CN111545167B - Method for preparing silver ion selective adsorbent by using pasture - Google Patents
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- CN111545167B CN111545167B CN202010287648.7A CN202010287648A CN111545167B CN 111545167 B CN111545167 B CN 111545167B CN 202010287648 A CN202010287648 A CN 202010287648A CN 111545167 B CN111545167 B CN 111545167B
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003463 adsorbent Substances 0.000 title claims abstract description 18
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 244000025254 Cannabis sativa Species 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000000197 pyrolysis Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 241000196324 Embryophyta Species 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 241000234642 Festuca Species 0.000 claims description 2
- 241000219823 Medicago Species 0.000 claims description 2
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 claims description 2
- 239000004459 forage Substances 0.000 claims 11
- 239000012190 activator Substances 0.000 claims 5
- 238000005554 pickling Methods 0.000 claims 2
- 241000746422 Stipa Species 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 45
- 229910052709 silver Inorganic materials 0.000 abstract description 29
- 239000004332 silver Substances 0.000 abstract description 29
- -1 silver ions Chemical class 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 108700024661 strong silver Proteins 0.000 abstract description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 3
- 238000012360 testing method Methods 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000003213 activating effect Effects 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 241000585809 Stipa capillata Species 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 201000004681 Psoriasis Diseases 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000008482 dysregulation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 210000004003 subcutaneous fat Anatomy 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 238000005303 weighing Methods 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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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- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A method for preparing a silver ion selective adsorbent by using pasture, and relates to a method for preparing a silver ion selective adsorbent. The invention aims to solve the technical problems that the existing adsorbing material is difficult to selectively adsorb silver ions from a complex environment, and has small adsorption quantity and high manufacturing cost. According to the invention, the mercapto is grafted on the surface of the biochar through dehydration condensation of thioglycolic acid and hydroxyl on the surface of the biochar, the mercapto is selective to silver ions, and the mercapto is grafted on the surface of the biochar to provide more adsorption sites for adsorption of the silver ions, so that the selectivity and the adsorption performance to the silver ions are greatly improved. The sulfhydrylation grass biochar is prepared by taking grass as a precursor, is a cheap silver ion selective adsorbent, has strong silver ion selective adsorption performance, is low in production cost and simple in preparation process, and has a great application prospect in actual wastewater treatment. The invention is applied to adsorbing silver ions.
Description
Technical Field
The invention relates to a method for preparing a silver ion selective adsorbent.
Background
The pasture grass has various varieties, wide distribution in China and strong regeneration capacity, can be harvested for many times in a year, is rich in various trace elements and vitamins, and therefore becomes the first choice for raising livestock. Data show that the number of commercial pasture planting enterprises in China is large at present, and the annual production of pasture in China is nearly 20000 ten thousand tons in recent years. The development market of the domestic pasture industry shows a growing trend in recent years, which is very favorable for the pasture recovery in the future.
Silver has good ductility, electrical conductivity, thermal conductivity, photosensitivity and antibacterial property, each of which isA very useful raw material in industry, and thus the demand for silver, which is one of the noble metals, is high. For example, silver and its compounds are commonly used in wastewater treatment, food, beverage, pharmaceutical processing, and as disinfectants. On the other hand, silver ions are of particularly great environmental concern due to their potential impact on human health and ecosystem. It has been reported that when silver ions enter the human body, silver is metabolized and deposited in subcutaneous fat, causing psoriasis, where the affected person causes discoloration of the skin. Furthermore, Na is inhibited by silver ion exposure+And Cl-Uptake thereby leads to dysregulation of ions in the human body. The World Health Organization (WHO) and the united states Environmental Protection Agency (EPA) limit the silver content of drinking water to 100ppb (100 g/L). Therefore, with increasing concerns about the toxicity of soluble silver ions in water and the scarcity of silver, it is highly desirable to remove and recover silver ions from water. However, the existing adsorbing material is difficult to selectively adsorb silver ions from a complex environment, and has small adsorption amount and high manufacturing cost.
Disclosure of Invention
The invention provides a method for preparing a silver ion selective adsorbent by using pasture, aiming at solving the technical problems that the existing adsorbing material is difficult to selectively adsorb silver ions from a complex environment, and has small adsorbing capacity and high manufacturing cost.
The method for preparing the silver ion selective adsorbent by using pasture comprises the following steps:
firstly, placing dried pasture in a plant grinder, grinding for 5-10 min, then passing through a 50-mesh sieve to obtain pasture powder, adding the pasture powder into a reaction kettle, adding deionized water, placing in an oven for hydrothermal carbonization, centrifuging a product after the hydrothermal carbonization by using the deionized water until a supernatant is clear and transparent, and drying a solid obtained by centrifugation to obtain hydrated carbon;
in the hydrothermal carbonization process, the mass ratio of the grass powder to the deionized water is 1 (10-12), the hydrothermal temperature is 220-240 ℃, and the hydrothermal time is 12-14 h;
the centrifugal rotating speed is 10000r/min to 12000r/min, and the centrifugal time is 8min to 10 min;
the drying temperature is 110-120 ℃, and the drying time is 12-14 h;
uniformly mixing the hydrated carbon prepared in the step one with an activating agent, grinding, performing high-temperature pyrolysis under the protection of protective gas, cooling to room temperature along with a furnace under the protection of protective gas to obtain a biochar crude product, performing acid washing in a beaker, washing with water to neutrality, performing suction filtration to obtain a black filter cake, and drying the product to obtain biochar;
the activating agent is KOH;
the mass ratio of the hydrated carbon to the activating agent is 1 (4-5);
under the high-temperature pyrolysis condition: the heating rate is 3 ℃/min to 5 ℃/min, the pyrolysis temperature is 800 ℃ to 1000 ℃, and the pyrolysis time is 2h to 3 h;
the flow rate of the protective gas is 150 mL/min-200 mL/min;
the acid for acid cleaning is hydrochloric acid aqueous solution, and the concentration of the hydrochloric acid aqueous solution is 2-3 mol/L;
the volume ratio of the mass of the activating agent to the hydrochloric acid aqueous solution is 8mg (1 mL-1.2 mL);
the drying temperature is 110-120 ℃, and the drying time is 12-14 h;
thirdly, uniformly mixing the biochar prepared in the second step with thioglycollic acid, placing the mixture in an oven for heating, and naturally cooling to room temperature; the heating temperature of the oven is 80-90 ℃, and the heating time is 8-9 h;
adding deionized water, stirring for 30-35 min, and performing suction filtration;
thirdly, repeating the second step until the filtrate after suction filtration is neutral, and placing the black filter cake obtained by suction filtration in an oven for drying to obtain the sulfhydrylation grass biochar; the temperature during drying is 60-70 ℃, and the time is 12-13 h;
the volume ratio of the mass of the biochar to the deionized water is 1mg (2 mL-3 mL);
the volume ratio of the mass of the biochar to the thioglycolic acid is (12.5 mg-15 mg) to 1 mL.
According to the invention, the mercapto is grafted on the surface of the biochar through dehydration condensation of thioglycolic acid and hydroxyl on the surface of the biochar, the mercapto is selective to silver ions, and the mercapto is grafted on the surface of the biochar to provide more adsorption sites for adsorption of the silver ions, so that the selectivity and the adsorption performance to the silver ions are greatly improved.
The sulfhydrylation grass biochar is prepared by taking grass as a precursor, is a cheap silver ion selective adsorbent, has strong silver ion selective adsorption performance, has the adsorption capacity of silver ions almost 12 times that of palladium ions and cadmium ions, and has low production cost, simple preparation process and great application prospect in actual wastewater treatment.
Drawings
FIG. 1 is an adsorption measurement attempt in test two;
FIG. 2 is a Langmuir adsorption isotherm model fitted curve for run three;
FIG. 3 is a Freundlich adsorption isotherm model fit curve in experiment three;
FIG. 4 is a graph of a pseudo first order kinetic model of experiment four;
FIG. 5 is a graph of a pseudo-secondary kinetic model of experiment four.
Detailed Description
The first embodiment is as follows: the embodiment is a method for preparing a silver ion selective adsorbent by using pasture, which is specifically carried out according to the following steps:
firstly, placing dried pasture in a plant grinder, grinding for 5-10 min, then passing through a 50-mesh sieve to obtain pasture powder, adding the pasture powder into a reaction kettle, adding deionized water, placing in an oven for hydrothermal carbonization, centrifuging a product after the hydrothermal carbonization by using the deionized water until a supernatant is clear and transparent, and drying a solid obtained by centrifugation to obtain hydrated carbon;
in the hydrothermal carbonization process, the mass ratio of the grass powder to the deionized water is 1 (10-12), the hydrothermal temperature is 220-240 ℃, and the hydrothermal time is 12-14 h;
the centrifugal rotating speed is 10000r/min to 12000r/min, and the centrifugal time is 8min to 10 min;
the drying temperature is 110-120 ℃, and the drying time is 12-14 h;
uniformly mixing the hydrated carbon prepared in the step one with an activating agent, grinding, performing high-temperature pyrolysis under the protection of protective gas, cooling to room temperature along with a furnace under the protection of protective gas to obtain a biochar crude product, performing acid washing in a beaker, washing with water to neutrality, performing suction filtration to obtain a black filter cake, and drying the product to obtain biochar;
the activating agent is KOH;
the mass ratio of the hydrated carbon to the activating agent is 1 (4-5);
under the high-temperature pyrolysis condition: the heating rate is 3 ℃/min to 5 ℃/min, the pyrolysis temperature is 800 ℃ to 1000 ℃, and the pyrolysis time is 2h to 3 h;
the flow rate of the protective gas is 150 mL/min-200 mL/min;
the acid for acid cleaning is hydrochloric acid aqueous solution, and the concentration of the hydrochloric acid aqueous solution is 2-3 mol/L;
the volume ratio of the mass of the activating agent to the hydrochloric acid aqueous solution is 8mg (1 mL-1.2 mL);
the drying temperature is 110-120 ℃, and the drying time is 12-14 h;
thirdly, uniformly mixing the biochar prepared in the second step with thioglycollic acid, placing the mixture in an oven for heating, and naturally cooling to room temperature; the heating temperature of the oven is 80-90 ℃, and the heating time is 8-9 h;
adding deionized water, stirring for 30-35 min, and performing suction filtration;
thirdly, repeating the second step until the filtrate after suction filtration is neutral, and placing the black filter cake obtained by suction filtration in an oven for drying to obtain the sulfhydrylation grass biochar; the temperature during drying is 60-70 ℃, and the time is 12-13 h;
the volume ratio of the mass of the biochar to the deionized water is 1mg (2 mL-3 mL);
the volume ratio of the mass of the biochar to the thioglycolic acid is (12.5 mg-15 mg) to 1 mL.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the pasture in the step one is stipa capillata pasture, alfalfa, sarsa or Chinese fescue. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: and the protective gas in the second step is argon. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: and the mass ratio of the hydrated carbon to the activating agent in the step two is 1: 4. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: and (2) under the high-temperature pyrolysis condition in the step two: the heating rate is 3 ℃/min, the pyrolysis temperature is 800 ℃, and the pyrolysis time is 2 h. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the fourth difference between this embodiment and the specific embodiment is that: the volume ratio of the mass of the biochar to the thioglycolic acid in the third step is 12.5mg to 1 mL. The rest is the same as the fourth embodiment.
The invention was verified with the following tests:
test one: the test is a method for preparing the silver ion selective adsorbent by using pasture, and is specifically carried out according to the following steps:
firstly, placing dried pasture into a plant grinder, grinding for 5min, then sieving with a 50-mesh sieve to obtain pasture powder (the powder can pass through a sieve), adding the pasture powder into a reaction kettle, adding deionized water, placing into an oven for hydrothermal carbonization, centrifuging a product after the hydrothermal carbonization with the deionized water until a supernatant is clear and transparent, and drying a solid obtained by centrifugation to obtain hydrated carbon;
the pasture is stipa capillata pasture;
in the hydrothermal carbonization process, the mass ratio of the pasture grass powder to the deionized water is 1:10, the hydrothermal temperature is 220 ℃, and the hydrothermal time is 12 hours;
the rotating speed of the centrifugation is 10000r/min, and the centrifugation time is 8 min;
the drying temperature is 110 ℃, and the drying time is 12 h;
uniformly mixing the hydrated carbon prepared in the step one with an activating agent, grinding, performing high-temperature pyrolysis under the protection of protective gas, cooling to room temperature along with a furnace under the protection of protective gas to obtain a biochar crude product, performing acid washing in a beaker, washing with water to neutrality, performing suction filtration to obtain a black filter cake, and drying the product to obtain biochar;
the protective gas is argon;
the activating agent is KOH;
the mass ratio of the hydrated carbon to the activating agent is 1: 4;
under the high-temperature pyrolysis condition: the heating rate is 3 ℃/min, the pyrolysis temperature is 800 ℃, and the pyrolysis time is 2 h;
the flow rate of the protective gas is 150 mL/min;
the acid for acid cleaning is hydrochloric acid aqueous solution, and the concentration of the hydrochloric acid aqueous solution is 2 mol/L;
the volume ratio of the mass of the activating agent to the hydrochloric acid aqueous solution is 8mg:1 mL;
the drying temperature is 110 ℃, and the drying time is 12 hours;
thirdly, uniformly mixing the biochar prepared in the second step with thioglycollic acid, placing the mixture in an oven for heating, and naturally cooling to room temperature; the heating temperature of the oven is 80 ℃, and the heating time is 8 h;
adding deionized water, stirring for 30min, and then carrying out suction filtration;
thirdly, repeating the second step until the filtrate after suction filtration is neutral, and placing the black filter cake obtained by suction filtration in an oven for drying to obtain the sulfhydrylation grass biochar; the drying temperature is 60 ℃, and the drying time is 12 hours;
the volume ratio of the mass of the biochar to the deionized water is 1mg:2 mL;
the volume ratio of the mass of the biochar to the thioglycolic acid is 12.5mg to 1 mL.
And (2) test II: the test is an adsorption contrast test of sulfhydrylation biochar on different heavy metal ions, and the specific process is as follows:
selection of Cd2+、Pd2+And Ag+And (3) comparison:
50mL of cadmium nitrate aqueous solution (Cd) is measured respectively2+At a concentration of 300mg/L), an aqueous copper sulfate solution (Pd2+At a concentration of 300mg/L) and an aqueous silver nitrate solution (Ag)+300mg/L) are added into a 250mL conical flask together, the concentration of three ions in the mixed solution is 100mg/L, 15mg of sulfhydrylation biochar prepared in the first test is weighed and added into the conical flask, the sulfhydrylation biochar is uniformly dispersed by ultrasonic treatment for 1min and is put into a shaking table to be oscillated for 20h for adsorption, after the adsorption process is finished, the concentration after adsorption is measured by an atomic spectrophotometer, and the Cd pair is calculated2+、Pd2+、Ag+Adsorption capacity of three metal ions; the shaking table is set at 25 ℃ and the rotating speed is 180 rpm.
FIG. 1 shows the adsorption measurement in test two, curve 1 shows Ag+Curve 2 is Pd2+Curve 3 is Cd2+It can be seen that the adsorption capacity of the sulfhydrylation biochar to silver ions is far greater than that of palladium ions and cadmium ions, the maximum adsorption capacity to the silver ions reaches 773.4mg/g, the maximum adsorption capacity to the palladium ions and the cadmium ions is only 96.74mg/g and 65.25mg/g, and the adsorption capacity to the silver ions is nearly 12 times that of the palladium ions and the cadmium ions, which indicates that the sulfhydrylation biochar prepared in the first test has very excellent selectivity to silver ion adsorption.
And (3) test III: the test is an adsorption isotherm test of silver ions adsorbed by sulfhydrylation biochar, and specifically comprises the following steps:
respectively measuring 8 parts of 50mL silver nitrate aqueous solutions with different silver ion concentrations, respectively adding the silver nitrate aqueous solutions into 100mL conical flasks, respectively measuring 5mg of sulfhydrylation biochar prepared by the test I, adding the sulfhydrylation biochar into the conical flasks, respectively carrying out ultrasonic treatment for 1min to ensure that the sulfhydrylation biochar is uniformly dispersed, respectively placing the sulfhydrylation biochar into a shaking table for oscillation and adsorption, measuring the concentration of adsorbed silver ions by an atomic spectrophotometer after the adsorption process is finished, and calculating the concentration of Ag+The data obtained were fitted to Langmuir and Freundlich isothermal adsorption models.
The concentration of silver ions in the 8 parts of silver nitrate aqueous solution is respectively 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L and 100 mg/L.
FIG. 2 is a Langmuir adsorption isothermal model fitting curve in experiment III, FIG. 3 is a Freundlich adsorption isothermal model fitting curve in experiment III, black points in the curve are actual test data, the curve is a corresponding fitting curve, and R of the curve 220.99011, R of Curve 32At 0.97629, it can be seen that test one prepared thiolated biochar on Ag+The adsorption of (A) is more consistent with Langmuir isothermal adsorption model, which shows that the adsorption sites of the sulfhydrylation biochar are uniform, and the adsorbed silver ions have no transverse interaction.
And (4) testing: the test is an adsorption kinetics test of silver ions adsorbed by sulfhydrylation biochar, and the specific process is as follows:
50mL of silver nitrate aqueous solution in which Ag is contained is measured+Adding the solution to a 100mL conical flask, weighing 5mg of the sulfhydrylated biochar prepared in the first step, adding the weighed sulfhydrylated biochar into the conical flask, performing ultrasonic treatment for 1min to uniformly disperse the sulfhydrylated biochar, placing the mixture into a shaking table to perform oscillation adsorption, sampling according to time in the adsorption process, measuring the concentration of each time point by an atomic spectrophotometer, and calculating the concentration of Ag+Amount of adsorption at each time point.
The sampling time is 1, 3, 5, 7, 10, 15, 20, 30, 60, 120, 180, 240, 300, 360, 420, 480, 600, 720, 840, 960, 1080, 1200, 1320, 1440 and 1740, and the units are minutes.
And performing quasi-first-stage and quasi-second-stage dynamics fitting on the obtained data, wherein FIG. 4 is a pseudo-first-stage dynamics model curve diagram in the fourth experiment, FIG. 5 is a pseudo-second-stage dynamics model curve diagram in the fourth experiment, black points in the diagram are actual test data, and the curves are corresponding fitting curves. Fitting of thiolated biochar to Ag using a quasi-second order kinetic model+The adsorption kinetics experimental data has higher correlation coefficient (R)2>0.99), see Table 1, thus illustrating the test-preparation of thiolated biochar against Ag+The adsorption of (A) is more in line with a pseudo-second order kinetic model. Meanwhile, the obtained sulfhydrylation biochar is calculated for Ag by utilizing a pseudo-second-order kinetic model+Theoretical adsorptionThe amount of 757.57mg/g is nearly the same as the actually measured equilibrium adsorption amount (769.59mg/g), so that the adsorption process can be proved to be more in line with a pseudo-second order kinetic model+The adsorption capacity of (a) is strongly correlated with the adsorption sites on the carbon.
TABLE 1 adsorption model of thiolated biochar
Claims (6)
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| DE2105515A1 (en) * | 1970-02-05 | 1971-09-30 | Osaka Soda Co. Ltd., Osaka-(Japan) | Process for removing metals and means therefor |
| EP3599016A1 (en) * | 2018-07-24 | 2020-01-29 | Omya International AG | Heavy metal removal using minerals being functionalized with thiols |
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| CN104069813A (en) * | 2014-07-11 | 2014-10-01 | 南开大学 | Method for preparing modified wheat straw hydrothermal charcoal by adopting KOH |
| CN104368316B (en) * | 2014-11-18 | 2016-05-04 | 辽宁大学 | A kind of hydrosulfide group cellulose class stalk adsorbent and preparation method and the recovery to noble silver |
| CN105921109A (en) * | 2016-06-01 | 2016-09-07 | 湖南农业大学 | Biological carbon prepared from tobacco stems as well as preparation method and application thereof |
| CN106861646B (en) * | 2017-04-01 | 2019-05-07 | 东华大学 | Preparation method of adsorbent material for selectively adsorbing silver ions |
| CN106968105A (en) * | 2017-04-28 | 2017-07-21 | 广州京诚检测技术有限公司 | A kind of Sulfhydryl Cotton and its application |
| CN108176361A (en) * | 2018-02-06 | 2018-06-19 | 广东环境保护工程职业学院 | Sulfhydryl modified charcoal based on agricultural wastes and its preparation method and application |
| CN109173994A (en) * | 2018-09-19 | 2019-01-11 | 南昌航空大学 | A kind of modified abandoned stub of high temperature carbonization prepares the method for charcoal and the application of charcoal |
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| DE2105515A1 (en) * | 1970-02-05 | 1971-09-30 | Osaka Soda Co. Ltd., Osaka-(Japan) | Process for removing metals and means therefor |
| EP3599016A1 (en) * | 2018-07-24 | 2020-01-29 | Omya International AG | Heavy metal removal using minerals being functionalized with thiols |
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