CN110227416A - A kind of preparation and its application in fluoroquinolone antibiotics removal in water of iron zinc and phosphoric acid modification sludge organism charcoal - Google Patents
A kind of preparation and its application in fluoroquinolone antibiotics removal in water of iron zinc and phosphoric acid modification sludge organism charcoal Download PDFInfo
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- CN110227416A CN110227416A CN201910549244.8A CN201910549244A CN110227416A CN 110227416 A CN110227416 A CN 110227416A CN 201910549244 A CN201910549244 A CN 201910549244A CN 110227416 A CN110227416 A CN 110227416A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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Abstract
The invention discloses the preparation of a kind of iron zinc and phosphoric acid modification sludge organism charcoal and its application in fluoroquinolone antibiotics removal in water, belong to charcoal preparation technical field.The preparation method is pyrolyzed after municipal sewage plant secondary settling tank sludge dewatering drying using high temperature process furnances, is then modified using iron zinc and phosphoric acid, finally carried out secondary clacining and obtain Fe/Zn+H3PO4-SBC.Fe/Zn+H prepared by the present invention3PO4- SBC is to the adsorption capacity of fluoroquinolone antibiotics Ciprofloxacin, Norfloxacin and Ofloxacin in water up to 25.43-88.73mg/g.Municipal sludge of the present invention reduces production cost as raw material, both the efficient removal of antibiotic in the resource utilization and water of municipal sludge had been realized, have many advantages, such as easy to operate, at low cost simultaneously, is the minimizing technology of fluoroquinolone antibiotics great potential in a kind of pair of water.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to using the sludge organism charcoal of iron zinc and phosphoric acid modification as
The method that adsorbent removes antibiotic in water removal.
Background technique
From after the appearance of nineteen twenty-nine penicillin, in order to improve and ensure the health of humans and animals, the use of antibiotic occurs quick-fried
The growth of hair property.Antibiotic has broad spectrum antibiotic activity, and the good feature of bactericidal effect is widely used in treating bacterium infection.According to
Market survey is the results show that China has become maximum antibiotics production and country of consumption in the world.The antibiosis of humans and animals intake
Element can not be metabolized and be absorbed completely, and about 50%-90% is discharged with former compound or metabolite form by urine and excrement
In vitro, and Natural Attenuation and traditional sewage disposal technology are difficult effectively to be completely removed and entered in environment.In water
Antibiotic is able to suppress the growth of algae extremely low concentration, its photosynthesis and growth metabolism is influenced, to aquatile
With potential endocrine.It is irrigated with antibiotic waste water, will lead to plants enriched antibiotic and enter
Food chain.Antibiotic can enhance the resistance of bacterium in environment, enhance that its is propagated, lead to resistance and superbacteria
It generates, animal and human health is constituted and greatly threatened, wherein Ciprofloxacin (CIP) etc. has been put into European quality of water environment
Watch list.
Traditional sewage disposal technology cannot be removed effectively the antibiotic in water, and current novel removal technology includes: height
Grade oxidation, biodegrade and adsorption technology.It is higher that advanced oxidation degradation process can then generate a large amount of energy consumption processing cost, degradation
The by-product of generation may generate more serious secondary pollution in the presence of uncertainty to environment；And biodegrade there may be
Time-consuming, removal efficiency is low, operating condition requires the disadvantages of stringent.Absorption is a kind of economical, efficiently and being capable of large-scale application
Method.
Municipal sludge is the principal by product of municipal sewage plant, and growing and huge production problems give environment band
Carry out great pressure, there is research to predict, is up to 45,470,000 tons/year to the year two thousand twenty end China sludge yield, recycling benefit
With being both the environmental problem for needing urgently to solve while also becoming the hot spot of current international Related Research Domain.Municipal sludge
It is set to be conducive to that charcoal product is made rich in organic matter, research shows that sludge organism charcoal has certain surface area and hole
Degree has certain adsorption capacity to the organic pollutant in environment.However because antibiotic has biggish molecular weight and molecule
Structure, sludge base charcoal can improve its adsorption capacity by suitable modification mode to its limited sorption capacity.Study table
Bright, iron zinc and phosphoric acid modification can significantly improve the physicochemical characteristic of charcoal, enhance the adsorption capacity of charcoal, but about
The two has not been reported in conjunction with the research for carrying out the absorption of modified sewage sludge charcoal system exploration antibiotic.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of high treating effect
A kind of iron zinc and phosphoric acid modification sludge organism charcoal, not only may be implemented the resource utilization of municipal sludge, but also can efficiently go to remove water
The method of middle antibiotic.
In order to solve the above technical problem, the present invention provides the preparation sides of a kind of iron zinc and phosphoric acid modification sludge organism charcoal
Method comprises the following steps:
(1) preparation of iron zinc and phosphoric acid modification sludge organism charcoal: by secondary settling tank municipal sludge centrifugal dehydration, after be dried to perseverance
Weight, grinds, is then pyrolyzed, milled 100-200 mesh, obtains sludge organism charcoal SBC；
(2) FeCl that volume ratio is 2:1-4:1 is added in SBC obtained by step (1)3·6H2O aqueous solution and ZnCl2Aqueous solution
Mixed solution in, the FeCl3·6H2The mass concentration of O is 4.8-9.6g/L, the ZnCl2The mass concentration of aqueous solution is
2.4g/L；The SBC and mixed solution ratio are that 1Kg:10L-1Kg:20L shakes for 24 hours, and 100 DEG C of drying repeat above-mentioned loaded
Journey at least 3 times is to improve the load capacity of iron and zinc；Then it calcines, obtains the sludge organism charcoal Fe/Zn-SBC of iron zinc modification；
(3) SBC obtained by step (1) is added to the H of 10.6-15mol/L3PO4In；The SBC and H3PO4Ratio is 1Kg:
2.5L-1Kg:10L shakes and impregnates 8-10h, and after filtration drying, high-temperature activation is permanent to filtrate pH with deionized water cleaning sample
Fixed, 60-80 DEG C of drying, milled 100-200 mesh obtains H3PO4Modified sewage sludge charcoal H3PO4-SBC；
(4) the preparation process sequential operation by SBC obtained by step (1) according to step (2) and step (3), the biology of acquisition
Charcoal is iron zinc and H3PO4Modified sewage sludge charcoal Fe/Zn+H3PO4- SBC is kept in dark place in drier.
As a preferred embodiment of the above technical solution, the preparation of a kind of iron zinc and phosphoric acid modification sludge organism charcoal provided by the invention
Method further comprises some or all of following technical characteristic:
As an improvement of the above technical solution, in the step (1), drying condition is 60-80 DEG C of forced air drying；The heat
Solution condition is N2Under protective condition, N2Flow velocity is 0.5-1L/min, and temperature rate-of-rise is 10-20 DEG C/min, at 300-700 DEG C
Under the conditions of be pyrolyzed 1.5-2h.
As an improvement of the above technical solution, in the step (2), calcination condition N2Under protective condition, N2Flow velocity is
0.5-1L/min, temperature rate-of-rise are 10-20 DEG C/min, are pyrolyzed 1.5-2h under the conditions of 300-700 DEG C.
As an improvement of the above technical solution, in the step (3), high-temperature activation is placed in Muffle furnace, and temperature rises
Rate is 10-20 DEG C/min, in 400-450 DEG C of heat preservation 1-2h.
A kind of iron zinc and phosphoric acid modification sludge organism charcoal, the iron zinc and phosphoric acid modification sludge organism charcoal are according to above-mentioned
Meaning method is prepared.
The application in fluoroquinolone antibiotics removal in water of a kind of iron zinc and phosphoric acid modification sludge organism charcoal, will be as above
Sludge organism charcoal Fe/Zn-SBC, H of the sludge organism charcoal SBC, iron zinc modification3PO4Modified sewage sludge charcoal H3PO4-SBC
With iron zinc and H3PO4Modified sewage sludge charcoal Fe/Zn+H3PO4- SBC is added to containing fluoroquinolones antibiotic as adsorbent
It is filtered in water, after adsorption equilibrium up to the water of fluoroquinolone antibiotics is removed.
As a preferred embodiment of the above technical solution, a kind of iron zinc and phosphoric acid modification sludge organism charcoal provided by the invention is in water
Application in fluoroquinolone antibiotics removal further comprises some or all of following technical characteristic:
As an improvement of the above technical solution, the fluoroquinolone antibiotics are Ciprofloxacin (CIP), Norfloxacin
(NOR) and one of Ofloxacin (OFL) or a variety of.
As an improvement of the above technical solution, antibiotic solubility is 5- in the water of the containing fluoroquinolones antibiotic
100mg/L, adsorbent dosage are 0.2-1.0g/L.
As an improvement of the above technical solution, adjusting after the adsorbent is added in the water of containing fluoroquinolones antibiotic
PH value of solution is 2-10.
Compared with prior art, technical solution of the present invention, which has the following beneficial effects: to provide, utilizes iron zinc and phosphoric acid
Modified sewage sludge charcoal removes the effective ways of antibiotic in water removal as adsorbent, can both effectively remove the antibiotic in water,
Mitigate its harm to environment, and can be realized the resource utilization of municipal sludge, at the same have it is at low cost, it is easy to operate etc. excellent
Point.
(1) Fe/Zn+H of the invention3PO4- SBC has optimal absorption property, adsorbent Fe/Zn+H3PO4-SBC
(0.5g/L) is to the removal rate that has of CIP, NOR and OFL that concentration is 10mg/L up to 60.29-94.81%.Meanwhile according to suction
Attached thermoisopleth its to the maximum adsorption capacity of CIP, NOR and OFL up to 25.43-83.73mg/g.
(2) compared with the methods of advanced oxidation, biodegrade, modified sewage sludge charcoal Adsorption water that the present invention uses
The method of middle antibiotic, easy to operate, at low cost, the prospect with large-scale application.
(3) adsorbent Fe/Zn+H prepared by the present invention3PO4- SBC can effectively facilitate the resource utilization of municipal sludge,
Mitigate it to endanger to environment bring, while realizing the removal of antibiotic in water.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, below in conjunction with preferred embodiment, detailed description are as follows.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below
It continues.
Fig. 1 is SBC as adsorbent the reaction time and the adsorbance of CIP, NOR, OFL and the relation curve of removal rate；
Fig. 2 is Fe/Zn-SBC as adsorbent the reaction time and the adsorbance of CIP, NOR, OFL and the relationship of removal rate
Curve；
Fig. 3 is H3PO4- SBC is as adsorbent the reaction time and the adsorbance of CIP, NOR, OFL and the relationship of removal rate
Curve；
Fig. 4 is Fe/Zn+H3PO4Adsorbance and removal rate of-the SBC as adsorbent the reaction time and CIP, NOR, OFL
Relation curve；
Fig. 5 is Fe/Zn+H3PO4The adsorbance and removal rate of pH value of solution and CIP, NOR, OFL when-SBC is as adsorbent
Relation curve；
Fig. 6 is Fe/Zn+H3PO4The pass of CIP, NOR, OFL concentration and its adsorbance and removal rate when-SBC is as adsorbent
It is curve；
Fig. 7 (a) is SBC and H3PO4The XRD spectrum of-SBC；
Fig. 7 (b) is Fe/Zn-SBC and Fe/Zn+H3PO4The XRD spectrum of-SBC；
Fig. 8 (a) is the SEM spectrum of SBC；
Fig. 8 (b) is the SEM spectrum of Fe/Zn-SBC；
Fig. 8 (c) is H3PO4The SEM spectrum of-SBC；
Fig. 8 (d) is Fe/Zn+H3PO4The SEM spectrum of-SBC；
Fig. 9 (a) is the distribution of pores map of SBC；
Fig. 9 (b) is the distribution of pores map of Fe/Zn-SBC；
Fig. 9 (c) is H3PO4The distribution of pores map of-SBC；
Fig. 9 (d) is Fe/Zn+H3PO4The distribution of pores map of-SBC
Figure 10 (a) is SBC, Fe/Zn-SBC, H3PO4- SBC and Fe/Zn+H3PO4FTIR map before-SBC absorption；
Figure 10 (b) is SBC, Fe/Zn-SBC, H3PO4- SBC and Fe/Zn+H3PO4FTIR map after-SBC absorption；
Figure 11 is SBC, Fe/Zn-SBC, H3PO4- SBC and Fe/Zn+H3PO4The Zeta potential map of-SBC.
Specific embodiment
The following detailed description of a specific embodiment of the invention, as part of this specification, by embodiment come
Illustrate that the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Example one: by secondary settling tank municipal sludge centrifugal dehydration, being placed in 70 DEG C of air dry ovens that drying to constant weight, grind,
Place it in N2Flow velocity is 1L/min, and temperature rate-of-rise is to grind sieving in 500 DEG C of pyrolysis 2h in the tube furnace of 10 DEG C/min
(0.15mm) obtains SBC.SBC, which is added, is dissolved with FeCl3·6H2O:ZnCl2It is shaken in the solution of=3:1 for 24 hours, 100 DEG C of drying,
Above-mentioned loading process is repeated 3 times to improve the load capacity of iron and zinc, is transferred in tube furnace and calcines 2h under above-mentioned condition, is obtained
Fe/Zn-SBC.H is added in above-mentioned Fe/Zn-SBC3PO4In (SBC:H3PO4=1:5) 10h is impregnated, being placed in temperature rate-of-rise is
In 450 DEG C of activation 1h in the Muffle furnace of 10 DEG C/min, cleaned with deionized water constant to filtrate pH, 70 DEG C of drying grind sieving
(0.15mm) obtains Fe/Zn+H3PO4- SBC is kept in dark place in drier.
Example two: SBC is added in the antibiotic solution that concentration is 10mg/L, SBC dosage is 0.5g/L, in 25 DEG C of perseverances
It is reacted in temperature oscillation case, in the residual concentration of time sampling measurement CIP, NOR and OFL of setting, calculates adsorbance and go
Except rate.
As shown in Figure 1, using SBC as adsorbent, it is 0.60- to CIP, NOR and OFL adsorbance when reaction balances
11.27mg/g, removal rate 1.32-55.87%, and it is most strong to the removal ability of CIP.
Example three: Fe/Zn-SBC is added in the antibiotic solution that concentration is 10mg/L, Fe/Zn-SBC dosage is
0.5g/L is reacted in 25 DEG C of constant temperature oscillation casees, measures the residual concentration of CIP, NOR and OFL in the time sampling of setting,
Calculate adsorbance and removal rate.
As shown in Figure 2, using Fe/Zn-SBC as adsorbent, at any time to CIP, NOR and OFL adsorbance and removal rate
It increases, its adsorbance is 7.29-13.35mg/g, removal rate 36.43-67.81% when reaction balance, and adsorption capacity is significantly high
In SBC, and it is most strong to the removal ability of CIP.
Example four: by H3PO4- SBC is added in the antibiotic solution that concentration is 10mg/L, H3PO4- SBC dosage is
0.5g/L is reacted in 25 DEG C of constant temperature oscillation casees, measures the residual concentration of CIP, NOR and OFL in the time sampling of setting,
Calculate adsorbance and removal rate.
From the figure 3, it may be seen that with H3PO4- SBC is used as adsorbent, at any time to CIP, NOR and OFL adsorbance and removal rate
It increases, its adsorbance is 10.58-15.03mg/g, removal rate 52.91-76.90% when reaction balance, and adsorption capacity is significantly high
In SBC, and it is most strong to the removal ability of CIP.
Example five: Fe/Zn+H3PO4- SBC is added in the antibiotic solution that concentration is 10mg/L, H3PO4- SBC dosage is
0.5g/L is reacted in 25 DEG C of constant temperature oscillation casees, measures the residual concentration of CIP, NOR and OFL in the time sampling of setting,
Calculate adsorbance and removal rate.
As shown in Figure 4, with Fe/Zn+H3PO4- SBC is adsorbent, to the adsorption capacity and removal rate of CIP, NOR and OFL
It is significantly higher than SBC, Fe/Zn-SBC and H3PO4- SBC, removal rate increase at any time and improve, its suction to antibiotic when balance
Attached amount is up to 12.04-19.12mg/g, and removal rate is up to 60.29-94.81%.
Example five: with Fe/Zn+H3PO4- SBC is adsorbent, is added in CIP, NOR and OFL solution that concentration is 10mg/L
(pH value of solution is adjusted to 2-10, dosage 0.5g/L, is reacted in 25 DEG C of constant temperature oscillation casees, and measurement is anti-when balance
The residual concentration of raw element, calculates adsorbance and removal rate.
As shown in Figure 5, with Fe/Zn+H3PO4- SBC is adsorbent, to the adsorption capacity of CIP, NOR and OFL by pH value of solution
Influence.Fe/Zn+H3PO4It is respectively pH=8, pH=7 that-SBC, which has the solution ph of best removal rate to CIP, NOR and OFL,
And pH=7, adsorbance up to 15.99-19.12mg/g, highest removal rate up to 79.93-97.10%,
Example six: with Fe/Zn+H3PO4- SBC is adsorbent, be separately added into 5,10,20,40,80, the CIP of 100mg/L,
In NOR and OFL solution, when dosage 0.5g/L, and pH value of solution is adjusted to optimum value, Yu Pingheng, measures the remnants of antibiotic
Concentration.
It will be appreciated from fig. 6 that with Fe/Zn+H3PO4- SBC is adsorbent, dense with antibiotic to the adsorbance of CIP, NOR and OFL
Degree increases and increases, to the maximal absorptive capacity of antibiotic up to 25.43-88.73mg/g.
The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (9)
1. the preparation method of a kind of iron zinc and phosphoric acid modification sludge organism charcoal, which is characterized in that comprise the following steps:
(1) preparation of iron zinc and phosphoric acid modification sludge organism charcoal: by secondary settling tank municipal sludge centrifugal dehydration, rear drying to constant weight,
It grinds, is then pyrolyzed, milled 100-200 mesh obtains sludge organism charcoal SBC；
(2) FeCl that volume ratio is 2:1-4:1 is added in SBC obtained by step (1)3·6H2O aqueous solution and ZnCl2Aqueous solution mixes
It closes in solution, the FeCl3·6H2The mass concentration of O is 4.8-9.6g/L, the ZnCl2The mass concentration of aqueous solution is
2.4g/L；The SBC and mixed solution ratio are that 1Kg:10L-1Kg:20L shakes for 24 hours, and 100 DEG C of drying repeat above-mentioned loaded
Journey at least 3 times is to improve the load capacity of iron and zinc；Then it calcines, obtains the sludge organism charcoal Fe/Zn-SBC of iron zinc modification；
(3) SBC obtained by step (1) is added to the H of 10.6-15mol/L3PO4In；The SBC and H3PO4Ratio is 1Kg:2.5L-
1Kg:10L, 8-10h is impregnated in concussion, after filtration drying, high-temperature activation, with deionized water cleaning sample to filtrate pH constant, 60-
80 DEG C of drying, milled 100-200 mesh obtain H3PO4Modified sewage sludge charcoal H3PO4-SBC；
(4) by SBC obtained by step (1) according to the preparation process sequential operation of step (2) and step (3), the charcoal of acquisition is
For iron zinc and H3PO4Modified sewage sludge charcoal Fe/Zn+H3PO4- SBC is kept in dark place in drier.
2. a kind of preparation method of iron zinc and phosphoric acid modification sludge organism charcoal as described in claim 1, it is characterised in that: described
In step (1), drying condition is 60-80 DEG C of forced air drying；The pyrolytical condition is N2Under protective condition, N2Flow velocity is 0.5-1L/
Min, temperature rate-of-rise are 10-20 DEG C/min, are pyrolyzed 1.5-2h under the conditions of 300-700 DEG C.
3. a kind of preparation method of iron zinc and phosphoric acid modification sludge organism charcoal as described in claim 1, it is characterised in that: described
In step (2), calcination condition N2Under protective condition, N2Flow velocity is 0.5-1L/min, and temperature rate-of-rise is 10-20 DEG C/min,
1.5-2h is pyrolyzed under the conditions of 300-700 DEG C.
4. a kind of preparation method of iron zinc and phosphoric acid modification sludge organism charcoal as described in claim 1, it is characterised in that: described
In step (3), high-temperature activation is placed in Muffle furnace, and temperature rate-of-rise is 10-20 DEG C/min, in 400-450 DEG C of heat preservation 1-
1.5h。
5. a kind of iron zinc and phosphoric acid modification sludge organism charcoal, it is characterised in that: the iron zinc and phosphoric acid modification sludge organism charcoal are
It is prepared according to method described in claim 1-4.
6. the application in fluoroquinolone antibiotics removal in water of a kind of iron zinc and phosphoric acid modification sludge organism charcoal, feature exists
In: by sludge organism charcoal SBC as claimed in claims 1-5, sludge organism charcoal Fe/Zn-SBC, H of iron zinc modification3PO4It is modified
Sludge organism charcoal H3PO4- SBC and iron zinc and H3PO4Modified sewage sludge charcoal Fe/Zn+H3PO4- SBC is added to as adsorbent to be contained
It is filtered in the water of fluoroquinolone antibiotics, after adsorption equilibrium up to the water of fluoroquinolone antibiotics is removed.
7. iron zinc as claimed in claim 6 and phosphoric acid modification sludge organism charcoal are in water in fluoroquinolone antibiotics removal
Using, it is characterised in that: the fluoroquinolone antibiotics are one of Ciprofloxacin, Norfloxacin and Ofloxacin or more
Kind.
8. iron zinc as claimed in claim 6 and phosphoric acid modification sludge organism charcoal are in water in fluoroquinolone antibiotics removal
Using, it is characterised in that: antibiotic solubility is 5-100mg/L in the water of the containing fluoroquinolones antibiotic, and adsorbent adds
Amount is 0.2-1.0g/L.
9. iron zinc as claimed in claim 6 and phosphoric acid modification sludge organism charcoal are in water in fluoroquinolone antibiotics removal
Using, it is characterised in that: the adsorbent adjusts pH value of solution after being added in the water of containing fluoroquinolones antibiotic be 2-10.
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| CN201910549244.8A CN110227416B (en) | 2019-06-24 | 2019-06-24 | Preparation of iron zinc and phosphoric acid modified sludge biochar and application of iron zinc and phosphoric acid modified sludge biochar in removal of fluoroquinolone antibiotics in water |
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| CN201910549244.8A CN110227416B (en) | 2019-06-24 | 2019-06-24 | Preparation of iron zinc and phosphoric acid modified sludge biochar and application of iron zinc and phosphoric acid modified sludge biochar in removal of fluoroquinolone antibiotics in water |
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| CN110683873A (en) * | 2019-10-22 | 2020-01-14 | 上海原本生物科技有限公司 | Method for efficiently degrading antibiotics in pig manure by using sludge charcoal |
| CN111018291A (en) * | 2019-11-25 | 2020-04-17 | 北京林业大学 | Method for preparing soluble black carbon from sludge, soluble black carbon and application of soluble black carbon |
| CN111268880A (en) * | 2020-02-26 | 2020-06-12 | 徐州工程学院 | Preparation method and application of metal ion modified sludge-based biochar |
| CN111871369A (en) * | 2020-07-10 | 2020-11-03 | 武汉理工大学 | Preparation method of potassium hydroxide modified magnetic corncob biochar composite material applied to removal of imidacloprid in water |
| CN112457851A (en) * | 2020-11-13 | 2021-03-09 | 湖南有色金属研究院 | Heavy metal contaminated soil remediation material and preparation method and application thereof |
| CN112551695A (en) * | 2020-12-11 | 2021-03-26 | 浙江清华长三角研究院 | Method for treating pharmaceutical wastewater by hydrolytic acidification-BAF-BAC combined process |
| CN113145073A (en) * | 2021-04-23 | 2021-07-23 | 桂林理工大学 | Preparation method and application of secondary lanthanum carbide modified sludge biochar |
| CN113620368A (en) * | 2021-09-07 | 2021-11-09 | 浙江清华长三角研究院 | Method for advanced treatment of fluoroquinolone antibiotic pharmaceutical wastewater by using pharmaceutical sludge biochar |
| CN113750976A (en) * | 2021-10-09 | 2021-12-07 | 东华理工大学 | Millimeter-sized sodium alginate/phosphorylated biochar composite bead as well as preparation method and application thereof |
| CN114160098A (en) * | 2021-12-07 | 2022-03-11 | 武汉理工大学 | Preparation method of alkali/double-metal salt water heat activated sludge biochar applied to removal of norfloxacin in water |
| CN114307963A (en) * | 2022-01-12 | 2022-04-12 | 杭州星宇炭素环保科技有限公司 | Modified activated carbon fiber based on waste cotton fabric and application |
| CN114604955A (en) * | 2022-01-24 | 2022-06-10 | 武汉理工大学 | Method for degrading levofloxacin by using ultrasonic and sewage peat activated periodate |
| CN115337898A (en) * | 2022-05-11 | 2022-11-15 | 广东工业大学 | Preparation method and application of basic zinc chloride loaded on diatomite |
| CN116328729A (en) * | 2023-05-26 | 2023-06-27 | 淄博致研环保科技有限公司 | Modified lignin-based biochar material, preparation method thereof and application thereof in wastewater defluorination |
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Cited By (18)
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| CN110683873A (en) * | 2019-10-22 | 2020-01-14 | 上海原本生物科技有限公司 | Method for efficiently degrading antibiotics in pig manure by using sludge charcoal |
| CN111018291A (en) * | 2019-11-25 | 2020-04-17 | 北京林业大学 | Method for preparing soluble black carbon from sludge, soluble black carbon and application of soluble black carbon |
| CN111268880A (en) * | 2020-02-26 | 2020-06-12 | 徐州工程学院 | Preparation method and application of metal ion modified sludge-based biochar |
| CN111871369A (en) * | 2020-07-10 | 2020-11-03 | 武汉理工大学 | Preparation method of potassium hydroxide modified magnetic corncob biochar composite material applied to removal of imidacloprid in water |
| CN112457851A (en) * | 2020-11-13 | 2021-03-09 | 湖南有色金属研究院 | Heavy metal contaminated soil remediation material and preparation method and application thereof |
| CN112457851B (en) * | 2020-11-13 | 2021-07-27 | 湖南有色金属研究院有限责任公司 | Heavy metal contaminated soil remediation material and preparation method and application thereof |
| CN112551695A (en) * | 2020-12-11 | 2021-03-26 | 浙江清华长三角研究院 | Method for treating pharmaceutical wastewater by hydrolytic acidification-BAF-BAC combined process |
| CN113145073A (en) * | 2021-04-23 | 2021-07-23 | 桂林理工大学 | Preparation method and application of secondary lanthanum carbide modified sludge biochar |
| CN113620368A (en) * | 2021-09-07 | 2021-11-09 | 浙江清华长三角研究院 | Method for advanced treatment of fluoroquinolone antibiotic pharmaceutical wastewater by using pharmaceutical sludge biochar |
| CN113750976A (en) * | 2021-10-09 | 2021-12-07 | 东华理工大学 | Millimeter-sized sodium alginate/phosphorylated biochar composite bead as well as preparation method and application thereof |
| CN114160098A (en) * | 2021-12-07 | 2022-03-11 | 武汉理工大学 | Preparation method of alkali/double-metal salt water heat activated sludge biochar applied to removal of norfloxacin in water |
| CN114160098B (en) * | 2021-12-07 | 2023-09-19 | 武汉理工大学 | Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water |
| CN114307963A (en) * | 2022-01-12 | 2022-04-12 | 杭州星宇炭素环保科技有限公司 | Modified activated carbon fiber based on waste cotton fabric and application |
| CN114604955A (en) * | 2022-01-24 | 2022-06-10 | 武汉理工大学 | Method for degrading levofloxacin by using ultrasonic and sewage peat activated periodate |
| CN114604955B (en) * | 2022-01-24 | 2023-12-12 | 武汉理工大学 | Method for degrading levofloxacin by utilizing ultrasonic to cooperate with sludge carbon activation periodate |
| CN115337898A (en) * | 2022-05-11 | 2022-11-15 | 广东工业大学 | Preparation method and application of basic zinc chloride loaded on diatomite |
| CN115337898B (en) * | 2022-05-11 | 2024-02-13 | 广东工业大学 | Preparation method and application of diatomite-supported basic zinc chloride |
| CN116328729A (en) * | 2023-05-26 | 2023-06-27 | 淄博致研环保科技有限公司 | Modified lignin-based biochar material, preparation method thereof and application thereof in wastewater defluorination |
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