CN110372062A - Magnetic bio coke is in waste water except the application in selenium - Google Patents
Magnetic bio coke is in waste water except the application in selenium Download PDFInfo
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- CN110372062A CN110372062A CN201910777338.0A CN201910777338A CN110372062A CN 110372062 A CN110372062 A CN 110372062A CN 201910777338 A CN201910777338 A CN 201910777338A CN 110372062 A CN110372062 A CN 110372062A
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- selenium
- magnetic bio
- coke
- bio coke
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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
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
-
- 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
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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
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/106—Selenium compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to waste water to remove selenium technical field more particularly to magnetic bio coke in waste water except the application in selenium.Magnetic bio coke provided by the invention is in waste water except the application in selenium, comprising the following steps: magnetic bio coke is placed in selenium-containing wastewater to be processed, is adsorbed;The magnetic bio coke includes porous charcoal and the ferriferous oxide that is supported in the porous charcoal.Record according to the embodiment, for magnetic bio coke of the present invention to the selenium adsorption efficiency with higher in waste water, the adsorption efficiency reaches as high as 95.1%, meanwhile, the magnetic bio coke also has preferable sorption cycle stability.
Description
Technical field
The present invention relates to waste water to remove selenium technical field more particularly to a kind of magnetic bio coke in waste water except the application in selenium.
Background technique
China is maximum coal production and country of consumption in the world, China's steam coal broad categories, arsenic, selenium and lead in coal
Average content be respectively 3.8 μ g/g, 2.8 μ g/g, 16.9 μ g/g.During burning of coal, selenium element is with Se0And SeO2's
Form volatilization.In the boiler of coal combustion, gaseous state SeO2Chemisorption can be carried out on the flying dust surface (FA) or be maintained at gas phase
In.Selenium in conjunction with particulate matter is removed in particulate collection device;Remaining selenium enters as gas phase or particulate matter selenium
Wet desulphurization device.In flue gas desulphurization system, particle selenium is dissolved in the water phase of absorbability mud, and gaseous state selenium passes through gas first
Body is diffused into water phase, dissolves in water phase and undergoes series of chemical (selenium in water phase is mainly with selenite and selenic acid
The form presence of salt).Therefore, the selenium dissolved in desulfurization wastewater causes biggish pressure to environment.
Summary of the invention
The purpose of the present invention is to provide a kind of magnetic bio coke in waste water except the application in selenium, the magnetic bio coke is right
In the removal mild condition of selenium, removal efficiency is high.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of magnetic bio coke in waste water except the application in selenium, comprising the following steps:
Magnetic bio coke is placed in selenium-containing wastewater to be processed, is adsorbed;
The magnetic bio coke includes porous charcoal and the ferriferous oxide that is supported in the porous charcoal.
Preferably, the temperature of the absorption is 20~50 DEG C.
Preferably, the absorption carries out under stirring conditions;
The rate of the stirring is 250~350rpm, and the time of the stirring is 2~5h.
Preferably, the selenium in the selenium-containing wastewater to be processed exists in the form of selenite or selenate.
Preferably, the mass ratio of the selenium in the selenium-containing wastewater to be processed and magnetic bio coke is 1:(800~1200).
Preferably, in terms of the quality of iron, ferriferous oxide accounts for the mass percent of magnetic bio coke in the magnetic bio coke
It is 5~20%;
The mass percent that the porous charcoal accounts for magnetic bio coke is 75~90%.
Preferably, the preparation method of the magnetic bio coke, comprising the following steps:
Biomass material is successively impregnated in ferric chloride solution, is pyrolyzed, magnetic bio coke is obtained.
Preferably, the atmosphere of the pyrolysis is nitrogen, and the temperature of the pyrolysis is 300~800 DEG C, the time of the pyrolysis
It is 30~120 minutes.
The present invention provides a kind of magnetic bio coke in waste water except the application in selenium, comprising the following steps: by magnetic bio
Coke is placed in selenium-containing wastewater to be processed, is adsorbed;The magnetic bio coke includes porous charcoal and is supported in the porous charcoal
Ferriferous oxide.Record according to the embodiment, magnetic bio coke of the present invention is to the selenium absorption with higher in waste water
Efficiency, the adsorption efficiency reach as high as 95.1%, meanwhile, the magnetic bio coke also has steady with preferable sorption cycle
It is qualitative.
Detailed description of the invention
Fig. 1 is adsorption rate of the magnetic bio coke described in embodiment 1,2 to selenium;
Fig. 2 is adsorption rate of the magnetic bio coke described in embodiment 3,4 to selenium;
Fig. 3 is the sorption cycle curve of stability of magnetic bio coke as described in example 4;
Fig. 4 is the flow chart that Selenium in Wastewater is removed using magnetic bio coke;
Fig. 5 is the preparation flow figure of magnetic bio coke.
Specific embodiment
In the present invention, if without specified otherwise, all raw materials being related to below are city well known to those skilled in the art
Sell product.
The present invention provides a kind of magnetic bio coke in waste water except the application in selenium, comprising the following steps:
Magnetic bio coke is placed in selenium-containing wastewater to be processed, is adsorbed;
The magnetic bio coke includes porous charcoal and the ferriferous oxide (as shown in Figure 4) that is supported in the porous charcoal.
In the present invention, the magnetic bio coke includes porous charcoal and the ferriferous oxide that is supported in the porous charcoal;Institute
Stating ferriferous oxide and accounting for the mass percent of magnetic bio coke is preferably 5~20%, more preferably 8~16%, most preferably 10~
12%, the content of the ferriferous oxide is in terms of iron;In the present invention, the ferriferous oxide preferably includes ferroso-ferric oxide, preferably
It further include iron oxide and/or ferrous oxide;The mass percent of the iron oxide and/or ferrous oxide in ferriferous oxide is preferred
≤ 2%.
In the present invention, the preparation method of the magnetic bio coke, preferably includes following steps:
Biomass material is impregnated in ferric chloride solution, is pyrolyzed, it is burnt (as shown in Figure 5) to obtain magnetic bio.
The present invention does not have any special restriction to the type of the biomass material, using known to those skilled in the art
Type, the biomass material can be selected specifically to poplar or pine in a specific embodiment of the present invention.At this
In invention, the partial size of the biomass material is preferably≤0.15mm.
In the present invention, the concentration of the ferric chloride solution is preferably 4.5~5.5g/L, more preferably 4.8~5.2g/L.
In the present invention, the dosage of the biomass material and iron chloride is to reach the matter of ferriferous oxide in target product magnetic bio coke
Measure the purpose of percentage.
In the present invention, the temperature of the dipping is preferably 20~50 DEG C, and more preferably 25~30 DEG C;The dipping is preferred
It carries out under stirring conditions, the revolving speed of the stirring is preferably 250~350rpm, more preferably 280~320rpm, most preferably
For 300rpm;The time of the stirring is preferably 2~5h, more preferably 2.5~4.5h, most preferably 4h.
After the completion of the dipping, preferably the biomass after dipping is dried by the present invention.In the present invention, the drying
Temperature be preferably 80~120 DEG C, more preferably 80~100 DEG C, most preferably 100 DEG C, the time of the drying is preferably 15
~20h, more preferably 16~18h, most preferably 18h.The present invention does not have any special restriction to the mode of the drying, adopts
It is carried out with mode well known to those skilled in the art.
In the present invention, the atmosphere of the pyrolysis is preferably nitrogen, and the temperature of the pyrolysis is preferably 300~800 DEG C, more
Preferably 300~700 DEG C, most preferably 700 DEG C;The time of the pyrolysis is preferably 30~120min, more preferably 50~
100min, most preferably 60~80min.
In the present invention, the selenium in the selenium-containing wastewater to be processed exists preferably in the form of selenite or selenate.
The present invention to the concentration of selenium in selenium-containing wastewater to be processed there is no any special restriction.In specific embodiments of the present invention
In, in terms of selenium element, the Se content in waste water to be processed of the present invention is preferably 0.1~1mg/L.
In a specific embodiment of the present invention, the waste water to be processed is the existence form according to practical sulphur removal Selenium in Wastewater
And the simulated wastewater that content is prepared.The simulated wastewater preferably according to the above-mentioned existence form to Selenium in Wastewater to be processed and contains
Amount is prepared;The present invention does not have any special restriction to the process for preparing simulated wastewater, using those skilled in the art
Process known to member carries out.In the present invention, the mass ratio of the selenium in the selenium-containing wastewater to be processed and magnetic bio coke
Preferably 1:(800~1200), more preferably 1:(900~1100), most preferably 1:1000.In the present invention, by magnetic green
The solid-to-liquid ratio that object coke is placed in the mixed liquor obtained after selenium-containing wastewater to be processed is preferably 8~12g:1L, more preferably 9~11g:
1L, most preferably 10g:1L.
In the present invention, the temperature of the absorption is preferably 20~50 DEG C, and more preferably 25~30 DEG C;The absorption is preferred
It carries out under stirring conditions, the rate of the stirring is preferably 250~350rpm, more preferably 280~320rpm, most preferably
For 300rpm;The time of the stirring is preferably 3.5~4.5h, more preferably 3.85~4.2h, most preferably 4.0h.
The application in selenium is removed in waste water to magnetic bio coke provided by the invention below with reference to embodiment to carry out specifically
It is bright, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(25 DEG C, 300rpm) under stirring conditions, the poplar by 10g partial size less than 0.15mm are impregnated in 200mL 5g/
LFeCl3240min in solution, dry (100 DEG C, 18h) and pyrolysis (nitrogen atmosphere, 500 DEG C, 1h) obtain magnetic bio coke and (contain
Iron is 10wt%);
The sodium selenite solution of 1mg/L is prepared, is simulated wastewater;
Magnetic bio coke described in 50mg is added in simulated wastewater described in 50mL, in the condition of stirring (25 DEG C, 300rpm)
Lower absorption 4h.
Embodiment 2
(25 DEG C, 300rpm) under stirring conditions, the poplar by 10g partial size less than 0.15mm are impregnated in 200mL 10g/
LFeCl3240min in solution, dry (100 DEG C, 18h) and pyrolysis (nitrogen atmosphere, 500 DEG C, 1h) obtain magnetic bio coke and (contain
Iron is 20wt%);
The sodium selenite solution of 1mg/L is prepared, is simulated wastewater;
Magnetic bio coke described in 50mg is added in simulated wastewater described in 50mL, in the condition of stirring (25 DEG C, 300rpm)
Lower absorption 4h.
Embodiment 3
(25 DEG C, 300rpm) under stirring conditions, the poplar by 10g partial size less than 0.15mm are impregnated in 200mL 5g/
LFeCl3240min in solution, dry (100 DEG C, 18h) and pyrolysis (nitrogen atmosphere, 300 DEG C, 1h) obtain magnetic bio coke and (contain
Iron is 10wt%);
The sodium selenite solution of 1mg/L is prepared, is simulated wastewater;
Magnetic bio coke described in 50mg is added in simulated wastewater described in 50mL, in the condition of stirring (25 DEG C, 300rpm)
Lower absorption 4h.
Embodiment 4
(25 DEG C, 300rpm) under stirring conditions, the poplar by 10g partial size less than 0.15mm are impregnated in 200mL 5g/
LFeCl3240min in solution, dry (100 DEG C, 18h) and pyrolysis (nitrogen atmosphere, 700 DEG C, 1h) obtain magnetic bio coke and (contain
Iron is 10wt%);
The sodium selenite solution of 1mg/L is prepared, is simulated wastewater;
Magnetic bio coke described in 50mg is added in simulated wastewater described in 50mL, in the condition of stirring (25 DEG C, 300rpm)
Lower absorption 4h.
Test case
By Examples 1 to 4 treated 45 μm of membrane filtrations of simulated wastewater, obtains supernatant and be placed in sample bottle
Afterwards, sample dilution is placed in sample cell for 50 times by the HCl solution for being 20% with mass concentration, utilizes AFS atomic fluorescence range meter
The content of selenium in simulated wastewater after measurement processing, and calculate the adsorption rate of selenium;
Final result is as depicted in figs. 1 and 2, and wherein Fig. 1 is embodiment 1, the adsorption rate of 2 selenium, and Fig. 2 is embodiment 3,4
Adsorption rate, by Fig. 1 and Fig. 2 it is found that magnetic bio coke of the present invention is to the selenium adsorption rate with higher in waste water;
Magnetic bio after absorption selenium in embodiment 4 is burnt, it is heat-treated (nitrogen atmosphere, 700 DEG C, 0.5h), makes it
In selenium desorption, then carry out 5 times absorption and desorption circulations, circulating effect data are as shown in figure 3, from the figure 3, it may be seen that by 5
After secondary circulation, adsorbent is to selenium adsorption rate still with higher.
As seen from the above embodiment, magnetic bio coke provided by the invention absorption effect with higher to the selenium in waste water
Rate, the adsorption efficiency reach as high as 95.1%, meanwhile, the magnetic bio coke also has preferable sorption cycle stability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of magnetic bio coke is in waste water except the application in selenium, which comprises the following steps:
Magnetic bio coke is placed in selenium-containing wastewater to be processed, is adsorbed;
The magnetic bio coke includes porous charcoal and the ferriferous oxide that is supported in the porous charcoal.
2. application as described in claim 1, which is characterized in that the temperature of the absorption is 20~50 DEG C.
3. application as described in claim 1, which is characterized in that the absorption carries out under stirring conditions;
The rate of the stirring is 250~350rpm, and the time of the stirring is 2~5h.
4. application as described in claim 1, which is characterized in that the selenium in the selenium-containing wastewater to be processed is with selenite or selenium
The form of hydrochlorate exists.
5. application as described in claim 1 or 4, which is characterized in that selenium and magnetic bio in the selenium-containing wastewater to be processed
Burnt mass ratio is 1:(800~1200).
6. application as claimed in claim 5, which is characterized in that in terms of the quality of iron, ferriferous oxide in the magnetic bio coke
The mass percent for accounting for magnetic bio coke is 5~20%;
The mass percent that the porous charcoal accounts for magnetic bio coke is 75~90%.
7. application as claimed in claim 6, which is characterized in that the preparation method of the magnetic bio coke, comprising the following steps:
Biomass material is successively impregnated in ferric chloride solution, is pyrolyzed, magnetic bio coke is obtained.
8. the use as claimed in claim 7, which is characterized in that the atmosphere of the pyrolysis is nitrogen, and the temperature of the pyrolysis is
300~800 DEG C, the time of the pyrolysis is 30~120 minutes.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114538544A (en) * | 2022-03-21 | 2022-05-27 | 中国科学院沈阳应用生态研究所 | Method for treating selenium-containing wastewater by taking waste iron filings as iron source and sulfur-induced stabilization |
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CN114538544A (en) * | 2022-03-21 | 2022-05-27 | 中国科学院沈阳应用生态研究所 | Method for treating selenium-containing wastewater by taking waste iron filings as iron source and sulfur-induced stabilization |
CN114538544B (en) * | 2022-03-21 | 2023-08-18 | 中国科学院沈阳应用生态研究所 | Method for treating selenium-containing wastewater by taking scrap iron as iron source sulfur induced stabilization |
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Application publication date: 20191025 |