CN113426415A - Iron-based biochar composite material and preparation method and application thereof - Google Patents
Iron-based biochar composite material and preparation method and application thereof Download PDFInfo
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- CN113426415A CN113426415A CN202110821836.8A CN202110821836A CN113426415A CN 113426415 A CN113426415 A CN 113426415A CN 202110821836 A CN202110821836 A CN 202110821836A CN 113426415 A CN113426415 A CN 113426415A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003763 carbonization Methods 0.000 claims abstract description 27
- 238000000197 pyrolysis Methods 0.000 claims abstract description 27
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 26
- 229910052785 arsenic Inorganic materials 0.000 abstract description 17
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002893 slag Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- 240000008564 Boehmeria nivea Species 0.000 description 8
- 239000013067 intermediate product Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000017060 Arachis glabrata Nutrition 0.000 description 5
- 244000105624 Arachis hypogaea Species 0.000 description 5
- 235000010777 Arachis hypogaea Nutrition 0.000 description 5
- 235000018262 Arachis monticola Nutrition 0.000 description 5
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000020232 peanut Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- -1 rolled sheet Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4837—Lignin
-
- 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)
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- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the field of environmental engineering materials and the technical field of water treatment, and provides an iron-based biochar composite material as well as a preparation method and application thereof. The preparation method of the composite material comprises the following steps: and (3) carrying out first pyrolysis and carbonization on agricultural and forestry waste to obtain biochar, mixing and acidifying the obtained biochar and iron-based waste residue, and carrying out second pyrolysis and carbonization to obtain the iron-based biochar composite material. In the process of preparing the iron-based biochar composite material, agricultural and forestry wastes and industrial iron-containing wastes are fully recycled, and the prepared iron-based biochar composite material has a removal rate of more than 90% of heavy metals in a low-concentration mixed heavy metal water sample with complex components, and has a removal rate of more than 99.7% of pentavalent arsenic in a pentavalent arsenic water sample containing 1-10 mg/L, so that the iron-based biochar composite material has a very excellent removal and adsorption effect.
Description
Technical Field
The invention relates to the field of environmental engineering materials and the technical field of water treatment, in particular to an iron-based biochar composite material and a preparation method and application thereof.
Background
The agricultural and forestry wastes are important members of wastes, are important biomass resources and mainly comprise straws, rice husks, edible fungus matrixes, leftover materials, firewood, barks, peanut shells, branch firewood, rolled barks, wood shavings and the like. The existing agricultural and forestry waste recycling comprises gasification and power generation of agricultural and forestry waste, and preparation of fuel ethanol by wood molding fuel or liquefaction, so that the existing research on recycling of agricultural and forestry waste only remains on how to convert the agricultural and forestry waste into energy resources. The agricultural and forestry wastes can be pyrolyzed and carbonized under the anoxic condition to generate the biochar, so that the biochar has great potential when being used for treating water body pollution, and a new mode can be provided for recycling the agricultural and forestry wastes.
However, the effect of treating pollutants by using biochar alone is not very ideal, and biochar loaded with metal ions has a good effect on pollutants, such as biochar containing iron base, aluminum base, manganese base, calcium base and the like. Wherein the treatment effect with the iron-based biochar is more excellent, however, the iron raw material for firing the iron-supported biochar is iron powder, FeCl3，Fe3O4Etc., these raw materials are relatively expensive and are not suitable for practical large-scale industrial production, and there is a need to find alternative inexpensive iron-containing materials.
Meanwhile, with the increase of the yield of Chinese steel, more and more solid wastes are generated, and in blast furnace iron making, 300-500 kg of blast furnace slag is generated when one ton of pig iron is produced, and the main components of the blast furnace slag are CaO and SiO2、MgO、Al2O3And Fe2O3. When steel is forged and hot-rolled by hot working, a large amount of iron scales are often formed on the surface of the steel due to the reaction of steel and oxygen in air, so that accumulation and resource waste are caused, wherein the iron content is as high as 80-90%, and how to effectively utilize the iron-based waste residues is the field of energyDomain has been a problem faced.
With the rapid development of industrial industries, heavy metals are continuously accumulated in the ecological environment, and the diversity of plants and microorganisms in the ecological environment is reduced. After entering the human body, the heavy metals entering the food chain react with various proteins and enzymes in the human body to lose their activity. Or the medicine is enriched in human body, and acute or subacute poisoning of human body can be caused after tolerance limit of human body is exceeded. Therefore, the understanding of the current situation of heavy metal pollution is deepened, and a scientific and safe method for treating heavy metal pollution is a hot spot of recent research of domestic and foreign scholars.
Coagulation-flocculation, oxidation/reduction reaction, ion exchange, membrane method and adsorption are the most commonly used methods for removing heavy metals in water, coagulation and flocculation can generate sludge containing arsenic, and treatment procedures are increased; the removal of heavy metals in water by ion exchange may be affected by other interfering ions; the membrane process is high in cost and not attractive to practical cases.
Therefore, the iron-based biochar composite material prepared from the agricultural and forestry waste and the iron-based waste residues is of great significance to researchers in the field when the iron-based biochar composite material is used for removing heavy metal elements in water.
Disclosure of Invention
In view of the above, the invention provides a preparation method of an iron-based biochar composite, which takes agricultural and forestry wastes and iron-based waste residues as raw materials and realizes double regeneration treatment of agricultural wastes and industrial wastes.
In order to achieve the above object, the present invention firstly provides a preparation method of an iron-based biochar composite material, comprising the following steps:
and (3) carrying out first pyrolysis and carbonization on agricultural and forestry waste to obtain biochar, mixing and acidifying the obtained biochar and iron-based waste residue, and carrying out second pyrolysis and carbonization to obtain the iron-based biochar composite material.
Further, the first pyrolysis and carbonization steps are as follows:
placing the agricultural and forestry waste which is naturally dried, ground and sieved in a tubular furnace, heating to 500-900 ℃ at a heating rate of 2-10 ℃/min, and then preserving heat for 1-3 h to finish primary pyrolysis and carbonization, wherein the furnace is in an inert atmosphere during pyrolysis and carbonization.
Further, the acidification step is as follows:
mixing the biochar and the iron-based waste residue, adding the mixture into acid liquor, uniformly stirring, standing, cleaning after standing, and drying to finish acidification.
Furthermore, the mass ratio of the biochar to the iron-based waste residue is 1: 1-3: 1.
Furthermore, the acid solution is one of hydrochloric acid, nitric acid and sulfuric acid, and the concentration of the acid solution is 30-60 wt%.
Furthermore, the standing time is 3-5 h.
Furthermore, the drying temperature is 50-70 ℃.
Further, the second pyrolysis and carbonization steps are as follows:
and (3) placing the acidified mixture into a tubular furnace, heating to 500-900 ℃ at a heating rate of 2-10 ℃/min, and then preserving heat for 1-3 h to finish secondary pyrolysis carbonization, wherein the furnace is in an inert atmosphere during pyrolysis carbonization.
The invention also aims to provide the iron-based biochar composite prepared by the preparation method of the iron-based biochar composite.
The invention further aims to provide application of the iron-based biochar composite material in removing heavy metal elements in a water body.
The invention has the following beneficial effects:
1. the invention makes the biological carbon fiber prepared by the agricultural and forestry waste through pyrolysis and carbonization have abundant free flowing pi electrons on a graphitized structure, and is a good electronic bridge for accelerating the electron transfer. The biochar has a large specific surface area and rich pore distribution, the surface not only has certain adsorption capacity to pollutants, but also provides uniform and large amount of load sites for substances with excellent effects on treating the pollutants, such as zero-valent iron, nitrogen elements and the like, and the adsorption capacity of the original biochar to heavy metal elements can be obviously enhanced after the biochar and iron-based waste residues are acidified and pyrolyzed and carbonized for the second time.
2. The materials and reagents used in the invention have low price and wide sources. Agricultural and forestry wastes which are rich in lignin and cellulose are selected as raw biochar preparation materials, so that the cost can be effectively reduced, the reutilization of agricultural wastes is enhanced, the effect of changing waste into valuable is realized by utilizing the industrial iron-containing wastes, and a new method is provided for the treatment of the industrial iron-containing wastes.
3. The preparation method of the iron-based biochar composite material provided by the invention is low in cost, simple and easy to implement, strong in operability, capable of preparing the iron-based biochar composite material with good specific surface area and rich pores, and excellent in treatment efficiency and stable in cycle performance in the aspect of water pollution treatment.
4. The iron-based biological composite material provided by the invention has a general adsorption and removal effect on heavy metals, the removal rate of the heavy metals in a low-concentration mixed heavy metal water sample with complex components is higher than 90%, the removal rate of pentavalent arsenic in a pentavalent arsenic water sample containing 1-10 mg/L is higher than 99.7%, and the iron-based biological composite material has a very excellent adsorption and removal effect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an electron microscope scanning image of a ramie biochar material prepared by the invention;
FIG. 2 is an electron microscope scanning image of the iron-based biochar composite modified by mixed iron scale and iron-making blast furnace slag prepared in the embodiment 1 of the invention;
FIG. 3 is an electron microscope scanning image of iron-based biochar composite modified by iron scale prepared in example 2 of the present invention;
fig. 4 is a graph showing the removal test kinetics of low-concentration pentavalent arsenic by three biochar materials (test conditions: initial concentration of pentavalent arsenic 1061 μ g/L, pH 7 of water sample, test temperature T25 ℃, and added amount of biochar material 1 g/L).
Detailed Description
The application provides a preparation method of an iron-based biochar composite, which comprises the following steps:
and (3) carrying out first pyrolysis and carbonization on agricultural and forestry waste to obtain biochar, mixing and acidifying the obtained biochar and iron-based waste residue, and carrying out second pyrolysis and carbonization to obtain the iron-based biochar composite material.
Further, the first pyrolysis and carbonization steps are as follows:
placing the agricultural and forestry waste which is naturally dried, ground and sieved in a tubular furnace, heating to 500-900 ℃ at a heating rate of 2-10 ℃/min, and then preserving heat for 1-3 h to finish primary pyrolysis and carbonization, wherein the furnace is in an inert atmosphere during pyrolysis and carbonization.
The agricultural and forestry waste used in the present invention is not particularly limited in source, and includes, but is not limited to, straw, rice hull, edible mushroom substrate, leftover, firewood, bark, peanut shell, tape wood, rolled sheet, and wood shavings.
Preferably, the rate of temperature rise is 10 ℃/min.
Preferably, the incubation is started after the temperature is raised to 500 ℃.
Preferably, the incubation time is 2 h.
Further, the acidification step is as follows:
mixing the biochar and the iron-based waste residue, adding the mixture into acid liquor, uniformly stirring, standing, cleaning after standing, and drying to finish acidification.
The iron-based slag used in the present invention is not particularly limited in its source, and includes, but is not limited to, iron-making blast furnace slag and iron scale.
Preferably, the iron-based waste slag can be a mixture of iron-making blast furnace slag and iron scale; more preferably, the mass ratio of the iron-making blast furnace slag to the iron scale is 1: 1.
Furthermore, the mass ratio of the biochar to the iron-based waste residue is 1: 1-3: 1.
Furthermore, the acid solution is one of hydrochloric acid, nitric acid and sulfuric acid, and the concentration of the acid solution is 30-60 wt%.
Preferably, the acid solution concentration is 50 wt%.
Furthermore, the standing time is 3-5 h.
Preferably, the standing time is 4 h.
Furthermore, the drying temperature is 50-70 ℃.
Preferably, the drying temperature is 60 ℃.
Further, the second pyrolysis and carbonization steps are as follows:
and (3) placing the acidified mixture into a tubular furnace, heating to 500-900 ℃ at a heating rate of 2-10 ℃/min, and then preserving heat for 1-3 h to finish secondary pyrolysis carbonization, wherein the furnace is in an inert atmosphere during pyrolysis carbonization.
Preferably, the rate of temperature rise is 10 ℃/min.
Preferably, the incubation is started after the temperature is raised to 500 ℃.
Preferably, the incubation time is 2 h.
The invention provides an iron-based biochar composite material prepared by the preparation method of the iron-based biochar composite material.
The invention provides an application of the iron-based biochar composite material in removing heavy metal elements in a water body.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An iron-based biochar composite is prepared by the following steps:
(1) taking ramie straws which are naturally air-dried, ground and sieved as a biochar raw material, placing the biochar raw material in a tubular furnace, heating at the speed of 10 ℃/min under the nitrogen atmosphere, and keeping the temperature for 2 hours after the temperature reaches 500 ℃ to obtain Ramie Biochar (RB);
(2) the method comprises the steps of taking the slag of the iron-making blast furnace and the iron scale as modified raw materials, uniformly mixing the ramie biochar with the iron scale and the slag of the iron-making blast furnace according to the mass of 900mg, 300mg and 300mg, adding the mixture into 50 wt% of nitric acid, standing and acidifying for 4 hours.
(3) And (3) filtering the acidified mixture by using a circulating water type vacuum pump, washing the acidified mixture by using deionized water, and drying the washed mixture in an oven at 60 ℃ overnight to obtain an intermediate product.
(4) Transferring the intermediate product into a tubular furnace, heating at a speed of 10 ℃/min under a nitrogen atmosphere, and keeping the temperature at 900 ℃ for 2 h;
(5) and naturally cooling after the reaction is finished, and finally obtaining the iron-based biochar composite (BOS) modified by the mixed iron scale and the ironmaking blast furnace slag.
Example 2
(1) Taking ramie straws which are naturally dried, ground and sieved as a biochar raw material, placing the biochar raw material in a tubular furnace, heating at the speed of 8 ℃/min under the nitrogen atmosphere, and keeping the temperature for 1.5h after the temperature reaches 700 ℃ to obtain the ramie biochar;
(2) the method comprises the steps of taking iron oxide scales as modified raw materials, uniformly mixing 900mg and 300mg of ramie biochar with the iron oxide scales, adding the mixture into 30 wt% hydrochloric acid, standing and acidifying for 4 hours.
(3) And (3) filtering the acidified mixture by using a circulating water type vacuum pump, washing the acidified mixture by using deionized water, and drying the washed mixture in an oven at 50 ℃ overnight to obtain an intermediate product.
(4) Transferring the intermediate product into a tubular furnace, heating at a speed of 8 ℃/min under a nitrogen atmosphere, and keeping the temperature for 1.5h after the temperature reaches 700 ℃;
(5) and naturally cooling after the reaction is finished, and finally obtaining the iron-based biochar composite (BO) modified by the iron scale.
Example 3
(1) Taking naturally air-dried, ground and sieved rice hulls as a biochar raw material, placing the biochar raw material in a tube furnace, heating at a speed of 2 ℃/min under a nitrogen atmosphere, and keeping the temperature for 1h after the temperature reaches 900 ℃ to obtain rice hull biochar;
(2) the method comprises the steps of taking iron-making blast furnace slag as a modified raw material, uniformly mixing 500mg and 500mg of rice hull biochar with 500mg of iron scale, adding the mixture into 40 wt% sulfuric acid, standing and acidifying for 3 hours.
(3) And (3) filtering the acidified mixture by using a circulating water type vacuum pump, washing the acidified mixture by using deionized water, and drying the washed mixture in an oven at 70 ℃ overnight to obtain an intermediate product.
(4) Transferring the intermediate product into a tubular furnace, heating at a speed of 2 ℃/min under the nitrogen atmosphere, and keeping the temperature for 1h after the temperature reaches 900 ℃;
(5) and naturally cooling after the reaction is finished, and finally obtaining the iron-based biochar composite modified by the iron-making blast furnace slag.
Example 4
(1) Taking ground and sieved peanut shells after natural air drying as a biochar raw material, placing the biochar raw material in a tube furnace, heating at a speed of 4 ℃/min under a nitrogen atmosphere, and keeping the temperature for 2 hours after the temperature reaches 800 ℃ to obtain the biochar of the peanut shells;
(2) the method comprises the steps of taking the iron-making blast furnace slag as a modified raw material, uniformly mixing 500mg and 500mg of peanut shell biochar and iron scale, adding the mixture into 40 wt% of nitric acid, standing and acidifying for 5 hours.
(3) And (3) filtering the acidified mixture by using a circulating water type vacuum pump, washing the acidified mixture by using deionized water, and drying the washed mixture in an oven at 65 ℃ overnight to obtain an intermediate product.
(4) Transferring the intermediate product into a tubular furnace, heating at a speed of 4 ℃/min under a nitrogen atmosphere, and keeping the temperature for 1h after the temperature reaches 800 ℃;
(5) and naturally cooling after the reaction is finished, and finally obtaining the iron-based biochar composite modified by the iron-making blast furnace slag.
Performance characterization
Specific surface areas and iron contents of Ramie Biochar (RB), the mixed iron scale and iron-making blast furnace slag modified iron-based biochar composite (BOS) prepared in example 1 and the iron scale modified iron-based biochar composite (BO) prepared in example 2 were measured, and SEM electron microscope scanning was performed to further understand the properties of the iron-based modified biochar composite, and the test results of the specific surface areas and the iron contents were shown in table 1, and the SEM electron microscope scanning results of the three biochar materials were shown in fig. 1, 2 and 3.
TABLE 1 specific surface area and iron content of three biochar materials
The specific surface area is measured to find that the specific surface area of the biochar is greatly increased by adding the iron scale and the iron-making blast furnace slag, and the biochar is beneficial to removing heavy metals in a water sample.
Adsorption test 1: low-concentration pentavalent arsenic water sample
RB biochar material, BO biochar material and BOS biochar material 50mg are respectively placed in a beaker filled with 50mL of 1mg/LAs to react for 24 hours, samples are taken at different time points to determine the removal rate of pentavalent arsenic, and the test result is shown in figure 4.
The result shows that in a low-concentration pentavalent arsenic (1mg/L) water body, the removal rate of RB biochar only reaches 7%, the removal effects of two biochar material agents, namely BO and BOS, are good, the removal rates respectively reach 99.5% and 99.9%, and the concentration of pentavalent arsenic in the treated water body is lower than 10 mug/L, so that the water body reaches the drinking water standard.
Adsorption test 2: high-concentration pentavalent arsenic water sample
And (3) putting 50mg of RB biochar material, BO biochar material and BOS biochar material into 50mL of beakers containing 10mg/LAs respectively, reacting for 24 hours, and measuring the removal rate of pentavalent arsenic after the reaction is finished, wherein the test results are shown in Table 2.
TABLE 2 removal rate of three biochar materials on high-concentration pentavalent arsenic water sample
The result shows that in a high-concentration pentavalent arsenic water sample, the treatment effect of the RB biochar material is still poor and is only 5.4%; the removal rate of the BO biochar material is greatly reduced and can only reach 71 percent; the removal effect of the BOS biochar material is far higher than that of the BO biochar material, and the removal rate of 99.7 percent is achieved.
Therefore, compared with the single iron-based waste residue component for modifying the biochar, the mixed iron-based waste residue component can obviously improve the treatment effect on pentavalent arsenic in a water sample after modifying the biochar.
Adsorption test 3: low-concentration mixed heavy metal water sample
50mg of the BOS biochar material prepared in example 1 was placed in a 50mL beaker containing 1mg/L of a mixed heavy metal solution of Cu, Zn, As and Cr, reacted for 24 hours, and the removal rate of each heavy metal by the BOS biochar was measured, and the test results are shown in Table 3.
TABLE 3 removal rate of BOS biochar material on low-concentration mixed heavy metal water sample
From the test results in table 3, the BOS biochar material prepared in example 1 of the present invention has a good removal effect on heavy metals in a mixed heavy metal water sample which is difficult to treat, both of which can reach over 90%, wherein the removal rate on Zn and Cu reaches over 99%, and the harm of heavy metals in a water body to an ecosystem is effectively reduced.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of an iron-based biochar composite material is characterized in that agricultural and forestry waste is subjected to primary pyrolysis carbonization to obtain biochar, and the obtained biochar and iron-based waste residue are mixed and acidified and then subjected to secondary pyrolysis carbonization to obtain the iron-based biochar composite material.
2. The preparation method of the iron-based biochar composite material according to claim 1, wherein the first pyrolysis and carbonization steps are as follows:
placing the agricultural and forestry waste which is naturally dried, ground and sieved in a tubular furnace, heating to 500-900 ℃ at a heating rate of 2-10 ℃/min, and then preserving heat for 1-3 h to finish primary pyrolysis and carbonization, wherein the furnace is in an inert atmosphere during pyrolysis and carbonization.
3. The method for preparing the iron-based biochar composite according to claim 1, wherein the acidification step is as follows:
mixing the biochar and the iron-based waste residue, adding the mixture into acid liquor, uniformly stirring, standing, cleaning after standing, and drying to finish acidification.
4. The preparation method of the iron-based biochar composite material according to claim 3, wherein the mass ratio of biochar to iron-based waste residue is 1: 1-3: 1.
5. The preparation method of the iron-based biochar composite material according to claim 4, wherein the acid solution is one of hydrochloric acid, nitric acid and sulfuric acid, and the concentration of the acid solution is 30-60 wt%.
6. The preparation method of the iron-based biochar composite material according to claim 5, wherein the standing time is 3-5 hours.
7. The preparation method of the iron-based biochar composite material according to claim 6, wherein the drying temperature is 50-70 ℃.
8. The preparation method of the iron-based biochar composite material according to claim 1, wherein the second pyrolysis and carbonization steps are as follows:
and (3) placing the acidified mixture into a tubular furnace, heating to 500-900 ℃ at a heating rate of 2-10 ℃/min, and then preserving heat for 1-3 h to finish secondary pyrolysis carbonization, wherein the furnace is in an inert atmosphere during pyrolysis carbonization.
9. The iron-based biochar composite prepared by the preparation method of any one of claims 1 to 8.
10. Use of the iron-based biochar composite of claim 9 for removing heavy metal elements from a body of water.
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