CN109174001A - Preparation method of calcium-modified litchi biochar and method for reducing estrone in water by using calcium-modified litchi biochar - Google Patents
Preparation method of calcium-modified litchi biochar and method for reducing estrone in water by using calcium-modified litchi biochar Download PDFInfo
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- CN109174001A CN109174001A CN201811209453.XA CN201811209453A CN109174001A CN 109174001 A CN109174001 A CN 109174001A CN 201811209453 A CN201811209453 A CN 201811209453A CN 109174001 A CN109174001 A CN 109174001A
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- Prior art keywords
- calcium
- modified
- lichee
- charcoal
- biochar
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- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 title claims abstract description 86
- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229960003399 estrone Drugs 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 30
- 241001629511 Litchi Species 0.000 title abstract 7
- 239000011575 calcium Substances 0.000 claims abstract description 57
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 56
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000001110 calcium chloride Substances 0.000 claims abstract description 22
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003610 charcoal Substances 0.000 claims description 97
- 230000004048 modification Effects 0.000 claims description 28
- 238000012986 modification Methods 0.000 claims description 28
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910001424 calcium ion Inorganic materials 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000009395 breeding Methods 0.000 abstract description 5
- 230000001488 breeding effect Effects 0.000 abstract description 5
- 238000000227 grinding Methods 0.000 abstract description 3
- 244000144972 livestock Species 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 244000144977 poultry Species 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract 1
- 239000002028 Biomass Substances 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229940011871 estrogen Drugs 0.000 description 5
- 239000000262 estrogen Substances 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 244000183278 Nephelium litchi Species 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008239 natural water Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
A method for preparing calcium-modified litchi biochar and reducing estrone in a water body by using the calcium-modified litchi biochar belongs to the field of ecological environment restoration. The calcium-modified litchi biochar is prepared by the following method: cleaning litchi wood chips, drying to constant weight, crushing, sieving with a 60-mesh sieve to obtain a powdery material, mixing with a calcium chloride solution with the concentration of 40g/L, performing ultrasonic reaction at the temperature of 40 ℃ for 2 hours, oscillating at normal temperature for 2 hours, performing fast pyrolysis at the temperature of 650 ℃ for 2 hours under the condition of introducing nitrogen, cooling, grinding, and sieving with a 60-mesh sieve to obtain calcium-modified litchi biochar; the prepared calcium modified biochar can effectively remove estrone in water, and obviously reduce point source pollution caused by intensive livestock and poultry breeding. And the method for preparing the biochar can obviously reduce the using amount of calcium chloride and effectively reduce the risk of secondary pollution.
Description
Technical field
The invention belongs to ecological environments to repair field, and in particular to a kind of modified lichee charcoal preparation of calcium and utilize its drop
The method of oestrone in low water body.
Background technique
It is continued to develop recently as China's livestock and poultry breeding industry, cultivation scale and intensive degree constantly expand, great Liang Han
Natural water body can be entered by having the livestock breeding wastewater of estrogenic chemicals, generate bad shadow to water body environment quality and ecological safety
It rings.And typical material of the oestrone as estrogen, it is detected in sewage disposal plant effluent and natural water body extensively, and oestrone is female
Hormone effect is stronger, therefore the removal of the oestrone in water body becomes the emphasis of research.
Absorption method is mostly used to the removal of oestrone in water body at present, and charcoal is as a kind of achievable changing rejected material to useful resource
Using and environmental-friendly adsorbent material just obtain extensive concern.Charcoal mainly passes through the municipal waste and straw of sewage plant sludge
The biological materials such as the agricultural wastes such as stalk, rice husk are prepared under anaerobism pyrolytical condition.With the expansion of biomass selection range,
Some industry of planting forest or fruit tress wastes such as lichee batten is also prepared into charcoal by gradually exploitation.Such as " 201711075539.3 " use lichee
Curing agent of the branch charcoal as bisphenol-A soil, carries out the immobilization of bisphenol-A, obtains preferable effect.With traditional stalk
Charcoal is compared, and lichee charcoal content of cellulose is higher, and more organic aromatic functional group can be generated after pyrolysis, can be organic
Pollutant provides more adsorption sites, therefore lichee charcoal has better absorption property to organic pollutant.
Although charcoal has aperture abundant and higher specific surface area, can be inhaled by Electrostatic Absorption, π-π effect etc.
Attached organic pollutant, but its adsorption capacity, adsorption efficiency are still to be improved, and use process is to the adaptability of Complex water body
Poor, carrying out functionalized modification modification appropriate to charcoal can help to overcome the above deficiency.In recent years, China also carries out successively
Related modification biological charcoal works to the R and D of the removal technology of organic pollutant.As " CN201710036752.7 " is sent out
A kind of preparation method and applications of clay mineral modification biological charcoal are illustrated, which can effectively remove 17 β-female two in water body
Alcohol, but its technique is related to charcoal and attapulgite while being modified, and needs montmorillonite powder and biomass with 1:2 matter
Amount is than being added in liquor zinci chloridi, and preparation step is complex, and process costs and use cost are higher.
" CN201610015361.2 " devises modified charcoal of a kind of calcium and preparation method thereof and purposes, the technology preparation step compared with
It is preferable to the removal effect of phosphorus to be simple, but the ratio of the calcium chloride quality and powdered biomass additional amount in its preparation process
It is 0.56, increases preparation cost, and Ca excessive in use2+It is easy to cause the salinization of soil of soil and water resources, secondary dirt
The risk of dye is higher.
Therefore, the high biomass of content of cellulose is chosen, exploitation preparation process is simple, functionalized modification chemicals usage
Less, the modification biological charcoal that environmental suitability is strong, material is more friendly, economic cost is low and absorption property is high is still charcoal exploitation
The research direction of application field.
Summary of the invention:
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of modified lichee charcoal of calcium
Preparation method and reduce oestrone in water with it, to solve, traditional straw biological charcoal adsorption capacity at present is high, modification biological charcoal
Preparation process is complicated, modifying agent adding proportion height easily causes secondary pollution, makes and uses problem at high cost.
The present invention solve above-mentioned technical problem the technical solution adopted is that: a kind of preparation of the modified lichee charcoal of calcium is provided
Method includes the following steps:
A. lichee batten is taken, is washed with deionized water three times, drying to constant weight, and dusty material is obtained after crushing, is sieved
It is spare.
B. it prepares calcium chloride solution: calcium chloride powder is added in aqueous solution, be mixed under room temperature, obtained chlorine
The concentration for changing calcium solution is 40g/L.
C. the calcium chloride solution resulting dusty material of step A and step B being prepared ultrasonic mixing at 40 DEG C,
Sufficiently reaction 2h, wherein the mass ratio of the calcium chloride and dusty material is 1:10.
D. mixed liquor is vibrated, logical nitrogen heating, cooling is ground up, sieved, and obtains the modified lichee charcoal of calcium.
Wherein, the preparation method of the modified lichee charcoal of the calcium, in step A, drying temperature is 105 DEG C.
Wherein, the preparation method of the calcium ion modification lichee charcoal, in step C, ultrasonic power 100W；
Wherein, the preparation method of the calcium ion modification lichee charcoal, in step D, the rate of oscillation be 150rpm,
Time is 2h, and the air inflow of nitrogen is 10mL/min, and the temperature of heating is 650 DEG C, time 2h, heating rate are 5 DEG C/min.
Wherein, the preparation method of the calcium ion modification lichee charcoal, step A, in B, C and D, the powdered material
Material and the modified lichee charcoal of calcium cross 60 meshes (0.25mm), extracting screen underflow.
The present invention also provides one kind by the preparation-obtained calcium ion modification lichee charcoal of above-mentioned preparation method.
It is including following the present invention also provides the method for reducing oestrone in water using above-mentioned calcium ion modification lichee charcoal
Step:
The modified lichee charcoal of calcium is mixed with waste water containing oestrone, vibrated, filtered, obtain purified solution.
Wherein, described to be reduced in water body in the method for oestrone using the modified lichee charcoal of calcium, the waste water containing oestrone
Middle concentration is 1mg/L, and added calcium modification biological charcoal is 0.05g.
Wherein, described to be reduced in water body in the method for oestrone using the modified lichee charcoal of calcium, the modified lichee is raw
Object charcoal dosage is 1.25g/L.
Wherein, described to be reduced in water body in the method for oestrone using the modified lichee charcoal of calcium, the pH value of waste water is
7, the rate of oscillation is 150rpm, and temperature is 25 DEG C.
Wherein, described to be reduced in water body in the method for oestrone using the modified lichee charcoal of calcium, the time of the oscillation
For 2h.
The beneficial effects of the present invention are:
The present invention is first by ultrasound is mixed under the conditions of 40 DEG C with the calcium chloride solution of debita spissitudo after lichee batten dries pulverizing
Reaction 2h is closed, then fast pyrogenation prepares the modified lichee charcoal of calcium in 2h under the conditions of logical nitrogen and temperature are 650 DEG C.Preparation
The modified lichee charcoal of calcium there are more adsorption sites, specific surface area is twice of lichee charcoal before modified.Calcium carbonate
On the one hand particle height scattered adsorption increases specific surface area on the surface of charcoal, on the other hand also increase ion friendship
Transducing power is obviously improved the adsorption capacity of estrogen compared with without modified lichee charcoal, is reducing modifying agent chlorine
The dosage of charcoal is effectively reduced under the premise of the usage amount of change calcium, cost-effectiveness is obvious.In addition, lichee is typical as south
Woods fruit planting industry, lichee wooden branch item is its important waste, and the present invention is reduced female in water body using calcium modification biological charcoal
Ketone not only realizes to adaptation to local conditions waste recycling, additionally it is possible to reduce in breeding wastewater estrogen etc. to natural water ring
It is impacted in border, there is significant social and economic benefit.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) schematic diagram of calcium ion modification charcoal of the present invention；
Fig. 2 is calcium modification biological charcoal scanning electron microscope of the present invention-X-ray energy dispersion spectrum (SEM-EDX) figure；
Fig. 3 is the unmodified charcoal (BC) of the present invention and calcium modification biological charcoal (Ca-BC) X-ray diffraction (XRD) figure；
Fig. 4 is modified activated carbon preparation of the present invention and experiment schematic diagram.
Specific embodiment
Specifically, a kind of preparation method of the modified lichee charcoal of calcium, includes the following steps:
A, lichee batten is taken, is washed with deionized water three times, drying to constant weight, and grinding and sieving obtains dusty material.
B, calcium chloride solution is configured, calcium chloride powder is added in aqueous solution, is stirred evenly, obtained calcium chloride is molten
The concentration of liquid is 40g/L.
C, the calcium chloride that lichee biomass obtained by step A and step B are prepared ultrasonic reaction under the conditions of 40 DEG C
2h, wherein the mass ratio of the calcium chloride and dusty material is 1:10.
D, mixed liquor is vibrated, logical nitrogen heating, cooling is ground up, sieved, and obtains the modified lichee charcoal of calcium.
Lichee batten is a kind of common waste in southern lichee industry of planting forest or fruit tress, while being also a kind of important natural plants
Material, wherein containing the ingredients such as a large amount of lignin, cellulose.Because its oxygen-containing functional group type is abundant, such as hydroxyl, carbonyl
Deng these functional groups lay a good foundation for suction-operated；Secondly as its coarse surface and porous structure, can be organic
Pollutant absorption provides a large amount of adsorption sites.The present invention, as absorption raw material, is first dried lichee batten using lichee batten
It smashes and is sufficiently reacted with calcium chloride solution, the modified lichee charcoal of calcium is then prepared under logical nitrogen hot conditions, enhances it
Adsorption capacity.
Lichee batten length is more uneven, in order to make the charcoal homogeneous of preparation, accelerates preparation efficiency, by lichee batten
It is cut into 1~2cm；When washing, in order to keep cleaning up, generally it is washed with deionized no less than three times；Most of biology material
Expect that moisture content is relatively high, before high-temperature heating, under the conditions of 105 DEG C of baking oven, drying to constant weight；In order to guarantee itself and calcium chloride
Solution sufficiently reacts, and further crushed 60 meshes to the lichee batten fragment of drying, forms dusty material.
After dusty material and 40g/L calcium chloride solution are sufficiently mixed, it is put into waters ultrasonic device, at 40 DEG C, power is
2h is reacted under conditions of 100W, so that calcium ion reacts under conditions of high degree of dispersion with biomass, reduces calcium chloride solution
Usage amount.
After the completion of ultrasonic reaction, lichee biomass and calcium chloride mixture are put into oscillator, room temperature oscillating reactions 2h,
Frequency of oscillation is 150rpm, so that lichee biomass and calcium chloride are sufficiently mixed uniformly.
The mixture of dusty material and calcium chloride carries out high temperature anaerobic heating, nitrogen speed in the case where tube furnace leads to condition of nitrogen gas
Rate is 10mL/min, and temperature is 650 DEG C, and heating rate is 5 DEG C/min, is heated at high temperature fast reaction 2h, prepares the modified life of lichee
Object charcoal, cooled to room temperature.
In the method for the present invention step D, needs to carry out pulverization process after the modified lichee charcoal of calcium is made, keep particle biggish
Charcoal becomes that particle size is suitable, uniform charcoal is to improve its adsorption capacity under the conditions of mortar grinder.After grinding
The modified lichee charcoal of calcium crosses 60 mesh (0.25mm) sieve, extracting screen underflow.
After the calcium chloride solution modification of debita spissitudo, the modified lichee charcoal of calcium is in adsorption calcium carbonate
Particle increases specific surface area and increases surface oxygen functional group, has more adsorption sites, calcium changes compared with before modified
The absorption property of property lichee charcoal significantly increases, and the calcium chloride solution that the present invention uses is 40g/L；In step B, calcium chloride with
The mass ratio of lichee biomass is 1:10.
The present invention also provides one kind by the preparation-obtained calcium ion modification lichee charcoal of above-mentioned preparation method.
The present invention also provides the methods using oestrone in the modified lichee charcoal absorption water of above-mentioned calcium, including following step
It is rapid:
The modified lichee charcoal of calcium is mixed with the waste water containing oestrone, vibrated, filtered, be purified solution.
Wherein, in the method using oestrone in the modified lichee charcoal absorption water of calcium, the waste water containing oestrone
Middle Estrone Concentration is 1mg/L.
It is capable of the oestrone in the absorption water of more efficient using the modified lichee charcoal of calcium of the invention, calcium modified litchi when use
Branch charcoal is 1.25g/L with modified lichee charcoal dosage is contained.
Wherein, when being modified oestrone in lichee charcoal adsorbed water body using calcium, according to experiment adsorption effect, the speed of oscillation
It is set as 150rpm, time 2h；PH value is 7, and oscillation general (i.e. 25 DEG C) at room temperature carries out.
Below by test example and embodiment, the present invention is described in further detail, but does not therefore protect the present invention
Scope limitation is protected among the practical range.
Embodiment 1
The modified lichee charcoal of the present embodiment calcium is prepared by following methods:
A, fresh lichee batten is taken, the slice fragment of 1~2cm is cut into scissors, cleans lichee batten with deionized water；It will
The lichee batten cleaned up is put under 105 DEG C of baking oven that drying to constant weight.The lichee batten that drying to constant weight is ground into litchi
Branch powdered rubber and the sieve for crossing 60 mesh, extracting screen underflow.
B, 4g calcium chloride is dissolved in 100mL deionized water, is configured to the calcium chloride solution of 40g/L；Weigh 40g step
The lichee dusty material that A is obtained is put into 50mL conical flask, and the calcium chloride solution that 100mL concentration is 40g/L is added.
C, under the conditions of 25 DEG C of room temperature, after lichee biomass and 40g/L calcium chloride solution are sufficiently mixed, it is super to be put into water-bath
Sound device, at 40 DEG C, power reacts 2h under conditions of being 100W.
D, it is placed in 150rpm in constant temperature oscillation case under the conditions of 25 DEG C of room temperature and vibrates 2h.
E, the mixed liquor of lichee dusty material and calcium chloride is placed in tube furnace, under the conditions of 650 DEG C, quick high-temp adds
Hot 2h, heating rate are 5 DEG C/min, and nitrogen is passed through into tube furnace as protection gas, Ventilation Rate 10mL/min.Then exist
Under conditions of nitrogen protection, make carbonizing production Temperature fall, obtains the modified lichee charcoal of calcium.It is ground with mortar, crosses 60
Mesh, extracting screen underflow, envelope are stand-by.
The method for reducing oestrone in water body using the modified lichee charcoal of above-mentioned calcium, comprising the following steps:
It weighs the modified lichee charcoal of 0.05g calcium to be placed in conical flask, the solution (concentration of oestrone of the 40mL containing oestrone is added
For 1mg/L), pH value 7.
It is placed in 150rpm in constant temperature oscillator under the conditions of 25 DEG C and vibrates 2h, the content of oestrone in supernatant is detected, through counting
It calculates, oestrone removal rate is 73%.
Embodiment 2
The modified lichee charcoal of the present embodiment calcium is prepared by following methods:
A, fresh lichee batten is taken, the slice fragment of 1~2cm is cut into scissors, cleans lichee batten with deionized water；It will
The lichee batten cleaned up is put under 105 DEG C of baking oven that drying to constant weight.The lichee batten that drying to constant weight is ground into litchi
Branch powdered rubber and the sieve for crossing 60 mesh, extracting screen underflow.
B, 4g calcium chloride is dissolved in 100mL deionized water, is configured to the calcium chloride solution of 40g/L；Weigh 40g step
The lichee dusty material that A is obtained is put into 50mL conical flask, and the calcium chloride solution that 100mL concentration is 40g/L is added.
C, under the conditions of 25 DEG C of room temperature, after lichee biomass and 40g/L calcium chloride solution are sufficiently mixed, it is super to be put into water-bath
Sound device, at 40 DEG C, power reacts 2h under conditions of being 100W.
D, it is placed in 150rpm in constant temperature oscillation case under the conditions of 25 DEG C of room temperature and vibrates 2h.
E, the mixed liquor of lichee dusty material and calcium chloride is placed in tube furnace, under the conditions of 650 DEG C, quick high-temp adds
Hot 2h, heating rate are 5 DEG C/min, and nitrogen is passed through into tube furnace as protection gas, Ventilation Rate 10mL/min.Then exist
Under conditions of nitrogen protection, make carbonizing production Temperature fall, obtains the modified lichee charcoal of calcium.It is ground with mortar, crosses 60
Mesh, extracting screen underflow, envelope are stand-by.
The method for reducing oestrone in water body using the modified lichee charcoal of above-mentioned calcium, comprising the following steps:
It weighs the modified lichee charcoal of 0.05g calcium to be placed in conical flask, the solution (concentration of oestrone of the 40mL containing oestrone is added
For 1mg/L), pH value 7.
It is placed in 150rpm in constant temperature oscillator under the conditions of 15 DEG C and vibrates 2h, detects oestrone content in supernatant, is computed
, oestrone removal rate is 79%.
Embodiment 3
The modified lichee charcoal of the present embodiment calcium is prepared by following methods:
A, fresh lichee batten is taken, the slice fragment of 1~2cm is cut into scissors, cleans lichee batten with deionized water；It will
The lichee batten cleaned up is put under 105 DEG C of baking oven that drying to constant weight.The lichee batten that drying to constant weight is ground into litchi
Branch powdered rubber and the sieve for crossing 60 mesh, extracting screen underflow.
B, 4g calcium chloride is dissolved in 100mL deionized water, is configured to the calcium chloride solution of 40g/L；Weigh 40g step
The lichee dusty material that A is obtained is put into 50mL conical flask, and the calcium chloride solution that 100mL concentration is 40g/L is added.
C, under the conditions of 25 DEG C of room temperature, after lichee biomass and 40g/L calcium chloride solution are sufficiently mixed, it is super to be put into water-bath
Sound device, at 40 DEG C, power reacts 2h under conditions of being 100W.
D, it is placed in 150rpm in constant temperature oscillation case under the conditions of 25 DEG C of room temperature and vibrates 2h.
E, the mixed liquor of lichee dusty material and calcium chloride is placed in tube furnace, under the conditions of 650 DEG C, quick high-temp adds
Hot 2h, heating rate are 5 DEG C/min, and nitrogen is passed through into tube furnace as protection gas, Ventilation Rate 10mL/min.Then exist
Under conditions of nitrogen protection, make carbonizing production Temperature fall, obtains the modified lichee charcoal of calcium.It is ground with mortar, crosses 60
Mesh, extracting screen underflow, envelope are stand-by.
The method for reducing oestrone in water body using the modified lichee charcoal of above-mentioned calcium, comprising the following steps:
It weighs the modified lichee charcoal of 0.05g calcium to be placed in conical flask, the solution (concentration of oestrone of the 40mL containing oestrone is added
For 1mg/L), pH value 7.
It is placed in 150rpm in constant temperature oscillator under the conditions of 35 DEG C and vibrates 2h, detects oestrone content in supernatant, is computed
, oestrone removal rate is 67%.
Compared with the prior art, the advantages of the present invention are as follows:
1. the selection higher typical industry of planting forest or fruit tress waste-lichee waste of content of cellulose is biomass material, pass through
(calcium chloride and biomass mass ratio 1:10) is mixed with a small amount of calcium chloride solution, under high temperature (650 DEG C) anaerobic condition quickly
(2h) prepares the modified lichee charcoal of calcium, the specific surface area (215m of modified charcoal2/ g) it is far longer than unmodified biology
Specific surface area (the 108m of charcoal2/g)
2. the preparation process of calcium ion modification lichee charcoal of the invention is relatively simple, process more optimizes, compared to existing
Have and prepare calcium modification biological charcoal in technology, effectively reduces the usage amount of calcium chloride solution.Furthermore the quick anaerobic condition of high temperature
So that the pyrolytic reaction of calcium ion and biomass disperse system is more abundant and rapid, it is more likely formed some ducts and increases adsorption potential
Point, scanning electron microscope result (SEM) is it can be seen that there is apparent calcium carbonate granule to be adsorbed on biological carbon surface.
3. present invention demonstrates that the modified lichee charcoal of calcium has good adsorption effect to natural estrogen, in 25 DEG C of conditions
Under, when Estrone Concentration is 1mg/L in waste water, the adsorbance of oestrone is 506 μ g/g, and the dosage of calcium modification biological charcoal is 1.25g/
L can be applied to the removal of estrogen in such as breeding wastewater well.
Claims (7)
1. a kind of preparation method of calcium ion modification lichee charcoal, which comprises the steps of:
A, lichee batten is taken, is washed with deionized water three times, drying to constant weight, and dusty material, sieving for standby are obtained after crushing.
B, it prepares calcium chloride solution: calcium chloride powder is added in aqueous solution, be mixed under room temperature, obtained calcium chloride
The concentration of solution is 40g/L.
C, the calcium chloride solution that the resulting dusty material of step A and step B are prepared ultrasonic mixing at 40 DEG C, sufficiently
2h is reacted, wherein the mass ratio of the calcium chloride and dusty material is 1:10.
D, mixed liquor is vibrated, logical nitrogen heating, cooling is ground up, sieved, and obtains the modified lichee charcoal of calcium.
2. the preparation method of calcium ion modification lichee charcoal as described in claim 1, it is characterised in that: wherein, in step A
Drying temperature is 105 DEG C.
3. the preparation method of calcium ion modification lichee charcoal as claimed in claim 1 or 2, it is characterised in that: in step C,
Ultrasonic power is 100W；In step D, the rate of oscillation is 150rpm, time 2h, and the air inflow of nitrogen is 10mL/min, is added
The temperature of heat is 650 DEG C, time 2h, heating rate are 5 DEG C/min.
4. the preparation method of calcium ion modification lichee charcoal a method according to any one of claims 1-3, it is characterised in that: step A,
B, in C and D, the dusty material and the modified lichee charcoal of calcium cross 60 meshes (0.25mm), extracting screen underflow.
5. a kind of preparation-obtained calcium ion modification lichee charcoal of preparation method as described in claim 1-4 is any.
6. a kind of method for reducing oestrone in water using calcium ion modification lichee charcoal as claimed in claim 5, feature
It is, comprising the following steps:
The modified lichee charcoal of the calcium is mixed with waste water containing oestrone, the modified lichee charcoal of the calcium and the waste water containing oestrone
Solid-to-liquid ratio be 1:800, wherein in mass, waste water solution containing oestrone is by volume for the modified lichee charcoal of calcium；Through oscillation, mistake
Filter, obtains purified solution.
7. reducing the method for oestrone in water as claimed in claim 6, it is characterised in that: the modified lichee charcoal dosage
For 1.25g/L.The pH value of waste water is 7, and the rate of oscillation is 150rpm, and the time of the oscillation is 2h, and temperature is 25 DEG C.
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