CN114130357B - Preparation method and application of salt lake brine-modified biochar - Google Patents
Preparation method and application of salt lake brine-modified biochar Download PDFInfo
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- CN114130357B CN114130357B CN202111466417.3A CN202111466417A CN114130357B CN 114130357 B CN114130357 B CN 114130357B CN 202111466417 A CN202111466417 A CN 202111466417A CN 114130357 B CN114130357 B CN 114130357B
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- old brine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000012267 brine Substances 0.000 claims abstract description 80
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 80
- 239000002028 Biomass Substances 0.000 claims abstract description 48
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 37
- 150000002500 ions Chemical class 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 4
- 240000006162 Chenopodium quinoa Species 0.000 claims description 49
- 239000010902 straw Substances 0.000 claims description 36
- 238000000197 pyrolysis Methods 0.000 claims description 22
- 241001494479 Pecora Species 0.000 claims description 18
- 210000003608 fece Anatomy 0.000 claims description 18
- 239000010871 livestock manure Substances 0.000 claims description 18
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 15
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 15
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 14
- 229910001414 potassium ion Inorganic materials 0.000 claims description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- 241000196324 Embryophyta Species 0.000 claims description 11
- 241001465754 Metazoa Species 0.000 claims description 11
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 7
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- -1 Cr 3+ and Pb 2+ Chemical class 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 54
- 229910052573 porcelain Inorganic materials 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000012086 standard solution Substances 0.000 description 22
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 18
- 238000001914 filtration Methods 0.000 description 16
- 239000011651 chromium Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 229910052793 cadmium Inorganic materials 0.000 description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 241001131796 Botaurus stellaris Species 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000010784 textile waste Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 240000006122 Chenopodium album Species 0.000 description 1
- 235000009344 Chenopodium album Nutrition 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 206010021143 Hypoxia Diseases 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- B01J20/04—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
-
- 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
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Fertilizers (AREA)
- Water Treatment By Sorption (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a preparation method of salt lake old brine modified biochar, which comprises the following steps: mixing the biochar with the salt lake old brine, and drying to obtain the salt lake old brine modified biochar, or (1) fully contacting the biomass raw material with the salt lake old brine; (2) Washing and drying the biomass raw material treated in the step (1), and then pyrolyzing and carbonizing under the anoxic or anaerobic condition to obtain the salt lake old brine modified biochar. Compared with the biochar before modification, the biochar modified by the salt lake old brine has obviously improved adsorption effect on heavy metal ions, particularly Cr 3+ and Pb 2+, and can be used as an adsorption material for treating heavy metal ion pollution. Compared with the prior art, the invention not only can utilize and reduce pollutants, avoid waste, but also can treat waste with waste, and reduce the treatment cost of pollutants.
Description
Technical Field
The invention belongs to the field of biochar, and particularly relates to a preparation method of salt lake old brine modified biochar and application of salt lake old brine modified biochar in heavy metal ion pollution treatment.
Background
The biochar (Biochar) is a solid substance rich in carbon, which is generated by high-temperature conversion of biomass raw materials under the condition of oxygen deficiency or anaerobic condition, and has the advantages of large specific surface area, simple preparation process, low raw material cost, obvious adsorption effect and wide application prospect in the field of printing and dyeing wastewater treatment.
The biomass raw materials for preparing the biochar mainly comprise plant sources, animal sources, sludge sources and the like, and the selection principle comprises the following steps:
(1) Low cost, easy obtainment and good economic benefit; (2) high adsorption efficiency; (3) the energy consumption in the preparation process is low, and the secondary pollution is small; (4) Preferably, the biomass is abandoned to prepare the biochar, so that the reutilization of abandoned resources and the treatment of waste by waste are realized.
Quinoa belongs to dicotyledonous quinoa crops, and is suitable for growing in areas with high altitude, soil impoverishment and even alkalinity. The unique geographical environment and climate condition of the Qidamu basin is the natural soil for cultivating the quinoa, and the quinoa is successfully introduced in 2012, so that the Qidamu basin becomes a high-quality quinoa planting base in Qinghai and even nationwide, wherein the Haizhou in the Qidamu basin is an important planting area of Chenopodium album in Qinghai. According to statistics, the planting area of the quinoa in the green sea, the firewood and the wood basin in 2017 reaches 2106 hectares, the yield of the quinoa in 2019 is about 8000 tons, the yield value is about 4 hundred million yuan, the planting area exceeds the Shanxi province, the Gansu province and the like, and the quinoa is the largest planting area in the whole country and has strong regional representativeness. However, with this, quinoa straw has become a non-negligible agricultural waste and a biomass resource to be developed and utilized. The quinoa straw is rich in various natural carbon-containing components such as cellulose, hemicellulose, lignin (cellulose: 33.88%, hemicellulose: 20.32%, lignin: 18.18%), and the like, is one of valuable renewable lignocellulose biomass resources, and the natural growth characteristics of quinoa give unique advantages to the quinoa straw, so that the quinoa straw has great potential for preparing carbon materials.
The reserves of potassium, sodium, magnesium, lithium and other resources in the Qinghai salt lake in China are rich, wherein the reserve of magnesium salt reaches 48.16 hundred million tons. At present, development of salt lake resources is mainly focused on potassium extraction, magnesium resources exist in salt lake bittern after potassium extraction, and the salt lake bittern mainly comprises 298-330 g/L of magnesium chloride solution, a small amount of salt substances such as potassium chloride, sodium chloride and lithium chloride, and a small amount of solid insoluble substances such as algae substances and clay. The potassium-extracted old brine is a high-quality magnesium chloride resource, and is an important raw material for preparing metal magnesium from the old brine and magnesium chloride and magnesium compound products. Once the development of magnesium resources in the potassium-extracted old brine is delayed, the chemical composition of salt lake brine can be interfered besides the resource waste, so that the structural damage of salt lake mineral resources is caused. From this point of view, the utilization of the old brine of the salt lake is very necessary.
Chinese patent CN106904610a discloses a method for preparing activated carbon based on polyester textile waste by using bittern solution as template-chemical activator, namely, using polyester textile waste as precursor of carbon, using bittern solution as template, mixing bittern solution and polyester textile waste, pyrolyzing to form carbon coated magnesia, then using hydrochloric acid to dissolve magnesia particles, and then rinsing to obtain activated carbon based on polyester textile waste. In this method, a bittern solution is used as a template-chemical activator to form a micro-mesoporous structure in activated carbon, and in the process of forming the micro-mesoporous structure, the template-chemical activator needs to be dissolved and removed, unlike the function and purpose of a general modifier, and the patent does not give a technical suggestion as to whether modifying biochar with a bittern solution as a modifier to improve the effect of biochar on removal of heavy metal ions.
Disclosure of Invention
In order to improve the adsorption effect of the biochar on heavy metal ions, the invention aims to provide a preparation method of the salt lake old brine modified biochar, and compared with the biochar before modification, the adsorption effect of the salt lake old brine modified biochar on heavy metal ions, particularly Cr 3+ and Pb 2+, is obviously improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The preparation method of the salt lake old brine modified biochar comprises the following steps: and mixing the biochar with the salt lake old brine, and drying to obtain the salt lake old brine modified biochar.
Preferably, the biochar is obtained by pyrolysis and carbonization of a biomass raw material under anoxic or anaerobic conditions, wherein the biomass raw material is plant-derived biomass, animal-derived biomass or sludge-derived biomass.
More preferably, the plant-derived biomass is quinoa straw and the animal-derived biomass is sheep manure.
Preferably, the pyrolysis carbonization temperature is 300-800 ℃ and the time is 1-2 hours.
The inert gases such as nitrogen, argon and the like can be used for providing the anoxic or anaerobic conditions required by the pyrolysis carbonization.
When the biomass raw material is plant-derived biomass, the pyrolysis carbonization temperature is preferably 500-800 ℃. When the biomass raw material is animal-derived biomass, the pyrolysis carbonization temperature is preferably 300-400 ℃.
Preferably, the salt lake old brine contains 70-130 g/L of magnesium ions, 0.01-0.5 g/L of calcium ions, 0.1-5 g/L of potassium ions and 0.1-5 g/L of sodium ions.
More preferably, the salt lake old brine contains 90-110 g/L of magnesium ions, 0.04-0.1 g/L of calcium ions, 0.5-1 g/L of potassium ions and 1-3 g/L of sodium ions.
Most preferably, the salt lake old brine contains 100-103 g/L of magnesium ions, 0.03-0.06 g/L of calcium ions, 0.5-0.6 g/L of potassium ions and 1.5-1.9 g/L of sodium ions.
Preferably, the biochar is mixed with the salt lake old brine in a soaking manner.
More preferably, the method comprises immersing overnight to allow the biochar to be in sufficient contact with the salt lake brine, and then removing the excess salt lake brine.
The preparation method of the salt lake old brine modified biochar comprises the following steps:
(1) Fully contacting the biomass raw material with the salt lake old brine;
(2) Washing and drying the biomass raw material treated in the step (1), and then pyrolyzing and carbonizing under the anoxic or anaerobic condition to obtain the salt lake old brine modified biochar.
Preferably, the biomass raw material is fully contacted with the salt lake old brine in a soaking mode.
More preferably, the soaking is carried out overnight so that the biomass feedstock is fully contacted with the salt lake brine, after which the excess salt lake brine is removed.
Preferably, the salt lake old brine contains 70-130 g/L of magnesium ions, 0.01-0.5 g/L of calcium ions, 0.1-5 g/L of potassium ions and 0.1-5 g/L of sodium ions.
More preferably, the salt lake old brine contains 90-110 g/L of magnesium ions, 0.04-0.1 g/L of calcium ions, 0.5-1 g/L of potassium ions and 1-3 g/L of sodium ions.
Most preferably, the salt lake old brine contains 100-103 g/L of magnesium ions, 0.03-0.06 g/L of calcium ions, 0.5-0.6 g/L of potassium ions and 1.5-1.9 g/L of sodium ions.
Preferably, the biomass feedstock is a plant-derived biomass, an animal-derived biomass, or a sludge-derived biomass.
More preferably, the plant-derived biomass is quinoa straw and the animal-derived biomass is sheep manure.
Preferably, the pyrolysis carbonization temperature is 300-800 ℃ for 1-2 hours.
When the biomass raw material is plant-derived biomass, the pyrolysis carbonization temperature is preferably 500-800 ℃. When the biomass raw material is animal-derived biomass, the pyrolysis carbonization temperature is preferably 300-400 ℃.
The inert gases such as nitrogen, argon and the like can be used for providing the anoxic or anaerobic conditions required by the pyrolysis carbonization.
The salt lake old brine modified biochar prepared by the preparation method is prepared.
The application of the salt lake old brine modified biochar as an adsorption material in treating heavy metal ion pollution, wherein the heavy metal ion is Cr 3+ and/or Pb 2+.
The beneficial effects are that:
Compared with the biochar before modification, the biochar modified by the salt lake old brine has obviously improved adsorption effect on heavy metal ions, particularly Cr 3+ and Pb 2+, and can be used as an adsorption material for treating heavy metal ion pollution. Compared with the prior art, the invention not only can utilize and reduce pollutants, avoid waste, but also can treat waste with waste, and reduce the treatment cost of pollutants.
Drawings
FIG. 1 is a photograph of quinoa straw and salt lake old brine modified quinoa straw biochar, wherein I-quinoa straw and II-salt lake old brine modified quinoa straw biochar.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the embodiment and the attached drawings.
Example 1
A preparation method of salt lake old brine modified quinoa straw biochar comprises the following steps:
Washing quinoa straw with deionized water, drying in an oven at 105 ℃, crushing into powder by a crusher, placing in salt lake old brine, uniformly stirring, soaking overnight, filtering, discarding the old brine, washing the quinoa straw with deionized water for 3 times, and drying in the oven at 105 ℃. And respectively placing the modified quinoa straw powder in a porcelain boat, placing the porcelain boat in a tube furnace, pyrolyzing the porcelain boat at the temperature of 750 ℃ under the protection of argon, wherein the heating rate is 10 ℃/min, the pyrolysis time is 1h, taking out the porcelain boat after cooling to room temperature, grinding the porcelain boat, sieving the porcelain boat with a 100-mesh sieve, placing the porcelain boat into a self-sealing bag, marking the porcelain boat for later use, and obtaining a product photo shown in figure 1.
The modified quinoa straw biochar has the performance of removing heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, the standard solutions are mixed and diluted 10 times, mixed standard solutions are prepared, the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions measured by ICP are 104.8mg/L,94.3mg/L and 106.1mg/L respectively, the pH value of the solutions is regulated to 6, 30mL of the solutions are taken, 0.0504g of biochar is respectively added into a 50mL centrifuge tube, vibration absorption is carried out for 20h at room temperature, filter paper is used for filtration, mass concentrations of cadmium, chromium and lead ions in the solutions are measured by ICP, the removal rate and removal amount of the biochar to heavy metals are calculated, and experimental results are shown in Table 1:
Example 2
The preparation process of the modified quinoa straw biochar is the same as in example 1.
The modified quinoa straw biochar has the performance of removing heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, mixing and diluting 5 times, preparing mixed standard solution, adopting ICP to measure the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions to be 229.8mg/L,222.0mg/L and 238.2mg/L respectively, regulating the pH value of the solutions to be 4.5, taking 30mL of the solution, taking 0.0505g of biochar, respectively adding the solution into a 50mL centrifuge tube, vibrating and adsorbing for 20h at room temperature, filtering by filter paper, adopting ICP to measure the mass concentrations of cadmium, chromium and lead ions in the solutions, and calculating the removal rate and removal amount of the biochar to heavy metals, wherein the experimental results are shown in Table 2:
example 3
A preparation method of salt lake old brine modified quinoa straw biochar comprises the following steps:
The quinoa straw is washed by deionized water, dried in an oven at 105 ℃, and then crushed into powder by a crusher. Placing the powder in a porcelain boat respectively, placing in a tube furnace, pyrolyzing at 750 ℃ under the protection of argon, wherein the heating rate is 10 ℃/min, the pyrolysis time is 1h, placing in salt lake old brine after cooling to room temperature, uniformly stirring, soaking overnight, filtering, discarding the old brine, and drying in a 105 ℃ oven. Taking out, grinding, sieving with 100 mesh sieve, and packaging into self-sealing bag for marking.
The modified quinoa straw biochar has the performance of removing heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, the standard solutions are mixed and diluted 5 times, the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions measured by ICP are 229.8mg/L,222.0mg/L and 238.2mg/L respectively, the pH value of the solutions is adjusted to 4.5, 30mL of the solutions are taken, 0.0504g of biochar is respectively added into 50mL centrifuge tubes, vibration absorption is carried out for 20h at room temperature, filter paper is used for filtration, mass concentrations of cadmium, chromium and lead ions in the solutions are measured by ICP, the removal rate and removal amount of the biochar to heavy metals are calculated, and experimental results are shown in Table 3:
Example 4
A preparation method of salt lake old brine modified quinoa straw biochar comprises the following steps:
washing quinoa straw with deionized water, drying in an oven at 105 ℃, crushing into powder by a crusher, placing in salt lake old brine, uniformly stirring, soaking overnight, filtering, discarding the old brine, washing the quinoa straw with deionized water for 3 times, and drying in the oven at 105 ℃. And respectively placing the modified quinoa straw powder in a porcelain boat, placing the porcelain boat in a tube furnace, pyrolyzing the porcelain boat at the temperature of 750 ℃ under the protection of argon, wherein the heating rate is 10 ℃/min, the pyrolysis time is 2h, taking out the porcelain boat after cooling to room temperature, grinding the porcelain boat, sieving the porcelain boat with a 100-mesh sieve, and placing the porcelain boat into a self-sealing bag for marking and standby.
The modified quinoa straw biochar has the performance of removing heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, the standard solutions are mixed and diluted 5 times, the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions measured by ICP are 229.8mg/L,222.0mg/L and 238.2mg/L respectively, the pH value of the solutions is adjusted to 4.5, 30mL of the solutions are taken, 0.0503g of biochar is respectively added into 50mL centrifuge tubes, vibration absorption is carried out for 20h at room temperature, filter paper is used for filtration, mass concentrations of cadmium, chromium and lead ions in the solutions are measured by ICP, the removal rate and removal amount of the biochar to heavy metals are calculated, and experimental results are shown in Table 4:
Example 5
The preparation method of the salt lake old brine modified sheep manure biochar comprises the following steps:
The sheep manure is sieved by a 50-mesh sieve, then is placed in salt lake old brine, is uniformly stirred, is soaked overnight, is filtered, is discarded, is washed by deionized water for 3 times, and is dried in a 105 ℃ oven. And (3) respectively placing the modified sheep manure in a porcelain boat, placing the porcelain boat in a tube furnace, pyrolyzing the sheep manure at the temperature of 750 ℃ under the protection of argon, wherein the heating rate is 10 ℃/min, the pyrolysis time is 1h, taking out the sheep manure after cooling to room temperature, grinding the sheep manure, sieving the sheep manure with a 100-mesh sieve, and placing the sheep manure in a self-sealing bag for marking for later use.
The removal performance of the modified sheep manure biochar on heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, the standard solutions are mixed and diluted by 12.5 times, the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions measured by ICP are 77.3mg/L,73.8mg/L and 76.8mg/L respectively, the pH value of the solutions is regulated to 6, 30mL of the solutions is taken, 0.0501g of biochar is respectively added into a 50mL centrifuge tube, vibration absorption is carried out for 20h at room temperature, filter paper is used for filtration, the mass concentrations of cadmium, chromium and lead ions in the solutions are measured by ICP, the removal rate and the removal amount of the biochar to heavy metal are calculated, and the experimental results are shown in Table 5:
Example 6
The preparation method of the salt lake old brine modified sheep manure biochar comprises the following steps:
And (3) sieving sheep manure with a 50-mesh sieve, respectively placing the sheep manure into a porcelain boat, placing the porcelain boat into a tube furnace, pyrolyzing the porcelain boat at the temperature of 350 ℃ under the protection of argon, wherein the heating rate is 10 ℃/min, the pyrolysis time is 1h, placing the porcelain boat into salt lake old brine after cooling to room temperature, uniformly stirring, soaking the porcelain boat overnight, filtering, discarding the old brine, and drying the porcelain boat in a 105 ℃ oven. Taking out, grinding, sieving with 100 mesh sieve, and packaging into self-sealing bag for marking.
The removal performance of the modified sheep manure biochar on heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, the standard solutions are mixed and diluted 10 times, mixed standard solutions are prepared, the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions measured by ICP are 104.8mg/L,94.3mg/L and 106.1mg/L respectively, the pH value of the solutions is regulated to 6, 30mL of the solutions are taken, 0.0508g of biochar is added into 50mL centrifuge tubes respectively, vibration absorption is carried out for 20h at room temperature, filter paper is used for filtration, mass concentrations of cadmium, chromium and lead ions in the solutions are measured by ICP, the removal rate and removal amount of the biochar to heavy metal are calculated, and experimental results are shown in Table 6:
Comparative example 1
The quinoa straw is washed by deionized water, dried in an oven at 105 ℃, and then crushed into powder by a crusher. Placing the powder in porcelain boats respectively, placing in a tube furnace, pyrolyzing at 750deg.C under the protection of argon gas, wherein the heating rate is 10deg.C/min, the pyrolysis time is 2h, cooling to room temperature, taking out, grinding, sieving with 100 mesh sieve, and placing in self-sealing bag for marking.
The quinoa biochar has the performance of removing heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, mixing and diluting 5 times, preparing mixed standard solution, adopting ICP to measure the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions to be 229.8mg/L,222.0mg/L and 238.2mg/L respectively, regulating the pH value of the solutions to be 4.5, taking 30mL of the solution, taking 0.0508g of biochar, respectively adding the solution into a 50mL centrifuge tube, vibrating and adsorbing for 20h at room temperature, filtering by filter paper, adopting ICP to measure the mass concentrations of cadmium, chromium and lead ions in the solutions, and calculating the removal rate and removal amount of the biochar to heavy metals, and the experimental results are shown in Table 7:
Comparative example 2
The quinoa straw is washed by deionized water, dried in an oven at 105 ℃, and then crushed into powder by a crusher. Placing the powder in porcelain boats respectively, placing in a tube furnace, pyrolyzing at 550 ℃ under the protection of argon, wherein the heating rate is 10 ℃/min, the pyrolysis time is 1h, taking out, grinding, sieving with a 100-mesh sieve, and placing in a self-sealing bag for marking and standby.
The quinoa biochar has the performance of removing heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, mixing and diluting 5 times, preparing mixed standard solution, adopting ICP to measure the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions to be 229.8mg/L,222.0mg/L and 238.2mg/L respectively, regulating the pH value of the solutions to be 4.5, taking 30mL of the solution, taking 0.0506g of biochar, respectively adding the solution into a 50mL centrifuge tube, vibrating and adsorbing for 20h at room temperature, filtering by filter paper, adopting ICP to measure the mass concentrations of cadmium, chromium and lead ions in the solutions, and calculating the removal rate and removal amount of the biochar to heavy metals, wherein the experimental results are shown in Table 8:
Comparative example 3
The quinoa straw is washed by deionized water, dried in an oven at 105 ℃, and then crushed into powder by a crusher. Placing the powder in porcelain boats, placing in a tube furnace, pyrolyzing at 750deg.C under the protection of argon gas, wherein the heating rate is 10deg.C/min, pyrolyzing time is 1h, cooling to room temperature, placing in magnesium chloride (MgCl 2·6H2 O) solution, stirring, soaking overnight, filtering, discarding magnesium chloride solution, and oven drying at 105deg.C. Taking out, grinding, sieving with 100 mesh sieve, and packaging into self-sealing bag for marking.
The modified quinoa biochar has the performance of removing heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, the standard solutions are mixed and diluted 5 times, the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions measured by ICP are 229.8mg/L,222.0mg/L and 238.2mg/L respectively, the pH value of the solutions is adjusted to 4.5, 30mL of the solutions are taken, 0.0510g of biochar is respectively added into 50mL centrifuge tubes, vibration absorption is carried out for 20h at room temperature, filter paper is used for filtration, mass concentrations of cadmium, chromium and lead ions in the solutions are measured by ICP, the removal rate and removal amount of the biochar to heavy metals are calculated, and the experimental results are shown in Table 9:
Comparative example 4
The quinoa straw is washed by deionized water, dried in an oven at 105 ℃, and then crushed into powder by a crusher. Placing into magnesium chloride (MgCl 2·6H2 O) solution, stirring, soaking overnight, filtering, discarding magnesium chloride solution, washing quinoa straw with deionized water for 3 times, and oven drying at 105deg.C. Placing the powder in porcelain boats respectively, placing in a tube furnace, pyrolyzing at 750deg.C under the protection of argon gas, wherein the heating rate is 10deg.C/min, the pyrolysis time is 2h, cooling to room temperature, taking out, grinding, sieving with 100 mesh sieve, and placing in self-sealing bag for marking.
The modified quinoa biochar has the performance of removing heavy metal ions:
The experiment adopts standard solutions with mass concentrations of Cd 2+、Cr3+ and Pb 2+ of 1000mg/L, the standard solutions are mixed and diluted 5 times, the concentrations of Cd 2+、Cr3+ and Pb 2+ in the solutions measured by ICP are 229.8mg/L,222.0mg/L and 238.2mg/L respectively, the pH value of the solutions is adjusted to 4.5, 30mL of the solutions are taken, 0.0507g of biochar is respectively added into 50mL centrifuge tubes, vibration absorption is carried out for 20h at room temperature, filter paper is used for filtration, mass concentrations of cadmium, chromium and lead ions in the solutions are measured by ICP, the removal rate and removal amount of the biochar to heavy metals are calculated, and experimental results are shown in Table 10:
The salt lake brine used in the above example was obtained from Qinghai Conghai sweat salt lake and Dongtai Ji Naier salt lake, wherein the magnesium ion content was about 100g/L, the calcium ion content was about 0.06g/L, the potassium ion content was about 0.6g/L, and the sodium ion content was about 1.9g/L.
The magnesium ion content of the magnesium chloride (MgCl 2·6H2 O) solution used in the above comparative example was the same as that of the above salt lake brine.
Summarizing:
As can be seen from the comparison of the removal rate and the removal amount of the salt lake old brine modified biochar in examples 1-6 and the unmodified biochar in comparative examples 1-2 on heavy metals, the removal effect of the modified biochar on Cd 2+、Cr3+ and Pb 2+ is significantly better than that of the unmodified biochar, in particular Cr 3+ and Pb 2+.
From comparison of example 3 and comparative example 3, and comparison of example 4 and comparative example 4, the removal rate and removal amount of Cd 2+、Cr3+ and Pb 2+ of the quinoa straw biochar modified by the salt lake old brine are obviously improved compared with those modified by magnesium chloride under the same conditions.
The removal rate and removal amount of heavy metals of the biochar of comparative example 1 are basically equivalent to those of the biochar of comparative example 2, and in the pyrolysis temperature and time range of the invention, carbonization temperature and time factors have no obvious influence on the adsorption of Cd 2+、Cr3+ and Pb 2+ by the biochar.
As can be seen from the comparison of the removal rate and the removal amount of the heavy metal of the salt lake old brine modified biochar in the example 2 and the example 3, the modified biochar prepared by carbonization and then soaking has obviously better removal effect on heavy metal ions than the modified biochar prepared by soaking and then carbonizing under the same condition.
As can be seen from the examples 1 and 5, under the same preparation conditions, the effect of the quinoa-based salt lake old brine modified biochar on removing heavy metal ions is obviously better than that of the sheep manure-based salt lake old brine modified biochar.
Example 7
The preparation process of the salt lake old brine modified quinoa straw biochar is the same as in example 1, and is different in that the content of magnesium ions in the salt lake old brine is about 121.1g/L, the content of calcium ions is about 0.32g/L, the content of potassium ions is about 2.34g/L, and the content of sodium ions is about 2.4g/L.
Example 8
The preparation process of the lake old brine modified quinoa straw biochar is the same as in example 3, except that the content of magnesium ions in the salt lake old brine is about 121.1g/L, the content of calcium ions is about 0.32g/L, the content of potassium ions is about 2.34g/L, and the content of sodium ions is about 2.4g/L.
Example 9
The preparation process of the lake old brine modified quinoa straw biochar is the same as in example 3, except that the magnesium ion content in the salt lake old brine is about 75g/L, the calcium ion content is about 0.045g/L, the potassium ion content is about 0.45g/L, and the sodium ion content is about 1.43g/L.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. The preparation method of the salt lake old brine modified biochar comprises the following steps: mixing the biochar with the salt lake old brine, and drying to obtain the salt lake old brine modified biochar;
The magnesium ion content of the salt lake old brine is 70-130 g/L, the calcium ion content is 0.01-0.5 g/L, the potassium ion content is 0.1-5 g/L, and the sodium ion content is 0.1-5 g/L.
2. The method of manufacturing according to claim 1, characterized in that: the biochar is obtained by pyrolysis and carbonization of biomass raw materials under anoxic or anaerobic conditions, wherein the biomass raw materials are plant-derived biomass, animal-derived biomass or sludge-derived biomass.
3. The preparation method according to claim 2, characterized in that: the plant-derived biomass is quinoa straw, and the animal-derived biomass is sheep manure.
4. The preparation method according to claim 2, characterized in that: the pyrolysis carbonization temperature is 300-800 ℃ and the time is 1-2 hours.
5. The method of manufacturing according to claim 1, characterized in that: the magnesium ion content of the salt lake old brine is 100-103 g/L, the calcium ion content is 0.03-0.06 g/L, the potassium ion content is 0.5-0.6 g/L, and the sodium ion content is 1.5-1.9 g/L.
6. The method of claim 1 or 5, wherein: and mixing the biochar with the salt lake old brine in a soaking mode.
7. The preparation method of the salt lake old brine modified biochar comprises the following steps:
(1) Fully contacting the biomass raw material with the salt lake old brine;
(2) Washing and drying the biomass raw material treated in the step (1), and performing pyrolysis carbonization under the anoxic or anaerobic condition to obtain the salt lake old brine modified biochar;
The magnesium ion content of the salt lake old brine is 70-130 g/L, the calcium ion content is 0.01-0.5 g/L, the potassium ion content is 0.1-5 g/L, and the sodium ion content is 0.1-5 g/L.
8. The method of manufacturing according to claim 7, wherein: and fully contacting the biomass raw material with the salt lake old brine in a soaking mode.
9. The method of manufacturing according to claim 7, wherein: the magnesium ion content of the salt lake old brine is 100-103 g/L, the calcium ion content is 0.03-0.06 g/L, the potassium ion content is 0.5-0.6 g/L, and the sodium ion content is 1.5-1.9 g/L.
10. The method of manufacturing according to claim 7, wherein: the biomass raw material is plant-derived biomass, animal-derived biomass or sludge-derived biomass.
11. The method of manufacturing according to claim 10, wherein: the plant-derived biomass is quinoa straw, and the animal-derived biomass is sheep manure.
12. The method of manufacturing according to claim 7, wherein: the pyrolysis carbonization temperature is 300-800 ℃ and the time is 1-2 hours.
13. The salt lake old brine modified biochar prepared by the preparation method of any one of claims 1-12.
14. The use of the salt lake old brine modified biochar as an adsorption material in treating heavy metal ion pollution, wherein the heavy metal ion is Cr 3+ and/or Pb 2+.
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