CN113578264B - Hydroxyapatite modified biochar and preparation method and application thereof - Google Patents
Hydroxyapatite modified biochar and preparation method and application thereof Download PDFInfo
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 66
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 24
- 238000007873 sieving Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 241000209140 Triticum Species 0.000 claims description 20
- 235000021307 Triticum Nutrition 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 241001024327 Oenanthe <Aves> Species 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 40
- 238000000034 method Methods 0.000 abstract description 9
- 239000002028 Biomass Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 2
- 239000000047 product Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 34
- 240000008042 Zea mays Species 0.000 description 29
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 29
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 29
- 235000005822 corn Nutrition 0.000 description 29
- 239000010902 straw Substances 0.000 description 20
- 210000003608 fece Anatomy 0.000 description 15
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010668 complexation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052585 phosphate mineral Inorganic materials 0.000 description 2
- 239000002367 phosphate rock Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J20/048—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 phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (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)
Abstract
The invention provides hydroxyapatite modified biochar, a preparation method and application thereof, and belongs to the technical field of wastewater treatment. Firstly, pretreating raw materials, calcining to obtain biochar, adding the biochar into a hydroxyapatite aqueous solution, stirring, filtering to obtain a product, and calcining the product to obtain the hydroxyapatite modified biochar. The hydroxyapatite modified biochar provided by the invention has stronger adsorption capacity on lead, and provides a new material and a method for controlling lead pollution of water and comprehensive utilization of agricultural and forestry waste biomass.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to hydroxyapatite modified biochar, and a preparation method and application thereof.
Background
Heavy metal pollution caused by wastewater produced by industrial departments such as mining, chemical industry, petroleum refining and the like has become a serious environmental problem. Pb (II) is a highly toxic heavy metal pollutant widely existing in industrial wastewater, and the exceeding discharge of Pb (II) can cause serious harm to the natural environment and human health. The biomass forms stable biochar after pyrolysis carbonization, so that carbon emission generated by biomass combustion and natural degradation can be greatly reduced, and the aim of recycling waste production and waste cultivation is fulfilled. The carbonized biomass can be used as a high-efficiency pollution control material for sewage treatment, and can also be applied to soil to store carbon in the soil, and simultaneously improve and repair the soil. The backfilling process of forming biomass charcoal after carbonization is actually a carbon dioxide capturing and carbon sinking process, and is a very effective new way of carbon fixation and emission reduction.
The biochar as a novel pollution treatment material has the characteristics of carbon enrichment, regeneration, abundant reserves, environmental friendliness, low price and the like, and has wide prospect in the field of wastewater treatment. Biomass sources such as straws, corncobs and the like produced in the agricultural planting process of China are wide and low in price, the prepared biochar has the characteristics of large surface area, large porosity, stable structure and the like, but the plant-derived biochar is complex in physicochemical property, difficult to have outstanding chemical functional property, and low in adsorption capacity to Pb (II), and the plant-derived biochar only needs to be derived from lignin in plants, and a large amount of cellulose and hemicellulose are gradually decomposed in the pyrolysis process, so that the yield of the plant-derived biochar is low and limited in environmental application. Based on the above, the invention provides the hydroxyapatite modified biochar, and the preparation method and the application thereof, so as to improve the removal capability of heavy metals in wastewater.
Disclosure of Invention
The invention provides hydroxyapatite modified biochar, a preparation method and application thereof, so as to improve the removal capability of heavy metals in wastewater.
The first object of the present invention is to provide a method for preparing hydroxyapatite-modified biochar, comprising the steps of:
step 1, raw material pretreatment: soaking the raw materials in deionized water, removing surface impurities, drying to constant weight, and crushing and sieving to obtain a pretreated raw material;
step 2, preparing biochar: placing the pretreated raw materials into an anaerobic tube furnace, heating to 450-550 ℃, preserving heat for 40-100min, and cooling to room temperature to obtain the biochar.
Step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water to prepare an aqueous solution with the concentration of 0.05-0.3 mol/L, carrying out ultrasonic treatment for 20-30min to uniformly disperse the aqueous solution, adding the biochar obtained in the step 2, stirring the mixture at room temperature for 2-3 hours, filtering the mixture to obtain a product, and crushing and sieving the product for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 450-550 ℃ at the heating rate of 10-20 ℃/min, preserving the heat for 40-100min, and cooling to the room temperature to obtain the hydroxyapatite modified biochar.
Preferably, the hydroxyapatite modified biochar has an average particle size of 3686.5-4795nm and a pH value of 6.41-8.26.
Preferably, the drying temperature in step 3 is 105-115 ℃ and the drying time is 8-9h.
Preferably, the raw materials in the step 1 are crushed and sieved by a sieve with 1-2 mm; and 3, crushing the dried product in the step 3 before placing the crushed product in an anaerobic tube furnace, and sieving the crushed product with a sieve of 1-2 mm.
Preferably, the raw material in the step 1 is one of wheat ears, wheat straws, corn straw and cow dung mixture.
Preferably, when the raw material is a mixture of corn stalk and cow dung, the pretreatment of the raw material in step 1 specifically includes: soaking corn straw in deionized water, removing surface impurities, drying to constant weight, crushing the corn straw, sieving with a 2mm sieve, drying cow dung to constant weight, sieving with a 2mm sieve, and uniformly mixing the corn straw and the cow dung to obtain pretreated biochar; wherein, the adding amount of the corn stalk is 20% of the cow dung.
Preferably, the temperature rising rate in the anaerobic tube furnace in the steps 2 and 3 is 15 ℃/min.
The second object of the present invention is hydroxyapatite-modified biochar prepared according to the above method.
A third object of the present invention is to provide the use of the above hydroxyapatite-modified biochar in wastewater treatment.
Compared with the prior art, the invention has the following beneficial effects:
the invention respectively takes wheat ears, wheat straws, corn straws and cow dung as raw materials to prepare biochar, and the biochar is modified by hydroxyapatite; the Pb (II) is removed by the biochar prepared by taking wheat as a raw material mainly because of chemical precipitation, and the content of phosphorite-containing substances is increased after the hydroxyapatite is loaded, so that the precipitation with lead is enhanced. The biochar prepared from corn is loose in pores, and many phosphate minerals are also contained in cow dung, pb (II) is removed mainly by complexation of functional groups of a surface adsorbent, and the number of the functional groups is increased after hydroxyapatite is modified. The hydroxyapatite modified biochar has stronger adsorption capacity on lead, and the invention provides a new material and a method for controlling the lead pollution of water bodies, the restoration of heavy metal polluted soil and the comprehensive utilization of agricultural and forestry waste biomass.
Drawings
FIG. 1 shows the average particle size of each biochar;
FIG. 2 shows the pH of each biochar;
FIG. 3 is a graph showing the comparison of lead adsorption amount of cow dung added to corn material;
FIG. 4 is a graph showing comparison of lead adsorption amounts of different biochars.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The average particle diameters of the biochar and the hydroxyapatite modified biochar in the examples were measured by a laser particle sizer; determination of pH according to the solid mass (g): liquid volume (mL) =1:20 ratio, 1.00g biochar or hydroxyapatite modified biochar was weighed, 20mL deionized water was added, stirred for 1h, left to stand for 10min, and the pH of the supernatant was measured.
Example 1
Step 1, soaking corn stalks in deionized water, removing impurities on the surfaces of the corn stalks, drying the corn stalks to constant weight, and crushing wheat ears and sieving the wheat ears with a 2mm sieve to obtain a pretreated raw material;
step 2, preparing biochar: the pretreated raw materials are placed in an anaerobic tube furnace, the temperature is increased from room temperature to 500 ℃ at the heating rate of 15 ℃/min, the heat is preserved for 50min, the temperature is reduced to the room temperature, and the biochar is obtained and is marked as CO.
Step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water to prepare a solution with the concentration of 0.1mol/L, carrying out ultrasonic treatment for 20min to uniformly disperse the solution, adding the biochar in the step 2, stirring the solution for 2 hours at room temperature, carrying out suction filtration, drying the solution at 105 ℃ for 8 hours to obtain a product, and crushing the product and sieving the product with a 2mm sieve for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 500 ℃ at a heating rate of 15 ℃/min, preserving the heat for 50min, and cooling to the room temperature to obtain the hydroxyapatite modified biochar, which is denoted as CO-HAP.
Example 2
Step 1, soaking corn stalks in deionized water, removing surface impurities, drying to constant weight, crushing the corn stalks, sieving with a 2mm sieve, drying cow dung to constant weight, sieving with a 2mm sieve, and uniformly mixing the corn stalks and the cow dung to obtain a pretreatment raw material; wherein, the adding amount of the corn stalk is 20% of the cow dung.
Step 2, preparing biochar: and (3) placing the pretreated raw materials into an anaerobic tube furnace, heating from room temperature to 500 ℃ at a heating rate of 15 ℃/min, preserving heat for 50min, and cooling to room temperature to obtain the biochar, which is denoted as COC.
Step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water to prepare a solution with the concentration of 0.1mol/L, carrying out ultrasonic treatment for 20min to uniformly disperse the solution, adding the biochar in the step 2, stirring the solution for 2 hours at room temperature, carrying out suction filtration, drying the solution at 105 ℃ for 8 hours to obtain a product, and crushing the product and sieving the product with a 2mm sieve for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 500 ℃ at a heating rate of 15 ℃/min, preserving the heat for 50min, and cooling to the room temperature to obtain the hydroxyapatite modified biochar, which is denoted as COC-HAP.
Example 3
Step 1, soaking wheat ears in deionized water, removing impurities on the surfaces of the wheat ears, drying the wheat ears to constant weight, and crushing the wheat ears and sieving the crushed wheat ears with a 2mm sieve to obtain a pretreated raw material;
step 2, preparing biochar: and (3) placing the pretreated raw materials into an anaerobic tube furnace, heating from room temperature to 500 ℃ at a heating rate of 15 ℃/min, preserving heat for 50min, and cooling to room temperature to obtain biochar, which is marked as EOW.
Step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water to prepare a solution with the concentration of 0.1mol/L, carrying out ultrasonic treatment for 20min to uniformly disperse the solution, adding the biochar in the step 2, stirring the solution for 2 hours at room temperature, carrying out suction filtration, drying the solution at 105 ℃ for 8 hours to obtain a product, and crushing the product and sieving the product with a 2mm sieve for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 500 ℃ at a heating rate of 15 ℃/min, preserving the heat for 50min, and cooling to the room temperature to obtain the hydroxyapatite modified biochar, which is marked as EOW-HAP.
Example 4
Step 1, soaking wheat straw in deionized water, removing impurities on the surface of the wheat straw, drying the wheat straw to constant weight, and crushing the wheat straw and sieving the crushed wheat straw with a 2mm sieve to obtain a pretreated raw material;
step 2, preparing biochar: the pretreated raw materials are placed in an anaerobic tube furnace, the temperature is increased from room temperature to 500 ℃ at a heating rate of 15 ℃/min, the temperature is kept for 50min, the temperature is reduced to the room temperature, and the biochar is obtained and is marked as WS.
Step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water to prepare a solution with the concentration of 0.1mol/L, carrying out ultrasonic treatment for 20min to uniformly disperse the solution, adding the biochar in the step 2, stirring the solution for 2 hours at room temperature, carrying out suction filtration, drying the solution at 105 ℃ for 8 hours to obtain a product, and crushing the product and sieving the product with a 2mm sieve for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 500 ℃ at a heating rate of 15 ℃/min, preserving the heat for 50min, and cooling to the room temperature to obtain the hydroxyapatite modified biochar, which is named WS-HAP.
Example 5
Step 1, soaking wheat straw in deionized water, removing impurities on the surface of the wheat straw, drying the wheat straw to constant weight, and crushing the wheat straw and sieving the crushed wheat straw with a 2mm sieve to obtain a pretreated raw material;
step 2, preparing biochar: the pretreated raw materials are placed in an anaerobic tube furnace, the temperature is increased from room temperature to 450 ℃ at the heating rate of 15 ℃/min, the heat is preserved for 100min, the temperature is reduced to the room temperature, and the biochar is obtained and is marked as WS.
Step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water, preparing a solution with the concentration of 0.05mol/L, carrying out ultrasonic treatment for 30min to uniformly disperse the solution, adding the biochar obtained in the step 2, stirring the solution at room temperature for 3 hours, carrying out suction filtration, drying the solution at 115 ℃ for 9 hours to obtain a product, and crushing the product and sieving the product with a 2mm sieve for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 450 ℃ at a heating rate of 10 ℃/min, preserving the heat for 100min, and cooling to room temperature to obtain the hydroxyapatite modified biochar, which is named WS-HAP.
Example 6
Step 1, soaking corn stalks in deionized water, removing impurities on the surfaces of the corn stalks, drying the corn stalks to constant weight, and crushing wheat ears and sieving the wheat ears with a sieve of 1.6mm to obtain a pretreated raw material;
step 2, preparing biochar: the pretreated raw materials are placed in an anaerobic tube furnace, the temperature is increased from room temperature to 550 ℃ at the heating rate of 15 ℃/min, the heat is preserved for 40min, the temperature is reduced to the room temperature, and the biochar is obtained and is marked as CO.
Step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water to prepare a solution with the concentration of 0.3mol/L, carrying out ultrasonic treatment for 25min to uniformly disperse the solution, adding the biochar in the step 2, stirring the solution for 3 hours at room temperature, carrying out suction filtration, drying the solution at 100 ℃ for 9 hours to obtain a product, and crushing the product and sieving the product with a 1.6mm sieve for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 550 ℃ at a heating rate of 20 ℃/min, preserving the heat for 40min, and cooling to room temperature to obtain the hydroxyapatite modified biochar, which is denoted as CO-HAP.
Example 7
Step 1, soaking wheat ears in deionized water, removing impurities on the surfaces of the wheat ears, drying the wheat ears to constant weight, and crushing the wheat ears and sieving the crushed wheat ears with a 1mm sieve to obtain a pretreated raw material;
step 2, preparing biochar: and (3) placing the pretreated raw materials into an anaerobic tube furnace, heating from room temperature to 500 ℃ at a heating rate of 15 ℃/min, preserving heat for 80min, and cooling to room temperature to obtain biochar, which is marked as EOW.
Step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water to prepare a solution with the concentration of 0.2mol/L, carrying out ultrasonic treatment for 20min to uniformly disperse the solution, adding the biochar obtained in the step 2, stirring the solution for 2.5 hours at room temperature, carrying out suction filtration, drying the solution at 105 ℃ for 8 hours to obtain a product, and crushing the product and sieving the product with a 2mm sieve for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 500 ℃ at a heating rate of 15 ℃/min, preserving the heat for 80min, and cooling to the room temperature to obtain the hydroxyapatite modified biochar, which is marked as EOW-HAP.
Comparative example 1
The preparation method of the biochar, denoted as CO, by using corn stalks as raw materials is the same as that of the step 1-2 in the example 1.
Comparative example 2
The preparation method of the biochar, which is COC, by using corn stalks as raw materials is the same as that of the step 1-2 in the example 2.
Comparative example 3
The biochar prepared by taking wheat ears as raw materials is marked as EOW, and the specific preparation method is the same as that in the step 1-2 in the example 3.
Comparative example 4
The biochar prepared from wheat straw, denoted WS, was prepared in the same manner as in step 1-2 of example 4.
The average particle diameter and pH value of each biochar are illustrated by examples 1 to 4 and comparative examples 1 to 4, as shown in FIGS. 1 and 2.
The adsorption and fixation of the biochar to the heavy metal in the water body mainly comes from the complexation of the functional groups on the surface of the biochar, and the exchange between the biochar and the heavy metal ions acts on the physical adsorption, wherein the influence of the physical adsorption on the overall adsorption effect is lower on the complexation. The specific surface area and pore structure of biochar are the main factors affecting their physical adsorption and are susceptible to modification conditions. The particle size of the hydroxyapatite-modified biochar in examples 1 to 4 was increased and the specific surface area was relatively decreased. As can be seen from FIG. 1, the average particle diameters of CO, COC, EOW, WS are 2958.3nm, 384.9nm, 1900nm and 826.3nm, respectively, and the average particle diameters of CO-HAP, COC-HAP, EOW-HAP and WS-HAP are increased by 728.2nm, 4410.1nm, 2393.7nm and 3917.1nm, respectively, from the average particle diameters of CO, COC, EOW, WS after the modification by hydroxyapatite.
FIG. 2 shows the pH values of the biochar, and as can be seen from FIG. 2, the pH values of CO-HAP, COC-HAP, EOW-HAP, WS-HAP are 8.20, 8.26, 6.41, and 7.80, respectively, the pH values of the original biochar are alkaline, probably due to the fact that alkaline salt is released during thermal cracking of the raw materials, wherein the pH value of the COC is 1.37 higher than that of CO, probably due to the fact that cow dung contains a large amount of mineral elements, and the elements possibly start to separate from an organic matrix after carbonization, so that the pH value of the biochar is increased. After the hydroxyapatite modified biochar, the pH was reduced to different degrees, but was kept between 6 and 8, indicating an increased content of acidic functional groups in the hydroxyapatite modified biochar.
The use of hydroxyapatite-modified biochar in wastewater treatment is described below with examples 1 to 4 and comparative examples 1 to 4 as examples.
The lead adsorption amount was calculated as follows
And (3) wastewater simulation: weighing lead nitrate, diluting with water to prepare 1000mg/L standard lead stock solution, adding nitric acid to maintain the stock solution stable, and simulating wastewater by using the stock solution.
With HNO of 0.1mol/L 3 And NaOH to adjust pH of the wastewater to 3, respectively weighing 0.05g of different biochar, adding 600mg/L lead nitrate solution, oscillating at 25deg.C for 24h at 180r/min, filtering, measuring lead concentration, and determining the initial lead concentration and residual lead concentration according to the formula Q= (C) 0 -C e )/C 0 Lead adsorption rate was calculated by x 100% by the formula q= (C 0 -C e ) Calculating lead adsorption amount by XV/(m×1000), wherein Q represents adsorption rate, C 0 Represents the initial concentration of the solution, the unit is mg/L, C e The adsorption equilibrium concentration of the solution is expressed, the unit is mg/L, and q represents the adsorption amount of the adsorbent per unit mass; v represents the volume of the reaction solution in mL, m represents the mass of the adsorbent in g.
Table 1 shows the lead adsorption capacity and adsorption rate of different biochars. Biochar from corn is more prone to absorb heavy metal lead than biochar from wheat, possibly due to the different structures of the two. The wheat raw material biochar has the advantages that the specific surface area is low, the pore structure is incomplete, part of pores are burnt, mineral ash and the like are more, the pore diameter is larger, in addition, the wheat raw material biochar has higher inorganic mineral components such as carbonate, phosphate and silicon dioxide and higher cation exchange capacity, the corn raw material biochar has loose structure, more active sites can be exposed, chemical adsorption is facilitated, more small pores are distributed in the loose macropores of the corn raw material biochar, the specific surface area is increased, in addition, the content of organic carbon and functional groups in the corn raw material biochar is higher, and the complexing effect of heavy metal ions and oxygen-containing functional groups also increases the adsorption capacity of heavy metals. The adsorption effect of the lead possibly with complexation is more obvious, so the biochar prepared by taking corn as the raw material has better adsorption effect than the biochar prepared by taking wheat as the raw material
TABLE 1 lead adsorption and adsorption Rate of different biochars
FIG. 3 is a graph showing the comparison of the adsorption capacity of cow dung added to corn raw materials to lead, and shows that the adsorption capacity of COC is slightly lower than that of CO (30.1 mg/g lower), but the adsorption capacity of COC-HAP is far higher than that of CO-HAP, and the adsorption capacity of COC-HAP is increased by 210.6mg/g compared with that of CO-HAP, so that the adsorption capacity of lead can be remarkably improved by adding cow dung to corn straw to prepare biochar and then modifying the biochar by hydroxyapatite.
FIG. 4 is a graph showing comparison of lead adsorption amounts of different biochars. The adsorption effect of the biochar on lead in water before modification is poor, and the adsorption amounts of CO, COC, EOW, WS are 112.4mg/g, 82.3mg/g, 50.9mg/g and 44.8mg/g respectively. Compared with CO, COC, EOW, WS, the adsorption amounts of CO-HAP, COC-HAP, EOW-HAP and WS-HAP are respectively increased by 38mg/g, 278.7mg/g, 507.9mg/g and 394.4mg/g, 337.3%, 34%, 997.7% and 880.4% respectively, and the adsorption effects of the hydroxyapatite modified biochar are greatly improved, wherein the adsorption amount of CO-HAP on lead is the largest compared with the adsorption amount of CO, and the adsorption rate is 93%.
By modifying biochar of different raw materials through hydroxyapatite, the adsorption capacity of EOW-HAP is increased by 507mg/g compared with EOW, 997.7% is improved, the adsorption capacity of COC-HAP is increased by 394.6mg/g compared with COC, 478.0% is improved, and the reason is probably that Pb (II) is removed by biochar prepared by taking wheat as raw materials mainly due to chemical precipitation, the amount of phosphorite-containing substances is increased after the hydroxyapatite is loaded, and the precipitation with lead is enhanced. The biochar prepared from corn is loose in pores, and many phosphate minerals are also contained in cow dung, pb (II) is removed mainly by complexation of functional groups of a surface adsorbent, and the number of the functional groups is increased after hydroxyapatite is modified. The modified hydroxyapatite has stronger adsorption capacity to lead, and the invention provides a new material and a method for controlling lead pollution in water and comprehensively utilizing waste biomass in agriculture and forestry.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (3)
1. The application of the hydroxyapatite modified biochar in wastewater treatment is characterized in that the wastewater is lead-containing wastewater; the preparation of the hydroxyapatite modified biochar comprises the following steps:
step 1, raw material pretreatment: soaking the raw materials in deionized water, removing surface impurities, drying to constant weight, and crushing and sieving to obtain a pretreated raw material; the raw material is wheat ears or wheat stalks;
step 2, preparing biochar: placing the pretreated raw materials into an anaerobic tube furnace, heating from room temperature to 550 ℃ at a heating rate of 15 ℃/min, preserving heat for 50min, and cooling to room temperature to obtain biochar;
step 3, preparing hydroxyapatite modified biochar: adding hydroxyapatite into deionized water to prepare an aqueous solution with the concentration of 0.05-0.3 mol/L, carrying out ultrasonic treatment for 20-30min to uniformly disperse the aqueous solution, adding the biochar in the step 2, stirring for 2-3 hours at room temperature, carrying out suction filtration, drying to obtain a product, crushing and sieving for later use; wherein the mass ratio of the hydroxyapatite to the biochar is 1:1;
and (3) placing the dried and sieved product into an anaerobic tube furnace, increasing the temperature from room temperature to 550 ℃ at a heating rate of 15 ℃/min, preserving the heat for 50min, and cooling to room temperature to obtain the hydroxyapatite modified biochar, wherein the average particle size of the hydroxyapatite modified biochar is 3686.5-4795nm, and the pH value is 6.41-8.26.
2. The use of a hydroxyapatite modified biochar according to claim 1 in wastewater treatment, wherein the drying temperature in step 3 is 105-115 ℃ and the drying time is 8-9h.
3. The use of a hydroxyapatite modified biochar in wastewater treatment according to claim 1, wherein in step 1 the raw materials are crushed through a 1-2mm screen; and 3, crushing the dried product in the step 3 before placing the crushed product in an anaerobic tube furnace, and sieving the crushed product with a sieve of 1-2 mm.
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