CN106914216A - A kind of preparation of feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal - Google Patents
A kind of preparation of feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal Download PDFInfo
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- CN106914216A CN106914216A CN201710136203.7A CN201710136203A CN106914216A CN 106914216 A CN106914216 A CN 106914216A CN 201710136203 A CN201710136203 A CN 201710136203A CN 106914216 A CN106914216 A CN 106914216A
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- livestock
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- poultry
- sulfa antibiotics
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of method for preparing and its removing sulfa antibiotics in water removal of feces of livestock and poultry charcoal, belong to utilization of waste as resource and water-treatment technology field.It is comprised the following steps：（1）Take feces of livestock and poultry to dry to constant weight, charcoal is made through Muffle furnace high temperature pyrolysis；（2）By step（1）The feces of livestock and poultry charcoal for obtaining uses 1:1 hydrochloric acid and hydrofluoric acid mixing acid soak, deionized water is cleaned to neutral left and right, drying to constant weight, grinding, sieving；（3）By step（2）In biological carbon adsorbent water body of the input containing sulfa antibiotics for obtaining, Adsorption sulfa antibiotics.The present invention compared with prior art, with advantages below and effect：Adsorbable sulfa antibiotics concentration range is big（10‑100mg/L）, clearance is high（50.2‑99.9%）；Adsorbent is prepared simply, easy to operate, with low cost；Turn waste into wealth, realize animal faeces wastes trans-utilization, with important social effect and economic worth.
Description
Technical field：
The present invention relates to a kind of method for preparing and its removing sulfa antibiotics in water removal of feces of livestock and poultry charcoal, this method tool
Body prepares biological carbon materials using organic waste-feces of livestock and poultry that livestock and poultry breeding industry is produced, and charcoal then is added into dirt
Sulfa antibiotics are removed in dye water body, belongs to utilization of waste as resource and water-treatment technology field.
Background technology：
Sulfa antibiotics（SAs）One class novel ionic organic pollution.It has the advantages that inexpensive, efficient, is at this stage
Most popular class antibiotic.After the antibiotic such as SAs are by use, have up to more than 85% in the form of original shape or metabolin
Enter soil or water environment with excretas such as biological excrement and urines, cause the severe contamination of ecological environment.At present, existing many
Country is in sludge sewage, surface water, the SAs that multiple types, various concentrations are even detected in drinking water.SAs's
Environmental Residues can change environmental microorganism species, destroy ecosystem balance, and the resistant gene of induction can be by the way such as food
Footpath enters human body, causes human body to form drug resistance to SAs.Therefore, the removal research of wastewater environment residual SAs is carried out with important
Meaning is also extremely urgent.
At present, the method for the treatment of SAs waste water mainly has ion-exchange, chemical oxidization method, membrane filter method, absorption method and work
Property sludge etc., its ion exchange methods, chemical oxidization method and membrane filter method even depth treatment technology high cost, treatment effect is not
Stabilization.And the most frequently used activated sludge process of sewage treatment plant, it is only 20%-77% to SAs removal efficiency, thereby increases and it is possible to introduce sterilization by-product
Thing, this is primarily due to SAs can suppress microbial activity, cause treatment effect relatively low.Therefore, efficiency high, energy consumption be low, operation is simple
Just absorption method is increasingly subject to researcher's extensive concern and research.
Absorption method is a kind of method that utilization adsorbent goes poisonous and harmful substance in water removal by suction-operated, is a kind of normal
Use water technology.Wherein adsorbent is often referred to the material of high-specific surface area, macropore volume, such as activated carbon, silica gel, molecular sieve
Deng.
The environment-friendly material such as charcoal for being prepared using organic waste in recent years, because it has high-specific surface area, rich
The advantage of rich surface functional group, chemical stability and the similar activated carbon such as porous, and closed extensively by government and environmentally friendly researcher
Note.It is both reality that the present invention will cause the feces of livestock and poultry of severe contamination to be prepared into the sorbing material with stronger adsorption capacity to environment
The important measures of existing changing rejected material to useful resource, can provide new approaches for water technology upgrading again.
The content of the invention：
For feces of livestock and poultry organic waste resource reutilization, it is an object of the invention to provide a kind of system of feces of livestock and poultry charcoal
Method that is standby and its removing SAs in water removal, the charcoal that the method is prepared by the use of feces of livestock and poultry organic waste as sorbing material,
Adsorption water environment SAs pollutants, with low cost, high treating effect；Animal faeces wastes are utilized effectively simultaneously, subtract
Lack its environmental pollution, improve ecological environment.
To reach goal of the invention, the technical solution adopted by the present invention：Organic waste-the poultry produced using livestock and poultry breeding industry
Poultry manure prepares biological carbon materials, then charcoal is added in polluted-water and removes SAs, it is characterised in that including following tool
Body step：
（1）Take feces of livestock and poultry to dry to constant weight, charcoal is made through Muffle furnace high temperature pyrolysis；
（2）By step（1）The feces of livestock and poultry charcoal for obtaining uses 1:1 hydrochloric acid and hydrofluoric acid mixing acid soak, deionization washing
Net extremely neutral left and right, drying to constant weight, grinding is sieved；
（3）By step（2）In biological carbon adsorbent water body of the input containing sulfa antibiotics for obtaining, Adsorption sulfamido resists
Raw element.
A kind of preparation of described feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal, its feature exist
In the step（1）The preparation of middle charcoal is ground to 2-6cm with drying feces of livestock and poultry as raw material, natural air drying, and masking foil is close
Envelope, 600 DEG C of anoxic high temperature pyrolysis 6 hours.
A kind of preparation of described feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal, its feature exist
In the step（2）Middle concentration of hydrochloric acid is 1mol/L, and hydrofluoric acid concentration is 1mol/L, and soak time is 12h, and immersion process is adjoint
Mechanical agitation, immersion process is repeated 3 times.
A kind of preparation of described feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal, its feature exist
In the step（2）Sieving be 60 mesh.
A kind of preparation of described feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal, its feature exist
In the step（3）Middle water body sulfa antibiotics initial concentration is 10-100mg/L, charcoal with containing sulfa antibiotics
The mass ratio of water body is 1:500-1000.
A kind of preparation of described feces of livestock and poultry charcoal and its method for removing sulfa antibiotics in water removal, its feature exist
In the step（3）Middle adsorption temp is 25 ± 2 DEG C, and absorption duration of oscillation is 48h, and pH value of solution is 5.65 after adsorption equilibrium.
Know-why of the invention is as follows：Excrement charcoal has large specific surface area and π keys and abundant hole knot
Structure and surface functional group, therefore charcoal can be acted on by distribution, adsorption and the mechanism such as electrostatic interaction effectively be removed
SAs in water.
The present invention compared with prior art, has the following advantages that and effect：
1st, the adsorbent used in the present invention is the charcoal that cow dung discarded object is transformed, therefore the cost of raw material is low,
And realize the resource of abandoned biomass；
2nd, the adsorbent used in the present invention has strong adsorption to SAs, under its optimal adsorption conditions, adsorbs initial concentration
For the adsorption efficiency of the SAs of 50mg/L is 99.9%.
Brief description of the drawings
Fig. 1 is that embodiment 1 is eliminating rate of absorption of the adsorbent to different SAs；
Fig. 2 is that embodiment 2 is the adsorption effect figure of the adsorbent amount to different SAs；
Fig. 3 is that embodiment 3 is the adsorption effect figures of the pH to different SAs.
Fig. 4 is that embodiment 4 is the adsorption effect figure of the adsorption time to different SAs.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further detailed explanation.
Embodiment 1：
The accurate cow dung charcoal for weighing 0.05g in 30mL tool plug glass tubes, add 25mL concentration to be respectively 10,20,40,
50th, 60,80, the solution of the sulphadiazine of 100mg/L, sulfamethyldiazine and bacteresulf, 0.01 is contained in the solution
mol/L CaC12With 0.01 mol/L NaN3 (0.01 mol/L CaC12Solution is supporting electrolyte, 0.01 mol/L NaN3
It is bacterial activity in suppression water）.At 25 DEG C, 200r/min lucifuges continuously shake 48h, supernatant is taken respectively and crosses 0.45 μm of filter membrane
Afterwards, with the content of sulphadiazine, sulfamethyldiazine and bacteresulf in high performance liquid chromatography determination sample, and removal is calculated
Rate, obtains removal scope of the cow dung charcoal to various concentrations sulfa antibiotics, as shown in Figure 1.When the input amount of adsorbent
In 0.05g, when sulphadiazine, sulfamethyldiazine and bacteresulf concentration are less than or equal to 40mg/L, clearance reaches
More than 95%.
Embodiment 2：Influence of the adsorbent amount to adsorption effect
Accurately the different amounts of cow dung charcoals of 0.0100,0.0200,0.0500,0.1000,0.2000,0.5000 g are weighed in 30
In ml tool plug glass tubes, the molten of 25 mL concentration 50mg/L sulphadiazines, sulfamethyldiazine and bacteresulf is separately added into
Liquid, contains 0.01 mol/L CaC1 in each SAs solution2 0.01 mol/L NaN3 (0.01 mol/L CaC12Solution is support
Electrolyte, 0.01 mol/LNaN3It is bacterial activity in suppression water）.Then at 25 DEG C, 200 r/min lucifuges vibrate 48 h, point
Do not take after supernatant crosses 0.45 μm of filter membrane, with sulphadiazine, sulfamethyldiazine and sulfanilamide (SN) in high performance liquid chromatography determination sample
The content of isoxazole, and clearance is calculated, the optimum amount of cow dung charcoal is drawn, as shown in Figure 2.When the input amount of adsorbent
In 0.01-0.0500 g, the eliminating rate of absorption of sulphadiazine, sulfamethyldiazine and bacteresulf with adsorbent increase
And raise, when the input amount of adsorbent is 0.1 g, to the removal effect of sulphadiazine, sulfamethyldiazine and bacteresulf
Preferably, clearance has reached 99.9% to fruit.As input amount 0.1 g of superelevation of adsorbent, adsorbent is to sulphadiazine, sulfalene
The clearance of yl pyrimidines and bacteresulf is held essentially constant.Therefore, 0.1 g cow dung charcoals are added in tool plug glass tube
The optimal Static Adsorption agent consumption of SAs is removed as sorbing material.
Embodiment 3：Influences of the pH to adsorption effect
The cow dung charcoal of 0.1 g accurately is weighed in 30 mL glass tubes, takes 25mL, the sulphadiazine of 50 mg/l, sulfalene
Yl pyrimidines and bacteresulf solution（Containing 0.01 mol/L CaC12With 0.01 mol/L NaN3）, then adjusted with HCl and NaOH
The pH value for saving solution is 2.5,3.5,4.5,5.5,6.5,7.5,8.5,9.5, and at 25 DEG C, lucifuge vibrates 48 h under 200 r/min
Afterwards, after crossing 0.45 μm of filter membrane, the concentration of SAs in determination sample calculates the adsorption coefficient of SAs.As shown in figure 3, as pH=4.5
Charcoal is maximum to the adsorption coefficient of SAs, sulphadiazine, sulfamethyldiazine and bacteresulf adsorption coefficient lgKd Respectively
3.8th, 4.2 and 4.1L/kg, when water pH value is more than 4.5, charcoal is reduced to the adsorbance of SAs with the rising of pH value,
When pH value is 8.5-9.5, adsorbance is held essentially constant.
Embodiment 4：Influence of the adsorption time to adsorption effect
Accurate to weigh the cow dung charcoal of 0.1 g in 30 mL glass tubes, the pH value for adjusting background solution is 4.5, adds 25
ML, the solution of 50 mg/l sulphadiazines, sulfamethyldiazine and bacteresulf（Containing 0.01 mol/L CaC12With 0.01
mol/L NaN3）, at 25 DEG C, 48 h are vibrated under 200 r/min, 0,0.5,1,2,4,6,8,10,12,16,24,36,48
H, takes supernatant, after crossing 0.45 μm of filter membrane, using the sulphadiazine in liquid chromatogram measuring sample, sulfamethyldiazine and sulfanilamide (SN)
Isoxazole concentration, calculates its adsorbance, it is determined that absorption Best Times.As shown in figure 4, when adsorption time is in 6 h, charcoal pair
The absorption of sulphadiazine, sulfamethyldiazine and bacteresulf is very fast, sulphadiazine in water body, sulfamethyldiazine and
The concentration of bacteresulf drastically declines, Adsorption of the charcoal to sulphadiazine, sulfamethyldiazine and bacteresulf
Rate is more than 80%；Adsorption time is about 24 h or so, and charcoal is to sulphadiazine, sulfamethyldiazine and bacteresulf
Eliminating rate of absorption is more than 99%, and kept stable is adsorbed in 24 subsequent h, therefore, 24 h are adsorbed for cow dung charcoal
Agent reaches the most short adsorption time of maximum adsorption capacity.
Claims (6)
1. a kind of feces of livestock and poultry charcoal preparation and its go water removal in sulfa antibiotics method, it is characterised in that including with
Lower specific steps：
（1）Take feces of livestock and poultry to dry to constant weight, charcoal is made through Muffle furnace high temperature pyrolysis；
（2）By step（1）The feces of livestock and poultry charcoal for obtaining uses 1:1 hydrochloric acid and hydrofluoric acid mixing acid soak, deionization washing
Net extremely neutral left and right, drying to constant weight, grinding is sieved；
（3）By step（2）In biological carbon adsorbent water body of the input containing sulfa antibiotics for obtaining, Adsorption sulfamido resists
Raw element.
2. a kind of feces of livestock and poultry charcoal according to claim 1 preparation and its go water removal in sulfa antibiotics side
Method, it is characterised in that the step（1）The preparation of middle charcoal is ground to 2- with drying feces of livestock and poultry as raw material, natural air drying
6cm, masking foil sealing, 600 DEG C of anoxic high temperature pyrolysis 6 hours.
3. a kind of feces of livestock and poultry charcoal according to claim 1 preparation and its go water removal in sulfa antibiotics side
Method, it is characterised in that the step（2）Middle concentration of hydrochloric acid is 1mol/L, and hydrofluoric acid concentration is 1mol/L, and soak time is 12h,
Immersion process is repeated 3 times with mechanical agitation, immersion process.
4. a kind of feces of livestock and poultry charcoal according to claim 1 preparation and its go water removal in sulfa antibiotics side
Method, it is characterised in that the step（2）Sieving be 60 mesh.
5. a kind of feces of livestock and poultry charcoal according to claim 1 preparation and its go water removal in sulfa antibiotics side
Method, it is characterised in that the step（3）Middle water body sulfa antibiotics initial concentration be 10-100mg/L, charcoal with contain sulfanilamide (SN)
The mass ratio of the water body of class antibiotic is 1:500-1000.
6. a kind of feces of livestock and poultry charcoal according to claim 1 preparation and its go water removal in sulfa antibiotics side
Method, it is characterised in that the step（3）Middle adsorption temp is 25 ± 2 DEG C, and absorption duration of oscillation is 48h, solution after adsorption equilibrium
PH is 5.65.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786736A (en) * | 2018-06-28 | 2018-11-13 | 普定县干河农业开发有限公司 | A kind of charcoal prepared using chicken manure as raw material and the application in chicken house purification of waste water |
| CN108947169A (en) * | 2018-06-28 | 2018-12-07 | 普定县宏康种养殖专业合作社 | A kind of method to clean in chicken manure |
| CN110228897A (en) * | 2018-03-06 | 2019-09-13 | 日立造船株式会社 | Drainage processing method and disintegrating system in waste pipe |
| CN110283636A (en) * | 2019-05-17 | 2019-09-27 | 湖北群盛环境科技发展有限公司 | A method of promoting the calorific value that feces of livestock and poultry prepares biomass carbon |
| CN112023925A (en) * | 2020-08-31 | 2020-12-04 | 井冈山大学 | Preparation method and application of livestock and poultry manure biochar loaded nano zero-valent iron composite material |
| CN112266274A (en) * | 2020-09-16 | 2021-01-26 | 河北中科定洋农业科技集团有限公司 | Environment-friendly livestock manure recycling method |
| CN112973658A (en) * | 2021-03-09 | 2021-06-18 | 天津大学 | Cow dung biogas residue carbon catalyst and degradation method of antibiotics by using same |
| CN113070035A (en) * | 2021-05-17 | 2021-07-06 | 中国科学院沈阳应用生态研究所 | Composite modified chicken manure biochar, preparation method thereof and application thereof in removing residual tetracycline in soil |
| CN113318724A (en) * | 2021-04-27 | 2021-08-31 | 湖北师范大学 | Preparation method of cow dung biogas residue carbon and application of cow dung biogas residue carbon in persulfate activation system |
| CN115196616A (en) * | 2022-08-04 | 2022-10-18 | 山东农业大学 | Magnesium salt modified biochar material and application thereof in reducing abundance of antibiotic resistance genes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110228897A (en) * | 2018-03-06 | 2019-09-13 | 日立造船株式会社 | Drainage processing method and disintegrating system in waste pipe |
| CN108786736A (en) * | 2018-06-28 | 2018-11-13 | 普定县干河农业开发有限公司 | A kind of charcoal prepared using chicken manure as raw material and the application in chicken house purification of waste water |
| CN108947169A (en) * | 2018-06-28 | 2018-12-07 | 普定县宏康种养殖专业合作社 | A kind of method to clean in chicken manure |
| CN110283636A (en) * | 2019-05-17 | 2019-09-27 | 湖北群盛环境科技发展有限公司 | A method of promoting the calorific value that feces of livestock and poultry prepares biomass carbon |
| CN112023925A (en) * | 2020-08-31 | 2020-12-04 | 井冈山大学 | Preparation method and application of livestock and poultry manure biochar loaded nano zero-valent iron composite material |
| CN112266274A (en) * | 2020-09-16 | 2021-01-26 | 河北中科定洋农业科技集团有限公司 | Environment-friendly livestock manure recycling method |
| CN112973658A (en) * | 2021-03-09 | 2021-06-18 | 天津大学 | Cow dung biogas residue carbon catalyst and degradation method of antibiotics by using same |
| CN113318724A (en) * | 2021-04-27 | 2021-08-31 | 湖北师范大学 | Preparation method of cow dung biogas residue carbon and application of cow dung biogas residue carbon in persulfate activation system |
| CN113070035A (en) * | 2021-05-17 | 2021-07-06 | 中国科学院沈阳应用生态研究所 | Composite modified chicken manure biochar, preparation method thereof and application thereof in removing residual tetracycline in soil |
| CN115196616A (en) * | 2022-08-04 | 2022-10-18 | 山东农业大学 | Magnesium salt modified biochar material and application thereof in reducing abundance of antibiotic resistance genes |
| CN115196616B (en) * | 2022-08-04 | 2023-08-11 | 山东农业大学 | Magnesium salt modified biochar material and application thereof in reducing abundance of antibiotic resistance genes |
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