfamethoxazole, sulphamethazine etc. in the waste water, these antibiotic compositions all can be at the medium-term and long-term existence of environment, harm environment.
China reports on antibiotic Research And Engineering application is degraded in the waste water advanced processing of raising pigs as yet at present.According to domestic and international research, the effective way that micro-microbiotic is removed in the water body has a lot, as membrane technique, charcoal absorption technology and ozonation technology etc.Ozone oxidation refers to that ozone contacts with pollutent, and the oxidation by ozone is with pollutant removal.But ozone oxidation has selectivity, and the utilization ratio of ozone is not high, speed of reaction is low, is difficult to the pollutent exhaustive oxidation is easy to generate oxidized byproduct in water body, salinity to pollutent is low, thereby has limited the application of ozonation technology aspect the degraded microbiotic.
Summary of the invention
Task of the present invention provides a kind of metal oxide-loaded gac and removes antibiotic method in the waste water of raising pigs, make it have the microbiotic that effectively to remove in the waste water of raising pigs, degraded other hard-degraded substances in the waste water of raising pigs, and have characteristics such as economy, convenient, workable and comprehensive treatment effect are good.
Realize that technical scheme of the present invention is:
Metal oxide-loaded gac provided by the invention is used for removing the antibiotic method of waste water of raising pigs, and may further comprise the steps:
Step 1: utilize solid-liquid separation of the prior art, anaerobic digestion, aerobic biochemical three technology couplings of processing or preceding two technology couplings that the waste water of raising pigs is handled, the removal suspended particle in the waste water of raising pigs, and COD, ammonia nitrogen and phosphoric acid salt in the waste water of raising pigs are removed in degraded;
Step 2: will add in the reaction vessel that is filled with metal oxide-loaded gac through the waste water of raising pigs after the step 1 processing and react 20～60min, the weightmeasurement ratio by ozone and the waste water of raising pigs in the reaction process is 3～150 milligrams: 1 liter amount ratio feeds ozone in reactor.
In the aforesaid method, the metal oxide of described metal oxide-loaded gac institute load is a kind of in the oxide compound of the oxide compound of the oxide compound of cerium, iron, manganese or more than two kinds; The weight ratio of metal oxide and gac is 0.1～30: 100 in the described metal oxide-loaded gac; Described gac is the mesopore coal mass active carbon, and described mesopore coal mass active carbon aperture is between 2～100nm, and activated carbon particle size is 0.5～2.0mm.
The metal oxide of the metal oxide-loaded gac institute load described in the aforesaid method specifically can be the oxide compound of cerium and the hopcalite of iron, the molar ratio of the oxide compound of cerium and the oxide compound of iron is 1～5: 1, and the weight ratio of metal oxide and gac is 0.1～30: 100 in the described metal oxide-loaded gac.
It also can be the oxidation of cerium and the hopcalite of manganese that metal oxide-loaded gac institute load described in the aforesaid method gets metal oxide, the molar ratio of the oxide compound of cerium and the oxide compound of manganese is 1～5: 1, and the weight ratio of metal oxide and gac is 0.1～30: 100 in the described metal oxide-loaded gac.
Metal oxide-loaded gac institute load described in the aforesaid method gets the oxide compound that metal oxide can also be cerium, the oxide compound of iron and the hopcalite of manganese, the molar ratio of the oxide compound of the oxide compound of the oxide compound of cerium, iron and manganese is 2～5 in this mixture: 1: 1, the weight ratio of metal oxide and gac was 0.1～30: 100 in the described metal oxide-loaded gac.
The present invention will solve is that traditional biological treatment is at present raised pigs and is difficult to efficiently remove the problem of microbiotic and other hardly degraded organic substances in the waster water process, and the method for the waste water advanced processing of a kind of large scale of pig farm is provided.This method can effectively be removed the microbiotic in the waste water of raising pigs, degraded other hard-degraded substances in the waste water of raising pigs, and effectively utilized the catalytic activity of the micro heavy Cu self that exists in the waste water of raising pigs.Have economical, convenient, can operate and plurality of advantages such as comprehensive treatment effect is good.
Remove antibiotic effect in order to improve ozone oxidation, the present invention combines metal oxide-loaded gac with ozonation technology, and ozone oxidation usefulness is significantly improved.Gac is as sorbent material, micro-microbiotic in can adsorbed water body makes it in the activated carbon surface enrichment, thus make ozone easier with the microbiotic contact reacts, gac also can be used as catalyzer simultaneously, and catalysis ozone decomposes the free radical that generation has strong oxidizing property.But and the metal oxide that loads on activated carbon surface also catalysis ozone decompose and produce free radical, quick molecule with antibiotic molecule oxygenolysis Cheng Gengxiao, and further mineralising is carbonic acid gas, water and inorganic salt, thereby reaches degraded and remove antibiotic purpose.
The present invention utilizes the raise pigs cupric ion of trace in the waste water of charcoal absorption and enrichment, but the cupric ion concerted catalysis ozone oxidation of absorption and enrichment is removed microbiotic, the effect of raising O3 catalytic oxidation.Lower (0.01～0.8mg/L), it is not obvious that the cupric ion of lower concentration is removed antibiotic concerted catalysis effect to O3 catalytic oxidation for the concentration of cupric ion in the waste water of raising pigs after biological treatment.But behind the reactor of the metal oxide-loaded gac of filling of flowing through, the cupric ion of lower concentration can be enriched in its surface by charcoal absorption in the waste water of raising pigs, and effects of antibiotics is removed in the concerted catalysis that has strengthened cupric ion.The initial stage that metal oxide-loaded gac is using, because the cupric ion of absorption is on the increase, the concerted catalysis effect of cupric ion also strengthens thereupon, after using for some time, because cupric ion is saturated in activated carbon surface absorption, the absorption of cupric ion and desorption reach a running balance, and the cupric ion of activated carbon surface absorption is brought in constant renewal in continuous absorption and desorption process, it is in all the time than higher activity, has guaranteed the concerted catalysis effect of cupric ion.
The metal oxide-loaded activated carbon catalysis ozone oxidation of the present invention is used for the waste water advanced processing of large scale of pig farm and removes antibiotic method, is the waste water of raising pigs after handling through traditional solid-liquid separation-anaerobic digestion-aerobic biochemical to be flowed into carry out catalytic ozonation removal microbiotic in the O3 catalytic oxidation reactor.The gac that reactor charge is metal oxide-loaded, flowing into waste water speed is 1～20m/h, the residence time 20～60min, total ozone dosage 3～150mg/L.
The present invention utilizes gac as carrier, can be effectively with the antibiotics material of trace in the waste water from the water body adsorption and enrichment to activated carbon surface, solved in the waste water of raising pigs at present because antibiotic concentration is low the problem of ozone oxidation microbiotic inefficiency.Simultaneously described carrier active carbon be the aperture between 2～100nm, particle diameter is the coal mass active carbon of 0.5～2.0mm.The specific surface area of the gac of microvoid structure is very big usually, yet micropore is unfavorable for the antibiotic absorption of macromolecular structure, and loads on the metal oxide in the micropore because diffusion and steric restriction effect also are difficult to bring into play effectively its catalytic activity; Although there is not the diffusion problem of organism and ozone in the gac of macroporous structure, specific surface area is less usually; And the gac of the central hole structure of 2～100nm has bigger specific surface area, the diffusion problem when having eliminated the activated carbon supported metal oxide of microvoid structure simultaneously, catalytic activity that can more effective performance metal oxide.Coal mass active carbon is more stable than wood activated charcoal, and in use be difficult for broken, but the repeating utilization factor height, thereby reduced the use cost of catalyzer.
The present invention proposes and metal oxide supported gac is used for O3 catalytic oxidation removes microbiotic, solved the some shortcomings that ozonation technology exists.Metal oxide is carried on the surface of gac by the method for dipping-roasting, and the metal oxide of load is one or several the mixing in the oxide compound of oxide compound, manganese of oxide compound, the iron of cerium.Metal oxide-loaded have a single metal oxide of following three kinds of classification: a. (oxide compound of the oxide compound of cerium, the oxide compound of iron, manganese); B. the oxide molar ratio of the oxide compound of cerium and iron be 1～5: 1 and the oxidation of cerium and the oxide molar ratio of manganese be 1～5: 1; C. the oxide molar ratio of the oxide compound of the oxide compound of cerium, iron and manganese is 2～5: 1: 1.The weight of metal oxide is 0.1%～30% of carrier active carbon weight in the catalyzer.The antibiotic clearance of O3 catalytic oxidation has improved 40～80% than independent ozone oxidation after having used metal oxide supported activated-carbon catalyst, and specific activity charcoal O3 catalytic oxidation clearance has improved 30～60%.
The metal oxide-loaded waste water advanced processing of the activated carbon catalysis ozone oxidation large scale of pig farm antibiotic method of degrading has following characteristics: the waste water of raising pigs after handle solid-liquid separation-anaerobic digestion-aerobic biochemical (1), metal oxide-loaded gac is O3 catalytic oxidation and the micro-microbiotic of removal effectively, and the residual hardly degraded organic substance of part degrading waste water; (2) utilize gac as carrier, the microbiotic of trace can be conducive to improve the efficient of O3 catalytic oxidation at activated carbon surface by enrichment; (3) existence of metal oxide in the metal oxide-loaded gac has effectively suppressed activated carbon surface owing in use being caused the active situation about reducing of activated carbon catalysis by ozone oxidation, thereby has prolonged the work-ing life of gac; (4) by the adsorption and enrichment effect of gac to trace copper ion in the waste water of raising pigs, effectively improved the concerted catalysis effect of the cupric ion of trace in the waste water of raising pigs, further improved the efficient of O3 catalytic oxidation.
Method of the present invention can reach 65-95% to the clearance of tetracycline antibiotics, and the clearance of quinolones can reach 60-90%, compares with activated carbon catalysis ozone Oxidation Treatment antibiotic waste water, and clearance has improved 30-60%.
Embodiment
The technology of the present invention is not limited to the following embodiment that gives an example.
Below among each embodiment, microbiotic adopts LC-MS/MS to detect, waters e2695 type liquid chromatograph (waters, the U.S.) is adopted in experiment, joins waters TQ Detector type triple level Four bar mass spectrums of connecting and carries out sample analysis.
The LC condition:
Chromatographic column: Aglient eclipse XDB C18 (4.6 * 150mm, 5 μ m); Column temperature: 30 ℃; Flow velocity: 0.3ml/min.; Sample size 10 μ L; Moving phase is formed, and adopts the two-phase flow phase, and A is 0.1% formic acid, and C is acetonitrile; Adopt and keep 10%C, 90%A in moving phase linear gradient leaching: the 2min; 2-8min is changed to 40%C, 60%A; 8-24min is changed to 90%C, 10%A; 24-26min keeps 10%C, 90%A, again with 4min balance chromatographic column again.Each sample analysis time is 30min.
The mass spectrum condition:
Ionization mode: the positive ionizer of electron spray(ES) (ESI+); Capillary voltage: 4KV; Dryer temperature: 350 ℃, moisture eliminator flow velocity: 550L/h; Collision air-flow velocity: 0.2ml/min; Ion source temperature: 120 ℃.
Embodiment 1
[technology is referring to vast stretch of wooded country dragon etc. after through solid-liquid separation and Anaerobic Digestion for certain large scale of pig farm field waste water; the progress of antibiotic waste water biological treatment. Chinese agronomy circular; 2012 (11): the 258-261 page or leaf]; existence microbiotic for animals (comprising terramycin and norfloxicin etc.) commonly used removal as yet in the water outlet [referring to: Kummerer; K.; Antibiotics in the aquatic environment-A review-Part I.CHEMOSPHERE, 2009.75 (4): p.417-434.].Adopt method of the present invention, the waste water of raising pigs after the biological treatment adds reaction vessel, flow velocity 5m/h, residence time 60min, constantly water inlet, constantly water outlet.The gac of carrier metal oxide is filled the entire reaction container, reacts total ozone dosage 5mg/L.
In the above-mentioned embodiment, the metal oxide of load is the oxide compound of cerium, the gac of the oxide compound of cerium-carrying makes by the method for dipping with roasting: the 5kg gac is soaked in distilled water fully, gac blotted to pour in the cerous nitrate solution that volumetric molar concentration is 1.2mol/L behind the surface water flood 2h, and constantly stir.After gac behind the dipping blotted surface impregnation liquid, roasting 2h in 500 ℃ nitrogen atmosphere can make the oxide compound of cerium.
In the gac as the oxide compound of the cerium-carrying of catalyzer, the weight of the oxide compound of cerium is 5: 100 with weight ratio as the gac of carrier.Present embodiment is 75% to the clearance of terramycin in the waste water, is 70% to the clearance of norfloxicin.
The removal of terramycin and norfloxicin in 1 pair of waste water of employing embodiment
Embodiment 2
The difference of present embodiment and embodiment 1 is that the described metal oxide that is carried on gac is the oxide compound of iron, and steeping fluid is the iron nitrate of volumetric molar concentration 1.2mol/L, and other are identical with embodiment 1.Present embodiment is 66% to the clearance of terramycin in the waste water of raising pigs, and is 61% to the clearance of norfloxicin.
The removal of terramycin and norfloxicin in 2 pairs of waste water of employing embodiment
Embodiment 3
Present embodiment 3 is that with the difference of embodiment 1 and 2 the described metal oxide that is carried on gac is the oxide compound of manganese, and steeping fluid is the manganous nitrate of volumetric molar concentration 1.2mol/L, and other are identical with embodiment 1.Present embodiment is 70% to the clearance of terramycin in the waste water, is 64% to the clearance of norfloxicin.
The removal of terramycin and norfloxicin in 3 pairs of waste water of employing embodiment
Embodiment 4
The difference of present embodiment and embodiment 1 to 3 is that the described metal oxide that is carried on gac is cerium, Iron mixed oxide, steeping fluid is that cerous nitrate and iron nitrate disposed by mole in dense 2: 1, and the total mol concentration of cerous nitrate and iron nitrate is 1.2mol/L.Other are identical with embodiment 1.Present embodiment is 79% to the clearance of terramycin in the waste water, is 76% to the clearance of norfloxicin.
The removal of terramycin and norfloxicin in 4 pairs of waste water of employing embodiment
Embodiment 5
The difference of present embodiment and embodiment 1 to 4 is described metal oxide-loaded be cerium, manganese mixed oxides, and steeping fluid is that cerous nitrate and manganous nitrate dispose by mole concentration at 2: 1, and the total mol concentration of cerous nitrate and manganous nitrate is 1.2mol/L.Other are identical with embodiment 1.Present embodiment is 81% to the clearance of terramycin in the waste water, is 78% to the clearance of norfloxicin.
The removal of terramycin and norfloxicin in 5 pairs of waste water of employing embodiment
Embodiment 6
The difference of present embodiment and embodiment 1 to 5 is described metal oxide-loaded be cerium, manganese, Iron mixed oxide, steeping fluid is that cerous nitrate, manganous nitrate and iron nitrate dispose by mole concentration at 2: 1: 1, and the total mol concentration of cerous nitrate, manganous nitrate and iron nitrate is 1.2mol/L.Other are identical with embodiment 1.Present embodiment is 81% to the clearance of terramycin in the waste water, is 79% to the clearance of norfloxicin.
The removal of terramycin and norfloxicin in 6 pairs of waste water of employing embodiment
Claims (7)
1. a metal oxide-loaded gac is used for removing the antibiotic method of waste water of raising pigs, and may further comprise the steps:
Step 1, utilize solid-liquid separation of the prior art, anaerobic digestion, aerobic biochemical three technology couplings of processing or preceding two technology couplings that the waste water of raising pigs is handled, the removal suspended particle in the waste water of raising pigs, and COD, ammonia nitrogen and phosphoric acid salt in the waste water of raising pigs are removed in degraded;
Step 2, to add in the reaction vessel that is filled with metal oxide-loaded gac through the waste water of raising pigs after the step 1 processing and react 20～60min, the weightmeasurement ratio by ozone and the waste water of raising pigs in the reaction process is 3～150 milligrams: 1 liter amount ratio feeds ozone in reactor.
2. method according to claim 1 is characterized in that, the metal oxide of described metal oxide-loaded gac institute load is a kind of in the oxide compound of the oxide compound of the oxide compound of cerium, iron, manganese or more than two kinds.
3. method according to claim 1 and 2 is characterized in that, the weight ratio of metal oxide and gac is 0.1～30: 100 in the described metal oxide-loaded gac.
4. method according to claim 1, it is characterized in that, the metal oxide of described metal oxide-loaded gac institute load is the oxide compound of cerium and the hopcalite of iron, the molar ratio of the oxide compound of cerium and the oxide compound of iron is 1～5: 1, and the weight ratio of metal oxide and gac is 0.1～30: 100 in the described metal oxide-loaded gac.
5. method according to claim 1, it is characterized in that, it is the oxidation of cerium and the hopcalite of manganese that described metal oxide-loaded gac institute load gets metal oxide, the molar ratio of the oxide compound of cerium and the oxide compound of manganese is 1～5: 1, and the weight ratio of metal oxide and gac is 0.1～30: 100 in the described metal oxide-loaded gac.
6. method according to claim 1, it is characterized in that, described metal oxide-loaded gac institute load gets the oxide compound that metal oxide is cerium, the oxide compound of iron and the hopcalite of manganese, the molar ratio of the oxide compound of the oxide compound of the oxide compound of cerium, iron and manganese is 2～5 in this mixture: 1: 1, the weight ratio of metal oxide and gac was 0.1～30: 100 in the described metal oxide-loaded gac.
7. method according to claim 1 is characterized in that, described gac is the mesopore coal mass active carbon, and described mesopore coal mass active carbon aperture is between 2～100nm, and activated carbon particle size is 0.5～2.0mm.
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Application publication date: 20130918 |