CN116408048A - Preparation and application of hydrothermal biochar/geopolymer composite material - Google Patents
Preparation and application of hydrothermal biochar/geopolymer composite material Download PDFInfo
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- CN116408048A CN116408048A CN202310280539.6A CN202310280539A CN116408048A CN 116408048 A CN116408048 A CN 116408048A CN 202310280539 A CN202310280539 A CN 202310280539A CN 116408048 A CN116408048 A CN 116408048A
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- 229920000876 geopolymer Polymers 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000010881 fly ash Substances 0.000 claims abstract description 42
- 239000002689 soil Substances 0.000 claims abstract description 36
- 239000010902 straw Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000012153 distilled water Substances 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 26
- 238000007789 sealing Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 15
- 238000002161 passivation Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000002985 plastic film Substances 0.000 claims description 13
- 229920006255 plastic film Polymers 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- -1 diethyl triamine pentaacetic acid Chemical compound 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 241000209140 Triticum Species 0.000 abstract description 3
- 235000021307 Triticum Nutrition 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011160 research Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000002956 ash Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000558306 Gynocardia odorata Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000207740 Lemna minor Species 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a preparation method of a hydrothermal biochar/geopolymer composite material, which comprises the steps of crushing wheat straw, uniformly mixing the crushed wheat straw with fly ash, adding potassium hydroxide solution, placing the mixture into a stirring device for stirring, curing to obtain a biochar/geopolymer composite material precursor, and carrying out hydrothermal carbonization to obtain the hydrothermal biochar/geopolymer composite material. Wherein the mixing amount of the straw powder, the potassium hydroxide and the distilled water is respectively 5-35 percent, 65-85 percent and 30-90 percent of the mass of the fly ash, the hydrothermal temperature is 220-260 ℃, the hydrothermal time is 4 hours, and the hydrothermal medium is 0-2 mol/L of potassium hydroxide solution; the prepared hydrothermal biochar/geopolymer composite material has good effects when being used for adsorbing and removing lead ions in water and passivating lead in soil in situ. The method has the advantages of simple process, low cost, low energy consumption, resource utilization of solid waste and environmental friendliness, and has wide application prospect in water and soil polluted by heavy metals.
Description
Technical Field
The invention belongs to the field of solid waste resource utilization and heavy metal pollution water and soil treatment, and particularly relates to a preparation method of a hydrothermal biochar/geopolymer composite material and application of the prepared hydrothermal biochar/geopolymer composite material in adsorbing lead ions in water and passivating lead in soil in situ.
Background
The biochar is a solid substance which is produced by thermochemical conversion of biomass raw materials such as straws, wood, livestock manure, sludge and the like under the condition of no (limited) oxygen, has high degree of aromaticity and mainly contains carbon elements, wherein the solid substance also comprises hydrogen (H), oxygen (O), nitrogen (N), sulfur (S), ash and trace elements, and the current preparation method of the biochar mainly comprises pyrolysis, gasification, hydrothermal carbonization and the like [ 1-3 ]. The biochar has the characteristics of larger specific surface area, abundant oxygen-containing functional groups, loose and porous microcosmic morphology, higher pH, CEC, stronger stability and the like, and can adsorb and deactivate heavy metals in the modes of surface complexation, precipitation generation, physical adsorption, cation exchange and the like, so that the biochar has wide application prospects [ 4-6 ] in water heavy metal adsorption removal and soil heavy metal deactivation. However, the original biochar is not ideal in adsorption and passivation performance on heavy metals, and needs to be modified to a certain extent or compounded with other materials [ 7 ].
Geopolymer, abbreviated as geopolymer, is an amorphous to semi-crystalline inorganic polymeric aluminosilicate obtained by dissolving and polycondensing calcined clay mineral or fly ash and other aluminosilicate raw materials under the action of strong alkaline excitant, and has the following characteristics of [ SiO 4 ] 4- Tetrahedra and [ AlO ] 4 ] 5- Zeolite-like porous anion skeleton structure formed by connecting tetrahedrons through covalent bonds formed by sharing vertex oxygen atoms, wherein the molecular structure can be abbreviated as R 2 O-Al 2 O 3 -SiO 2 -H 2 O (r=na, K) [ 8 ]. The unique zeolite-like structure of the geopolymer enables the geopolymer to have ion exchange and adsorption properties similar to those of zeolite, and has good application potential in the treatment of water and soil heavy metal pollution. Darmayanti et al [ 9 ] report that the structural order of sodium type geopolymer is higher than that of potassium type geopolymer, and thus has higher Cu 2+ The adsorption capacity can reach 40mg/g, and the adsorption process accords with Langmuir isotherm and pseudo-second-order kinetics. In addition, recent studies have found that polymers are converted to zeolites with higher structural order under certain hydrothermal reaction conditions, thereby improving their pore structure and adsorption properties [ 10,11 ]. The preparation of the hydrothermal biochar and the hydrothermal conversion of the geopolymer are synchronously carried out, so that the biochar can be modified by utilizing the alkaline environment of the geopolymer, the energy consumption can be saved, and the two purposes can be achieved.
A large number of domestic and foreign patents and literature data are consulted through the system, and no report is found about the hydrothermal biochar/geopolymer composite material and the relative report about the adsorption removal of lead in water and the in-situ passivation of soil lead.
The following are references given by the inventors:
【1】 The method comprises the steps of (1) long crane (Wang Jianlong, lixin, su Huihui, sun Zheng, wang Xueting) biological charcoal repair of polycyclic aromatic hydrocarbon polluted soil research progress [ J/OL ]. Applied chemical industry: 1-7[2023-03-13].
【2】 Zhang Xiaoying, chen Su, liu Ying, feng Tianzhen, chaulmoogra. Biochar aging and effect on heavy metal adsorption fixation research progress [ J/OL ]. Programming for agricultural resources and environmental sciences: 1-15[2023-03-13].
【3】 Ginger crystal, wu Yi, cheng Guang remote. Biochar modification and research on removal of pollutants in water [ J ]. Functional material, 2022, 53 (12): 12073-12084.
【4】 Guo Dandan, xiaowei. Modified biochar has adsorption performance to Pb (2+) and Cd (2+) and mechanism research [ J/OL ]. Applied chemical industry: 1-8[2023-03-14].
【5】 Song Shaohua, xu Jinlan, song Xiaoqiao, in the same general as the research progress of magnetic biomass charcoal for repairing heavy metal contaminated water [ J ]. Functional materials, 2023, 54 (01): 1058-1069.
【6】 Zong Dapeng, tian Wen, li Wei, zhang Mengyan, xu Wumei, development of mechanism for passivating typical soil heavy metals with duckweed, agroforestry waste biochar [ J/OL ]. Ecotoxicological report: 1-18[2023-03-14].
【7】 Huang Shiyuan, lin Senhuan, deng Jian, wangguo Hua, li Yingjie. Research progress of clay mineral/biochar composite materials in water treatment [ J ]. Applied chemical, 2022, 51 (11): 3362-3368.
【8】Davidovits J.Geopolymers:inorganic polymeric new materials[J].Journal of Thermal Analysis and Calorimetry，1991，37(8)：1633-1656。
【9】Darmayanti L，Kadja G T，Notodarmojo S，Damanhuri E，Mukti RR.Structural alteration within fly ash-based geopolymers governing the adsorption of Cu 2+ from aqueous environment：Effect of alkali activation[J].Journal of Hazardous Materials，2019，377：305-314。
【10】He P Y，Zhang Y J，Zhang X M,Chen H.Diverse zeolites derived from a circulating fluidized bed fly ash based geopolymer for the adsorption of lead ions from wastewater.Journal of Cleaner Production，2021，312，127769。
【11】 Zhang Yaojun, zhang She, han Zhichao, he Panyang, chen Hao. Research progress on geopolymer in situ conversion of zeolite molecular sieves [ J ]. Materials guide, 2020, 34 (23): 23033-23041.
Disclosure of Invention
The invention aims to provide a preparation method of a hydrothermal biochar/geopolymer composite material, and the prepared composite material is applied to improving water environment or soil environment.
In order to achieve the above task, the present invention adopts the following technical solutions:
the preparation method of the hydrothermal biochar/geopolymer composite material is characterized by comprising the steps of placing pulverized fuel ash, straw powder and aqueous solution of potassium hydroxide into a stirring device for stirring to form uniformly mixed slurry, and forming and curing to obtain a biochar/pulverized fuel ash geopolymer precursor, wherein: the mixing amount of the straw powder, the potassium hydroxide and the water is based on the mass of the fly ash; the mixing amount of the straw powder is 5-35% of the mass of the fly ash, the mixing amount of the potassium hydroxide is 65-85% of the mass of the fly ash, the mixing amount of the water is 30-90% of the mass of the fly ash, the hydrothermal temperature is set to 220-260 ℃, and the hydrothermal time is set to 4 hours.
The method specifically comprises the following steps:
(1) Weighing fly ash according to the formula amount, and placing the fly ash in an automatic stirrer with a set program;
(2) Weighing straws according to the formula amount, drying, crushing by using a crusher, sieving by using a 100-mesh sieve, and adding the crushed straws into the automatic stirrer in the step (1) for fully and uniformly dry mixing;
(3) Weighing solid potassium hydroxide according to the formula amount;
(4) Weighing water according to the formula, and dissolving solid potassium hydroxide in water;
(5) Cooling the potassium hydroxide solution to room temperature, adding the potassium hydroxide solution into the stirrer in the step (2), and stirring for 10min to obtain uniform slurry;
(6) Placing the slurry into a plastic film sealing bag, placing the plastic film sealing bag into an incubator, curing for 8 hours at 80 ℃, taking out the incubator, and curing for 48 hours at room temperature to obtain a biochar/geopolymer composite material precursor;
(7) Filling the precursor in the step (6) into a hydrothermal reaction kettle, wherein the solid-to-liquid ratio is 1:10, weighing potassium hydroxide solution, adding the potassium hydroxide solution into a reaction kettle, and carrying out hydrothermal carbonization at 220-260 ℃ for 4 hours;
(8) Washing the product obtained in the step (7) with distilled water and absolute ethyl alcohol alternately, filtering until the filtrate is neutral, drying for 12 hours at 105 ℃ in a constant-temperature drying oven, and granulating to obtain particles with the particle size of 0.250-0.600 mm, namely the hydrothermal biochar/geopolymer composite material.
Experiments of the applicant show that the prepared hydrothermal biochar/geopolymer composite material can be applied to adsorption removal of lead ions in water and in-situ passivation of lead in soil.
The specific implementation is as follows:
(1) A certain amount of waterPlacing the thermal biochar/geopolymer composite material into a container with a certain volume and a concentration of C o Pb (NO) 3 ) 2 In the solution, the solution was subjected to centrifugation by shaking with a water bath constant temperature shaker for 24 hours, and Pb in the supernatant was detected by ICP 2+ The concentration, and the removal rate and the adsorption quantity of the hydrothermal biochar/geopolymer composite material on lead ions in water are calculated;
(2) Adding a certain amount of hydrothermal biochar/geopolymer composite material particles into simulated lead polluted soil, uniformly mixing, adding distilled water to keep 50% of field water holding capacity, taking out after 7d, air-drying, leaching effective-state lead in the soil by using diethyl triamine pentaacetic acid, detecting the concentration of lead ions in the extracting solution by using ICP, and calculating the passivation rate of the hydrothermal biochar/geopolymer composite material on the lead in the soil.
The invention is characterized in that the alkaline environment of the geopolymer is skillfully modified on the biochar, the biochar is prepared by utilizing the water heat, and the structural transformation of the geopolymer is promoted to be combined, so that the water heat biochar-fly ash geopolymer composite material for removing or passivating heavy metals is obtained.
Drawings
FIG. 1 is a process flow for preparing and applying a hydrothermal biochar/geopolymer composite;
FIG. 2 is a scanning electron micrograph of the hydrothermal biochar/geopolymer composite prepared in example 2;
FIG. 3 is a schematic illustration of Pb in soil passivated by a hydrothermal biochar/geopolymer composite 2+ Is a graph of the effect of (3).
FIG. 4 shows the adsorption removal rate and adsorption amount of lead ions in water by the hydrothermal biochar/geopolymer composite materials of application examples 1-3.
The invention will now be described in further detail with reference to the drawings and examples.
Detailed Description
In the examples below, the applicant gives examples of the preparation of hydrothermal biochar/geopolymer composites and their use in the adsorption removal of lead ions from water or in-situ passivation of soil lead.
The following examples are only for better explanation of the present invention, and the present invention is not limited to these examples.
The preparation of the hydrothermal biochar/geopolymer composite material adopts the main raw materials of industrial solid waste fly ash, agricultural solid waste straw powder and potassium hydroxide, wherein the mixing amount of the straw powder, the potassium hydroxide and the water is based on the mass of the fly ash; the mixing amount of the straw powder is 5-35% of the mass of the fly ash, the mixing amount of the potassium hydroxide is 65-85% of the mass of the fly ash, the mixing amount of the water is 30-90% of the mass of the fly ash, the hydrothermal temperature is set to 220-260 ℃, the hydrothermal time is set to 4h, and the hydrothermal medium is set to distilled water or potassium hydroxide aqueous solution.
The preparation method comprises the following steps:
(1) Wheat straw is collected in a local farmland, dried, crushed and sieved by a 100-mesh sieve for standby.
(2) The fly ash is selected from class I fly ash of Henan Sanjia power plant, the fly ash is dried in an oven for 10 hours at 105 ℃, and the main oxide composition (mass percent) of the fly ash is shown in table 1.
Table 1: oxide composition of fly ash (wt%)
| Oxide compound | SiO 2 | Al 2 O 3 | Fe 2 O 3 | CaO | Na 2 O | MgO | K 2 O | SO 3 | TiO 2 | Loss | Impurity(s) |
| wt％ | 52.77 | 29.14 | 5.81 | 4.49 | 0.48 | 0.98 | 2.53 | 0.81 | 1.44 | 0.84 | Allowance of |
(3) Potassium hydroxide, available from national pharmaceutical chemicals, inc.
Preparation example 1:
200g of fly ash raw material is accurately weighed, and based on the weighing (100%), the mass of straw powder is 20% of the mass of the fly ash, the doping amount of potassium hydroxide is 75% of the mass of the fly ash, and the mass of water is 50% of the mass of the fly ash by adopting an externally doping method.
Before preparation, water and potassium hydroxide are prepared into potassium hydroxide solution for standby.
Placing the fly ash and straw powder into an automatic stirrer, pouring the prepared potassium hydroxide solution, uniformly mixing and stirring, and reacting to form uniform slurry; and filling the slurry into a plastic film sealing bag for sealing, placing the plastic film sealing bag into an incubator for curing for 8 hours at 80 ℃, taking out the plastic film sealing bag, and curing for 48 hours at room temperature to obtain the biochar/geopolymer composite material precursor.
12g of the precursor is weighed and put into a hydrothermal reaction kettle, 120mL of distilled water is added, and the hydrothermal reaction is carried out for 4 hours at 220 ℃. Taking out after the hydrothermal reaction is finished, alternately flushing and filtering with distilled water and absolute ethyl alcohol until filtrate is neutral, drying at 105 ℃ for 12 hours, crushing, and sieving with a 30-60-mesh standard sieve to obtain the particle with the particle size of 0.25-0.60 mm, namely the hydrothermal biochar/geopolymer composite material (marked as 30 HBCGC-220-0).
Preparation example 2:
200g of fly ash raw material is accurately weighed, and based on the weighing (100%), the mass of straw powder is 20% of the mass of the fly ash, the solid potassium hydroxide doping amount is 75% of the mass of the fly ash, and the mass of water is 50% of the mass of the fly ash by adopting an externally doping method.
Before preparation, water and potassium hydroxide are prepared into potassium hydroxide solution for standby.
Placing the fly ash and straw powder into an automatic stirrer, pouring the prepared potassium hydroxide solution, uniformly mixing and stirring, and reacting to form uniform slurry; and filling the slurry into a plastic film sealing bag for sealing, placing the plastic film sealing bag into an incubator for curing for 8 hours at 80 ℃, taking out the plastic film sealing bag, and curing for 48 hours at room temperature to obtain the biochar/geopolymer composite material precursor.
12g of the precursor is weighed and put into a hydrothermal reaction kettle, 120mL of distilled water is added, and the hydrothermal reaction is carried out for 4 hours at 240 ℃. Taking out after the hydrothermal reaction is finished, alternately flushing and filtering with distilled water and absolute ethyl alcohol until filtrate is neutral, drying at 105 ℃ for 12 hours, crushing, and sieving with a 30-60-mesh standard sieve to obtain the particle with the particle size of 0.25-0.60 mm, namely the hydrothermal biochar/geopolymer composite material (marked as 30 HBCGC-240-0). FIG. 2 is a scanning electron micrograph of the sample prepared in example 2. Preparation example 3:
200g of fly ash raw material is accurately weighed, and based on the weighing (100%), the mass of straw powder is 20% of the mass of the fly ash, the solid potassium hydroxide doping amount is 75% of the mass of the fly ash, and the mass of water is 50% of the mass of the fly ash by adopting an externally doping method.
Before preparation, water and potassium hydroxide are prepared into potassium hydroxide solution for standby.
Placing the fly ash and straw powder into an automatic stirrer, pouring the prepared potassium hydroxide solution, uniformly mixing and stirring, and reacting to form uniform slurry; and filling the slurry into a plastic film sealing bag for sealing, placing the plastic film sealing bag into an incubator for curing for 8 hours at 80 ℃, taking out the plastic film sealing bag, and curing for 48 hours at room temperature to obtain the biochar/geopolymer composite material precursor.
12g of the precursor is weighed and put into a hydrothermal reaction kettle, 120mL of distilled water is added, and the hydrothermal reaction is carried out for 4 hours at 260 ℃. Taking out after the hydrothermal reaction is finished, alternately flushing and filtering with distilled water and absolute ethyl alcohol until filtrate is neutral, drying at 105 ℃ for 12 hours, crushing, and sieving with a 30-60-mesh standard sieve to obtain the particle with the particle size of 0.25-0.60 mm, namely the hydrothermal biochar/geopolymer composite material (marked as 30 HBCGC-260-0).
Experiments of the inventor prove that the hydrothermal biochar/geopolymer composite material prepared by the embodiment can efficiently adsorb and remove Pb in water 2+ And in situ passivating Pb (II) in the soil.
The specific implementation is as follows:
(1) Putting a certain amount of hydrothermal biochar/geopolymer composite material into a container with a certain volume and a concentration of C o Pb (NO) 3 ) 2 In the solution, oscillating for 24h with a water bath constant temperature oscillator, centrifuging, removing supernatant, and detecting Pb with ICP 2 + Concentration of C t And calculating the removal rate and adsorption quantity of the hydrothermal biochar/geopolymer composite material on lead ions in water;
(2) Adding a certain amount of hydrothermal biochar/geopolymer composite material particles into simulated lead polluted soil, uniformly mixing, adding distilled water to keep 50% of field water holding capacity, taking out after 7d, air-drying, leaching effective-state lead in the soil by using diethyl triamine pentaacetic acid, detecting the concentration of lead ions in the extracting solution by using ICP, and calculating the passivation rate of the hydrothermal biochar/geopolymer composite material on the lead in the soil.
Application experiment example 1:
(1) Adsorption: accurately weighing 0.05g of the hydrothermal biochar/geopolymer composite material sample (30 HBCGC-220-0) prepared in preparation example 1, adding into 100mL of 100mg/L lead nitrate solution, oscillating for 24h by a water bath constant temperature oscillator, centrifuging, and detecting Pb in the supernatant by ICP 2+ Concentration, and its removal rate and adsorption amount for lead ions were calculated to be 81.85% and 163.71mg/g, respectively (FIG. 4);
(2) And (3) in-situ passivation: 3.6g of the hydrothermal biochar/geopolymer composite sample (30 HBCGC-220-0) prepared in preparation example 1 was accurately weighed, 40g of simulated lead-contaminated soil was added, distilled water was added after uniform mixing to maintain 50% of field water holding capacity, and after 7d, the soil was taken out, air-dried, and the effective state lead in the soil was leached with diethyl triamine pentaacetic acid, and the lead ion concentration in the extract was detected with ICP, and the passivation rate of the soil lead was calculated to be 45.33% (FIG. 3).
Application experiment example 2:
(1) Adsorption: accurately weighing 0.05g of the hydrothermal biochar/geopolymer composite material sample (30 HBCGC-240-0) prepared in preparation example 2, adding into 100mL of 100mg/L lead nitrate solution, oscillating for 24h by a water bath constant temperature oscillator, centrifuging, and detecting Pb in the supernatant by ICP 2+ Concentration, and the removal rate and adsorption amount of lead ions were calculated to be 93.88% and 187.76mg/g, respectively (FIG. 4);
(2) And (3) in-situ passivation: 3.6g of the hydrothermal biochar/geopolymer composite sample (30 HBCGC-240-0) prepared in preparation example 2 was accurately weighed, 40g of simulated lead-contaminated soil was added, distilled water was added after uniform mixing to maintain 50% of field water holding capacity, and after 7d, the soil was taken out, air-dried, and the effective state lead in the soil was leached with diethyl triamine pentaacetic acid, and the lead ion concentration in the extract was detected with ICP, and the passivation rate of the soil lead was calculated to be 72.86% (FIG. 3).
Application experiment example 3:
(1) Adsorption: accurately weigh 0.05gPreparation of the sample of the hydrothermal biochar/Geopolymer composite (30 HBCGC-260-0) prepared in example 3, adding to 100mL of 100mg/L lead nitrate solution, shaking with a water bath constant temperature shaker for 24 hours, centrifuging, and detecting Pb in the supernatant with ICP 2+ Concentration, and its removal rate and adsorption amount for lead ions were calculated to be 76.06% and 152.12mg/g, respectively (FIG. 4);
(2) And (3) in-situ passivation: 3.6g of the hydrothermal biochar/geopolymer composite material sample (30 HBCGC-260-0) prepared in preparation example 3 was accurately weighed, 40g of simulated lead-contaminated soil was added, distilled water was added after uniform mixing to maintain 50% of field water holding capacity, and after 7d, the soil was taken out, air-dried, the effective state lead in the soil was leached with diethyl triamine pentaacetic acid, the lead ion concentration in the extract was detected with ICP, and the passivation rate of the soil lead was calculated to be 48.71% (FIG. 3).
Claims (5)
1. A method for preparing a hydrothermal biochar/geopolymer composite material is characterized in that fly ash, straw powder and aqueous solution of potassium hydroxide are placed into a stirring device to be stirred to form evenly mixed slurry, a biochar/geopolymer precursor is obtained through curing, and then the hydrothermal biochar/geopolymer composite material is obtained through hydrothermal reaction, washing, drying and granulating. Wherein the dosages of the straw powder, the potassium hydroxide and the distilled water are respectively 5% -35%, 65% -85% and 30% -90% of the mass of the fly ash, the hydrothermal temperature is 220 ℃ -260 ℃, the hydrothermal time is 4 hours, and the hydrothermal medium is 0-2 mol/L of potassium hydroxide solution.
2. The method according to claim 1, characterized in that it comprises in particular the following steps:
(1) Weighing fly ash according to the formula amount, and placing the fly ash in an automatic stirrer with a set program;
(2) Weighing straws according to the formula amount, drying, crushing by using a crusher, sieving by using a 100-mesh sieve, and adding the crushed straws into the automatic stirrer in the step (1) for fully and uniformly dry mixing;
(3) Weighing solid potassium hydroxide according to the formula amount;
(4) Weighing water according to the formula, and dissolving solid potassium hydroxide in water;
(5) Cooling the potassium hydroxide solution to room temperature, adding the potassium hydroxide solution into the stirrer in the step (2), and stirring for 10min to obtain uniform slurry;
(6) Placing the slurry into a plastic film sealing bag, placing the plastic film sealing bag into an incubator, curing for 8 hours at 80 ℃, taking out the incubator, and curing for 48 hours at room temperature to obtain a biochar/geopolymer composite material precursor;
(7) Filling the biochar/geopolymer composite material precursor obtained in the step (6) into a hydrothermal reaction kettle, and obtaining a solid-liquid ratio of 1:10, weighing potassium hydroxide solution, adding the potassium hydroxide solution into a reaction kettle, and carrying out hydrothermal carbonization at 220-260 ℃ for 4 hours to obtain a product;
(8) Washing the product obtained in the step (7) with distilled water and absolute ethyl alcohol alternately, filtering until the filtrate is neutral, drying for 12 hours at 105 ℃ in a constant-temperature drying oven, and granulating to obtain particles with the particle size of 0.250-0.600 mm, namely the hydrothermal biochar/geopolymer composite material.
3. The method of claim 1, wherein the fly ash comprises the following oxides in mass percent: siO (SiO) 2 ：52.77％，Al 2 O 3 ：29.14％，Fe 2 O 3 ：5.81％，CaO：4.49％，Na 2 O：0.48％，MgO：0.98％，K 2 O：2.53％，SO 3 ：0.81％，TiO 2 :1.44%, loss:0.84% and the balance of unavoidable impurities.
4. Use of the hydrothermal biochar/geopolymer composite material prepared by the method of claim 1 or 2 or 3 for adsorption removal of lead ions from water and in-situ passivation of lead in soil.
5. The use according to claim 4, characterized by the following implementation:
(1) Putting a certain amount of hydrothermal biochar/geopolymer composite material into a container with a certain volume and a concentration of C o Pb (NO) 3 ) 2 In the solution, the solution is oscillated for 24 hours by a water bath constant temperature oscillatorCentrifugal separation, detecting Pb in supernatant by ICP 2+ The concentration, and the removal rate and the adsorption quantity of the hydrothermal biochar/geopolymer composite material on lead ions in water are calculated;
(2) Adding a certain amount of hydrothermal biochar/geopolymer composite material particles into simulated lead polluted soil, uniformly mixing, adding distilled water to keep 50% of field water holding capacity, taking out after 7d, air-drying, leaching effective-state lead in the soil by using diethyl triamine pentaacetic acid, detecting the concentration of lead ions in the extracting solution by using ICP, and calculating the passivation rate of the hydrothermal biochar/geopolymer composite material on the lead in the soil.
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