CN117303491A - Sewage treatment method using iron/calcium oxide loaded biochar - Google Patents
Sewage treatment method using iron/calcium oxide loaded biochar Download PDFInfo
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- CN117303491A CN117303491A CN202311046091.8A CN202311046091A CN117303491A CN 117303491 A CN117303491 A CN 117303491A CN 202311046091 A CN202311046091 A CN 202311046091A CN 117303491 A CN117303491 A CN 117303491A
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- Prior art keywords
- biochar
- iron
- calcium oxide
- loaded
- ferrous chloride
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000000292 calcium oxide Substances 0.000 title claims abstract description 49
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims abstract description 49
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000010865 sewage Substances 0.000 title claims abstract description 20
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 23
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000004343 Calcium peroxide Substances 0.000 claims abstract description 17
- 235000019402 calcium peroxide Nutrition 0.000 claims abstract description 17
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 12
- 230000010355 oscillation Effects 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 23
- 244000060011 Cocos nucifera Species 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000000197 pyrolysis Methods 0.000 claims description 9
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000001179 sorption measurement Methods 0.000 description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 35
- 229910052698 phosphorus Inorganic materials 0.000 description 35
- 239000011574 phosphorus Substances 0.000 description 35
- 229910052742 iron Inorganic materials 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
- 230000004048 modification Effects 0.000 description 19
- 238000012986 modification Methods 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000011575 calcium Substances 0.000 description 15
- 239000003610 charcoal Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910014472 Ca—O Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
-
- 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
- C02F2101/105—Phosphorus compounds
Abstract
The invention relates to a sewage treatment method using iron/calcium oxide loaded biochar. The invention is suitable for the field of water treatment. The invention aims to solve the technical problems that: provides a sewage treatment method using iron/calcium oxide loaded biochar. The technical scheme adopted by the invention is as follows: a sewage treatment method using iron/calcium oxide loaded biochar is characterized in that: adding the iron/calcium oxide loaded biochar into sewage for sewage treatment; the iron/calcium oxide loaded biochar is prepared by the following method: s1, preparing ferrous chloride solution; s2, immersing the biochar into a ferrous chloride solution, and then adding calcium peroxide powder into the ferrous chloride solution for oscillation and aging treatment; s3, taking out the biochar in the solution, and pyrolyzing the biochar to obtain the biochar loaded with the iron/calcium oxide.
Description
Technical Field
The invention relates to a sewage treatment method using iron/calcium oxide loaded biochar. Is suitable for the field of water treatment.
Background
Biochar is often used as a filler in the existing sewage technology to remove phosphorus in water. Research on adsorption of phosphorus in water by biochar focuses on both the mechanism and performance of adsorption. A great deal of researches show that the surface adsorption mechanism is the main mechanism of adsorbing phosphorus by biochar; research on adsorption performance focuses on different biochar raw materials and different modification methods, common methods include physical modification and chemical modification, for example, the phosphorus removal performance of biochar can be remarkably improved through iron modification. However, the existing iron modified biochar has limited dephosphorization effect, complex preparation process and difficult industrial production.
Disclosure of Invention
The invention aims to solve the technical problems that: aiming at the problems, a sewage treatment method using the iron/calcium oxide loaded biochar is provided to efficiently remove phosphorus in sewage.
The technical scheme adopted by the invention is as follows: a sewage treatment method using iron/calcium oxide loaded biochar is characterized in that: adding the iron/calcium oxide loaded biochar into sewage for sewage treatment;
the iron/calcium oxide loaded biochar is prepared by the following method:
s1, preparing ferrous chloride solution;
s2, immersing the biochar into a ferrous chloride solution, and then adding calcium peroxide powder into the ferrous chloride solution for oscillation and aging treatment;
s3, taking out the biochar in the solution, and pyrolyzing the biochar to obtain the biochar loaded with the iron/calcium oxide.
By the technical means, the characteristic that the adsorption quantity of the biochar to ferrous ions is more than 1.5 times of that of ferric ions is utilized, so that the biochar is loaded with more ferric ions, and the dephosphorization capability of the biochar is improved; the method comprises the steps of generating calcium hydroxide and oxygen by utilizing calcium peroxide when meeting water, enabling the calcium hydroxide to react with ferrous chloride to generate ferrous hydroxide and calcium chloride, enabling the ferrous hydroxide generated by adsorption on the surface of the biochar to be oxidized into ferric hydroxide by the oxygen, and finally preparing the biochar loaded with iron/calcium oxide through high-temperature calcination.
A preparation method of iron/calcium oxide loaded biochar is characterized by comprising the following steps:
s1, preparing ferrous chloride solution;
s2, immersing the biochar into a ferrous chloride solution, and then adding calcium peroxide powder into the ferrous chloride solution for oscillation and aging treatment;
s3, taking out the biochar in the solution, and pyrolyzing the biochar to obtain the biochar loaded with the iron/calcium oxide.
The concentration of the ferrous chloride solution is 0.5-2mol/L.
The biochar is coconut shell biochar.
In the step S2, biochar is added into the ferrous chloride solution according to the iron-carbon ratio of 10:1-5:1.
In the step S2, the oscillation temperature is 25 ℃, the rotation speed is 200rpm, and the oscillation time is 24 hours.
And in the step S3, the pyrolysis temperature is 800 ℃, and the pyrolysis time is 1h.
The iron/calcium oxide loaded biochar prepared by the preparation method.
Use of the iron/calcium oxide loaded biochar in sewage treatment.
Use of the iron/calcium oxide loaded biochar in dephosphorization.
The beneficial effects of the invention are as follows:
the iron/calcium oxide loaded biochar composite material prepared by the invention can rapidly adsorb phosphate radical in water, thereby realizing efficient dephosphorization. The iron oxide has selective adsorption capacity to phosphate radical in water, and calcium ions can be quickly combined with the phosphate radical in water to form stable calcium phosphate precipitate, so that the aim of high-efficiency dephosphorization is fulfilled.
The invention adopts the coconut shell charcoal as the raw material, the material is easy to obtain, the mechanical strength of the coconut shell charcoal is high, the use is convenient, the cost is low, and the invention is more suitable for industrial production.
Because the adsorption quantity of the coconut shell charcoal to ferrous ions is more than 1.5 times of that of ferric ions, the ferrous chloride solution is selected as the iron solution, so that the coconut shell charcoal loads more ferric ions, and the dephosphorization capability of the charcoal is improved.
The calcium peroxide is a novel oxidant and oxygen release agent, and compared with the traditional oxidant, the calcium peroxide is more stable, continuous, efficient and low in cost. According to the invention, calcium peroxide can generate calcium hydroxide and oxygen when meeting water, strong calcium oxide can react with ferrous chloride to generate ferrous hydroxide and calcium chloride, and oxygen can oxidize ferrous hydroxide generated by adsorption on the surface of the biochar into ferric hydroxide, and finally the biochar loaded with iron/calcium oxide is prepared through high-temperature calcination.
The invention synchronously realizes the loading of iron and calcium oxide on the coconut shell biochar based on the screened coconut shell biochar, and prepares the iron/calcium oxide loaded biochar composite material. The production and preparation process is simple, the production steps are simplified to three steps, and the method is suitable for industrial production.
The iron/calcium oxide loaded biochar composite material prepared by the method can be used as a slow-release fertilizer for returning to the field after adsorption saturation, does not cause secondary pollution, and has good application prospect.
Drawings
FIG. 1 is a graph showing morphology comparison of unmodified biochar (a) and modified biochar (b) in example one;
FIG. 2 is a graph of an EDS spectrum Fe, ca, O, C scan of unmodified biochar (a) and modified biochar (b) in example one;
FIG. 3 is XRD patterns of biochar before and after modification in example one;
FIG. 4 is a FT-IR chart of biochar before and after modification in example one;
FIG. 5 shows the effect of adsorption of phosphorus by biochar before and after modification (effect of removal of phosphorus by modified biochar and unmodified biochar) in example two;
FIG. 6 is the effect of different pyrolysis temperatures on the adsorption of phosphorus by the modified biochar (removal effect of phosphorus by the modified biochar at different pyrolysis temperatures) in example three;
FIG. 7 is a graph of adsorption kinetics of phosphorus (quasi-first and quasi-second adsorption kinetics) for the modified biochar of example four;
FIG. 8 is a graph showing adsorption isotherms (adsorption isotherms) of the modified biochar versus phosphorus in example five;
FIG. 9 is the effect of initial pH on adsorption of phosphorus by modified and unmodified biochars (effect of initial pH on phosphorus removal by modified and unmodified biochars) in example six;
FIG. 10 is the effect of coexisting ions on the adsorption of phosphorus by modified biochar (effect of coexisting ions on the removal of phosphorus by modified biochar) in example seven.
Detailed Description
Embodiment one: the embodiment provides a sewage treatment method using iron/calcium oxide loaded biochar, which adopts the iron/calcium oxide loaded biochar to efficiently remove phosphorus in sewage. The preparation method of the iron/calcium oxide loaded biochar in the embodiment comprises the following steps:
s1, preparing 4-10 mesh coconut shell biochar; preparing FeCl of 0.5mol/L 2 A solution.
S2, immersing the coconut shell charcoal into FeCl 2 In the solution, the ratio of iron to carbon is 1:10, then calcium peroxide powder is added into the solution until the pH value is 7, the solution is stirred and immersed for 30min at 25 ℃ and 200r/min, and then aged for 24h, and the iron and calcium mixture is uniformly loaded on the surface of the biochar.
In this example, the coconut shell charcoal was impregnated with FeCl 2 After the solution, the coconut shell charcoal adsorbs ferrous ions in the solution.
In the embodiment, after the calcium peroxide powder is added into the solution, calcium hydroxide and oxygen can be generated when the calcium peroxide meets water, the strong calcium oxide can react with ferrous chloride to generate ferrous hydroxide and calcium chloride, and the oxygen can oxidize ferrous hydroxide generated by adsorption on the surface of the biochar into ferric hydroxide. The specific reaction chemistry equation is as follows:
2CaO 2 +2H 2 O＝2Ca(OH) 2 ten O 2 ↑
FeCl 2 +Ca(OH) 2 ＝Fe(OH) 2 ↓+CaCl 2
4Fe(OH) 2 +O 2 +2H 2 O＝4Fe(OH) 3 ↓
And S3, taking out the biochar in the solution in the step S2, and pyrolyzing at 800 ℃ for 1h to obtain the biochar loaded with the iron/calcium oxide.
The method comprises the steps of respectively carrying out structural characterization on the biochar before and after modification, analyzing the change of the surface morphology before and after modification by a Scanning Electron Microscope (SEM), analyzing the abundance of C, O, ca and Fe on the surface of the biochar before and after modification by an Energy Dispersive Spectroscopy (EDS), analyzing the crystal structure of the biochar before and after modification by an X-ray diffraction (XRD), and carrying out Fourier transform infrared absorption spectroscopy (FT-IR) on characteristic functional groups of the biochar before and after modification.
As shown in fig. 1, SEM analysis was performed on the coconut shell charcoal before and after modification, respectively. Under the microscopic scale, after 2K and 10K times amplification, the surfaces of the unmodified biochar (a 1 and a 2) are relatively flat, and flaky scraps with different sizes are loaded; after the biochar is modified by iron/calcium (b 1 and b 2), surface loading particles can be obviously observed, and rich void structures and larger specific surface area are formed, so that the adsorption capacity of the material is enhanced. SEM results show that iron and calcium are successfully loaded on the biochar, the surface morphology of the biochar is changed, the pore structure is increased, and the specific surface area is increased.
C, O, ca, fe content of the biochar surface before and after modification is analyzed by EDS (electron discharge spectroscopy), and the spectral line scanning result is shown in figure 2. After normalization treatment, the weight percentages of the biochar C, O, ca before modification and Fe are 79.80%,18.49%,0.91% and 0.79%, respectively, and the weight percentages of the biochar C, O, ca after modification and Fe are 66.10%,20.91%,7.35% and 5.64%, respectively. The modified Fe and Ca amount is increased in proportion, which can indicate that the modified Fe and Ca are successfully loaded on the surface of the biochar.
XRD results are shown in FIG. 3, and characteristic peaks appear in biochar before and after modification at 2 theta angles of 24.3 DEG and 43.1 deg. But compared with the biochar before modification, the characteristic peak intensity after modification is obviously weakened. As can be seen from the spectrum, there is a relatively broad peak at 24 ° for the unmodified biochar, indicating that the carbon in the unmodified biochar exists predominantly in an amorphous form. Warp CaO 2 And FeCl 2 The modified biochar is obtained after mixing modification, the modified biochar still has wide wrap peaks at 24 degrees, and derivative peaks appear at 23.02 degrees, 29.41 degrees, 31.42 degrees, 35.97 degrees, 39.40 degrees, 43.15 degrees, 47.12 degrees, 47.49 degrees and 48.51 degrees, and the modified biochar is compared with CaCO (CaCO) 3 (PDF # 05-0586) crystal planes (012), (104), (006), (110), (113), (202), (024), (018) and (116) match (Affolter-Zbaraszczuk et al 2017,Mohan et al 2018), indicating CaO in the sample after compounding and calcination 2 React with carbon to produce CaCO 3 . Derivative peaks appear at 24.13 °, 33.16 °, 35.61 °, 39.22 °, 40.84 °, 43.47 °, 49.42 °, 54.00 °, 57.51 °, 62.38 ° and 63.97 °, which are compared with Fe 2 O 3 (PDF # 24-0072) crystal planes (012), (104), (110), (006), (113), (202), (024), (116), (122), (214) and (300) match (Gu et al 2016), illustrating FeCl in the sample after compounding and calcination 2 Mainly converted into hematite Fe 2 O 3 . In addition, derivative peaks appear at 11.98 °, 16.93 °, 22.86 °, 24.10 °, 29.24 °, 31.97 °, 33.03 °, 33.46 °, 34.32 °, 36.51 ° and 38.25 °, which are compared to Ca 2 Fe 2 O 5 The (020), (011), (101), (040), (131), (002), (200), (141), (051), (112) and (122) crystal planes of (PDF # 47-1744) match, indicating FeCl in the sample after compounding and calcination 2 And CaO (CaO) 2 Can react to produce the Ca of the perovskite 2 Fe 2 O 5 (Sun et al 2019,Molinar Díaz et al 2020)。
FT-IR results are shown in FIG. 4, which shows that 3448cm was obtained from the infrared spectra of the modified biochar and the unmodified biochar -1 The broad peak in the vicinity is the telescopic vibration absorption peak of O-H. 1627cm -1 The absorption peak at the position is the telescopic vibration absorption peak of C-H in aromatic hydrocarbon, the C-H of the modified biochar shifts and appears at 1646cm -1 Where it is located. 1565cm -1 The stretching vibration absorption peak of the c=c double bond is shown, and the modified c=c double bond absorption peak appears at 1509. 1066cm -1 The absorption peak at this point is the C-O telescopic vibration absorption peak. In the modified biochar, a new infrared absorption peak appears. 877cm -1 The infrared characteristic absorption peak of Ca-O is 603cm -1 The position is the expansion vibration absorption peak of Fe-O, 466cm -1 The tensile vibration absorption peak of Fe-OH is shown. The FT-IR results again indicate successful iron and calcium loading on the biochar.
Embodiment two: influence of different pyrolysis temperatures on the phosphorus adsorption effect of the modified biochar.
Preparing 4-10 mesh coconut shell activated carbon. Preparing FeCl of 0.5mol/L 2 Solution, immersing coconut shell charcoal into FeCl 2 In the solution, the ratio of iron to carbon is 1:10, then calcium peroxide powder is added into the solution until the pH value is 7, the solution is stirred and immersed for 30min at 25 ℃ and 200r/min, and then aged for 24h, and the iron and calcium mixture is uniformly loaded on the surface of the biochar. Taking out the biochar, placing the biochar in a muffle furnace, and pyrolyzing the biochar at 300, 400, 500, 600, 700, 800 and 900 ℃ for 1h respectively to obtain the biochar loaded with the iron/calcium oxide.
0.5g of the modified biochar at different pyrolysis temperatures is weighed into a 100ml centrifuge tube, 10mg/L (calculated as phosphorus, the same applies below) is added into the centrifuge tube, 50ml of KH with pH of 7 is added 2 PO 4 The solution is aged for 24 hours after shaking for 30 minutes at 200r/min at 25 ℃, and then filtered by a 0.45 mu m water-based filter membrane to determine the concentration of total phosphorus in the water sampleDegree, three per group in parallel.
As shown in FIG. 6, the modified biochar with pyrolysis temperature of 800 ℃ has the best effect of adsorbing phosphorus, and the removal rate reaches 99.18 percent.
Embodiment III: adsorption kinetics experiments.
Preparing 4-10 mesh coconut shell activated carbon. Preparing FeCl of 0.5mol/L 2 Solution, immersing coconut shell charcoal into FeCl 2 In the solution, the ratio of iron to carbon is 1:10, then calcium peroxide powder is added into the solution until the pH value is 7, the solution is stirred and immersed for 30min at 25 ℃ and 200r/min, and then aged for 24h, and the iron and calcium mixture is uniformly loaded on the surface of the biochar. Taking out the biochar, and pyrolyzing the biochar at 800 ℃ for 1h to obtain the biochar loaded with the iron/calcium oxide.
Weighing 0.5g of the modified biochar obtained by the preparation method, putting the modified biochar into a 100mL centrifuge tube, and adding KH with the concentration of 10mg/L,50mL and the pH of 7 2 PO 4 The solution is oscillated at a speed of 200r/min at 25 ℃ for 5, 15, 30, 60, 180, 360 and 720min respectively, and then filtered by a 0.45 mu m water system filter membrane, and the concentration of total phosphorus in the water sample is measured, wherein each group is three times in parallel.
As shown in fig. 7, the fitting coefficients R of the quasi-primary dynamics model and the quasi-secondary dynamics model 2 The difference is 0.975 and 0.995 respectively, which indicates that the quasi-first-order dynamics and the quasi-second-order dynamics are suitable for the adsorption process of the modified biochar on the phosphate, and the adsorption process of the modified biochar on the phosphate is physical adsorption and chemical adsorption. The modified biochar basically reaches adsorption equilibrium after 6 hours. KH at initial concentration of 10mg/L 2 PO 4 The adsorption amount of the solution at the adsorption equilibrium was 1.26mg/g.
Embodiment four: adsorption isotherm experiments.
Preparing 4-10 mesh coconut shell activated carbon. Preparing FeCl of 0.5mol/L 2 Solution, immersing coconut shell charcoal into FeCl 2 In the solution, the ratio of iron to carbon is 1:10, then calcium peroxide powder is added into the solution until the pH value is 7, the solution is stirred and immersed for 30min at 25 ℃ and 200r/min, and then aged for 24h, and the iron and calcium mixture is uniformly loaded on the surface of the biochar. Taking out the biochar, and pyrolyzing the biochar at 800 ℃ for 1h to obtain the biochar loaded with the iron/calcium oxide.
Weighing 0.5g of the modified biochar into a 100mL centrifuge tube, and adding 50mL of KH with the concentration of 5, 10, 20, 50, 70, 100, 150mg/L and the pH of 7 into the centrifuge tube 2 PO 4 The solution was subjected to shaking at a speed of 200r/min at 25℃for 12h, and then filtered through a 0.45 μm aqueous filter, and the total phosphorus concentration in the water sample was determined, three replicates each.
As shown in fig. 8, wherein the correlation coefficient R of Langmuir model fitting and Freundlich model fitting 2 0.952 and 0.909 respectively, which show that the Langmuir isothermal adsorption equation has better fitting effect on the adsorption of phosphorus by the modified biochar, and show that the adsorption behavior of the material on phosphorus is mainly monolayer adsorption. Meanwhile, according to the Langmuir fitting result, the maximum saturated adsorption quantity of the modified biochar to phosphorus is 3.67mg/g under the experimental condition.
Fifth embodiment: effect of different initial pH on the phosphorus adsorption effect of modified biochar and unmodified biochar.
Preparing 4-10 mesh coconut shell activated carbon. Preparing FeCl of 0.5mol/L 2 Solution, immersing coconut shell charcoal into FeCl 2 In the solution, the ratio of iron to carbon is 1:10, then calcium peroxide powder is added into the solution until the pH value is 7, the solution is stirred and immersed for 30min at 25 ℃ and 200r/min, and then aged for 24h, and the iron and calcium mixture is uniformly loaded on the surface of the biochar. Taking out the biochar, and pyrolyzing the biochar at 800 ℃ for 1h to obtain the biochar loaded with the iron/calcium oxide.
Weighing 0.5g of the modified biochar and the unmodified biochar into a 100mL centrifuge tube, adding 10mg/L,50mL and KH with pH of 3, 5, 7, 9 and 11 respectively 2 PO 4 The solution was subjected to shaking at a speed of 200r/min at 25℃for 12h, and then filtered through a 0.45 μm aqueous filter, and the total phosphorus concentration in the water sample was determined, three replicates each.
As shown in FIG. 9, the unmodified biochar has no obvious change on the removal rate of phosphorus at the pH value of 3-11, and is less than 10%. At pH 3, the phosphorus removal effect of the modified biochar is remarkably reduced to 45.72%, which indicates that the acidic condition is unfavorable for the removal of phosphorus by the modified biochar. When the pH is 5-11, the removal rate of the modified biochar to phosphorus is more than 92%, and when the pH is 11, the removal rate of the modified biochar to phosphorus is 99.43% along with the increase of the pH.
Example six: influence of coexisting ions on the phosphorus adsorption effect of the modified biochar.
Preparing 4-10 mesh coconut shell activated carbon. Preparing FeCl of 0.5mol/L 2 Solution, immersing coconut shell charcoal into FeCl 2 In the solution, the ratio of iron to carbon is 1:10, then calcium peroxide powder is added into the solution until the pH value is 7, the solution is stirred and immersed for 30min at 25 ℃ and 200r/min, and then aged for 24h and 24h, and the iron and calcium mixture is uniformly loaded on the surface of the biochar. Taking out the biochar, and pyrolyzing the biochar at 800 ℃ for 1h to obtain the biochar loaded with the iron/calcium oxide.
As shown in FIG. 10, SO compared with the blank group 4 2- ,CO 3 2- ,HCO 3 - And F - All have inhibition effect on the dephosphorization effect of the modified biochar, wherein HCO 3 - The inhibition of (c) is maximum and the removal rate is reduced to 49.38%. The reason is presumed to be a part of SO 4 2- ,CO 3 2- ,HCO 3 - And F - Easy to combine with Ca 2+ And insoluble precipitate is formed, so that the phosphorus removal rate of the modified biochar is reduced. NO (NO) 3 - The effect of removing phosphorus on the modified biochar is not greatly influenced.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (10)
1. A sewage treatment method using iron/calcium oxide loaded biochar is characterized in that: adding the iron/calcium oxide loaded biochar into sewage for sewage treatment;
the iron/calcium oxide loaded biochar is prepared by the following method:
s1, preparing ferrous chloride solution;
s2, immersing the biochar into a ferrous chloride solution, and then adding calcium peroxide powder into the ferrous chloride solution for oscillation and aging treatment;
s3, taking out the biochar in the solution, and pyrolyzing the biochar to obtain the biochar loaded with the iron/calcium oxide.
2. A preparation method of iron/calcium oxide loaded biochar is characterized by comprising the following steps:
s1, preparing ferrous chloride solution;
s2, immersing the biochar into a ferrous chloride solution, and then adding calcium peroxide powder into the ferrous chloride solution for oscillation and aging treatment;
s3, taking out the biochar in the solution, and pyrolyzing the biochar to obtain the biochar loaded with the iron/calcium oxide.
3. The preparation method according to claim 2, characterized in that: the concentration of the ferrous chloride solution is 0.5-2mol/L.
4. The preparation method according to claim 2, characterized in that: the biochar is coconut shell biochar.
5. The preparation method according to claim 2, characterized in that: in the step S2, biochar is added into the ferrous chloride solution according to the iron-carbon ratio of 10:1-5:1.
6. The preparation method according to claim 2, characterized in that: in the step S2, the oscillation temperature is 25 ℃, the rotation speed is 200rpm, and the oscillation time is 24 hours.
7. The preparation method according to claim 2, characterized in that: and in the step S3, the pyrolysis temperature is 800 ℃, and the pyrolysis time is 1h.
8. A loaded iron/calcium oxide biochar prepared by the method of any one of claims 2 to 7.
9. Use of the iron/calcium oxide loaded biochar according to claim 8 in wastewater treatment.
10. Use of the iron/calcium oxide loaded biochar of claim 8 for phosphorous removal.
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