CN113893821B - Porous carbon material noble metal adsorbent based on nitrogen and sulfur doping and preparation method thereof - Google Patents
Porous carbon material noble metal adsorbent based on nitrogen and sulfur doping and preparation method thereof Download PDFInfo
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- CN113893821B CN113893821B CN202111200874.8A CN202111200874A CN113893821B CN 113893821 B CN113893821 B CN 113893821B CN 202111200874 A CN202111200874 A CN 202111200874A CN 113893821 B CN113893821 B CN 113893821B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 14
- 239000011593 sulfur Substances 0.000 title claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 title abstract description 16
- 239000003463 adsorbent Substances 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical group NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 239000011812 mixed powder Substances 0.000 claims description 16
- 239000012190 activator Substances 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ADPOBOOHCUVXGO-UHFFFAOYSA-H dioxido-oxo-sulfanylidene-$l^{6}-sulfane;gold(3+) Chemical compound [Au+3].[Au+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S ADPOBOOHCUVXGO-UHFFFAOYSA-H 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229940006280 thiosulfate ion Drugs 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- -1 gold thiosulfate ions Chemical class 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 14
- 239000010931 gold Substances 0.000 abstract description 9
- 229910052737 gold Inorganic materials 0.000 abstract description 8
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 101150116344 PCGF1 gene Proteins 0.000 description 4
- 102100040921 Polycomb group RING finger protein 1 Human genes 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 101150050759 outI gene Proteins 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0262—Compounds of O, S, Se, Te
- B01J20/0266—Compounds of S
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A porous carbon material noble metal adsorbent based on nitrogen and sulfur doping relates to the technical field of noble metal adsorption recovery, and is based on the problem of low adsorption capacity of the existing gold thiosulfate ions. The carbon material has a micro porous structure, and nitrogen and sulfur elements are doped on the surface of the carbon material; the raw materials of the carbon material comprise a carbon source, a template agent and an activating agent; the carbon source is 2-aminothiazole. The invention also discloses a preparation method of the porous carbon material noble metal adsorbent based on nitrogen and sulfur doping. According to the invention, 2-aminothiazole is used as a raw material, under the action of a template agent and an activating agent, the nitrogen-sulfur doped porous carbon material is obtained through high-temperature calcination, the adsorption capacity of the carbon material can be improved through a porous structure constructed by a template method, and the adsorption capacity of gold ions can be improved through doping nitrogen and sulfur elements.
Description
Technical Field
The invention relates to the technical field of noble metal adsorption recovery, in particular to a porous carbon material noble metal adsorbent based on nitrogen and sulfur doping and a preparation method thereof.
Background
Gold, silver, platinum, palladium, ruthenium, rhodium, osmium and iridium are used as 8 noble metal elements, and are widely applied to the modern technological and industrial fields of aerospace, military industry, electronic and electric appliances, traffic, petrochemical industry and the like, and have important strategic significance. Precious metal resources are rare and expensive, the recycling value of waste materials is much higher than that of common metals, and the waste materials are valuable secondary resources, so that the method for recycling the precious metals from the waste materials has important significance.
Conventional methods for recovering noble metals include ion exchange, reverse osmosis, neutral precipitation, and adsorption. The adsorption method has the advantages of low cost, easy operation, small pollution and the like, and becomes an ideal green extraction technology. The adsorption method is used for extracting noble metals, and the types of adsorbents required by the adsorption method are more, and comprise chelate resin, mesoporous materials, activated carbon and the like. The carbon material has the characteristics of acid resistance, alkali resistance, corrosion resistance, difficult poisoning, regeneration recovery and the like, and is widely concerned, but the carbon material has lower adsorption capacity to gold thiosulfate ions, so that the popularization of the gold ion adsorption technology of the carbon material is limited.
In order to improve the adsorption capacity of the carbon material to gold thiosulfate ions, 2-mercaptobenzothiazole is adopted as a doping agent in the patent CN107215872A, and the carbon material is doped by using an organic solvent or strong alkali as a solvent, but expensive doping agents are used in the process, and toxic wastes are easily generated; the patent CN109574008A uses ammonium thiocyanate to dope the carbon material, but the process requires severe conditions such as high temperature and high pressure. The porous structure is designed to improve the specific surface area and pore channels of the material and also can improve the loading capacity of the adsorbent, and the porous sodium alginate adsorbent is prepared by a template method in the patent CN109433164A, so that the adsorption capacity is improved.
Disclosure of Invention
The invention aims to solve the technical problems that the existing gold thiosulfate ion adsorption capacity is low, and the popularization of the gold ion adsorption technology of carbon materials is limited.
The invention solves the technical problems by the following technical means:
a porous carbon material noble metal adsorbent based on nitrogen and sulfur doping, wherein the carbon material has a micro porous structure, and the surface of the carbon material is doped with nitrogen and sulfur elements;
the raw materials of the carbon material comprise a carbon source, a template agent and an activating agent;
the carbon source is 2-aminothiazole;
the mass of the template agent is 2-10 times of that of the carbon source;
the mass of the activator is 5-30 times of that of the carbon source.
According to the invention, nitrogen and sulfur elements are doped on the surface of the carbon material, and the carbon material has a porous structure, so that the adsorption capacity of gold ions can be improved.
Preferably, the template agent comprises calcium hydroxide, F 127 One or both of which are mixed.
Preferably, the activator comprises H 3 PO 4 、ZnCl 2 At least one of KOH.
The invention also discloses a preparation method of the porous carbon material noble metal adsorbent based on nitrogen-sulfur doping, which comprises the following steps:
(1) Weighing 2-aminothiazole, a template agent and an activating agent with certain mass, and performing ball milling and mixing uniformly to obtain mixed powder;
(2) Placing the mixed powder obtained in the step (1) in a quartz boat, and adding N 2 Heating to 600-900 deg.c in a tubular furnace under protection for 6-20 hr to obtain black powder;
(3) Washing the black powder obtained in the step (2) with hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for multiple times;
(4) Drying the powder washed in the step (3) in a vacuum drying oven, and finally, placing the dried powder in a tube furnace in N 2 And (5) keeping the temperature of 200 ℃ for 2 hours under the atmosphere to obtain the product.
Further, the rotational speed of the ball milling in the step (1) is 380r/min.
Further, the ball milling time in the step (1) is 2 hours.
Further, the concentration of hydrochloric acid in the step (3) is 30%.
Further, deionized water and ethanol are washed 3 times in the step (3).
Further, the drying temperature in the step (4) is 70-90 ℃.
Further, the drying time in the step (4) is 5-7h.
The invention has the following beneficial effects:
1. according to the invention, nitrogen and sulfur elements are doped on the surface of the carbon material, and the carbon material has a porous structure, so that the adsorption capacity of gold ions can be improved.
2. According to the invention, 2-aminothiazole is used as a raw material, under the action of a template agent and an activating agent, the nitrogen-sulfur doped porous carbon material is obtained through high-temperature calcination, the adsorption capacity of the carbon material can be improved through a porous structure constructed by a template method, and the adsorption capacity of gold ions can be improved through doping nitrogen and sulfur elements.
3. The nitrogen-sulfur doped porous carbon material has better adsorption capacity for silver ions.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a porous carbon material noble metal adsorbent based on nitrogen-sulfur doping in accordance with an embodiment of the present invention;
fig. 2 is an SEM image of the product prepared in example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings and the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
A preparation method of a porous carbon material noble metal adsorbent (NSPC 1) based on nitrogen-sulfur doping comprises the following steps:
(1) 0.1282g of 2-aminothiazole and 0.7692g of Ca (OH) were weighed out 2 0.7692g of ZnCl 2 Ball milling is carried out for 2 hours at the rotating speed of 380r/min, and the mixture is evenly mixed to obtain mixed powder;
(2) Mixing the mixture obtained in step (1)Placing the powder in a quartz boat, at N 2 Heating to 800 ℃ in a tube furnace under the protection of (30 mL/min) and preserving heat for 12 hours to obtain black powder;
(3) Washing the black powder obtained in the step (2) with 30% hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for 3 times;
(4) Drying the powder washed in the step (3) for 6 hours at 80 ℃ in a vacuum drying oven, and finally using N in a tube furnace 2 (30 mL/min) was kept at 200℃for 2 hours under an atmosphere to obtain a product, designated NSPC1.
The product NSPC1 prepared in this example was subjected to Scanning Electron Microscope (SEM) analysis, and the analysis results are shown in fig. 2.
Example 2
A preparation method of a porous carbon material noble metal adsorbent (NSPC 2) based on nitrogen-sulfur doping comprises the following steps:
(1) 0.1282g of 2-aminothiazole and 0.7692g of Ca (OH) were weighed out 2 1.2820g of ZnCl 2 Ball milling is carried out for 2 hours at the rotating speed of 380r/min, and the mixture is evenly mixed to obtain mixed powder;
(2) Placing the mixed powder obtained in the step (1) in a quartz boat, and adding N 2 Heating to 800 ℃ in a tube furnace under the protection of (30 mL/min) and preserving heat for 12 hours to obtain black powder;
(3) Washing the black powder obtained in the step (2) with 30% hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for 3 times;
(4) Drying the powder washed in the step (3) for 6 hours at 80 ℃ in a vacuum drying oven, and finally using N in a tube furnace 2 (30 mL/min) was kept at 200℃for 2 hours under an atmosphere to obtain a product, designated NSPC2.
Example 3
A preparation method of a porous carbon material noble metal adsorbent (NSPC 3) based on nitrogen-sulfur doping comprises the following steps:
(1) 0.1282g of 2-aminothiazole and 1.2820g of Ca (OH) were weighed out 2 1.2820g of ZnCl 2 Ball milling is carried out for 2 hours at the rotating speed of 380r/min, and the mixture is evenly mixed to obtain mixed powder;
(2) The step (1) is carried outIs placed in a quartz boat, at N 2 Heating to 800 ℃ in a tube furnace under the protection of (30 mL/min) and preserving heat for 12 hours to obtain black powder;
(3) Washing the black powder obtained in the step (2) with 30% hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for 3 times;
(4) Drying the powder washed in the step (3) for 6 hours at 80 ℃ in a vacuum drying oven, and finally using N in a tube furnace 2 (30 mL/min) was kept at 200℃for 2 hours under an atmosphere to obtain a product, designated NSPC3.
Comparative example 1
0.1282g of 2-methylimidazole and 0.7692g of Ca (OH) were weighed out 2 1.2820g of ZnCl 2 Ball milling is carried out for 2 hours at the rotating speed of 380r/min, and the mixed powder is prepared; placing the mixed powder in a quartz boat, at N 2 Heating to 800 ℃ in a tube furnace under the protection of (30 mL/min) and preserving heat for 12 hours to obtain black powder; washing the black powder with 30% hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for 3 times; drying the washed powder in a vacuum drying oven at 80deg.C for 6 hr, and finally using N in a tube furnace 2 (30 mL/min) was kept at 200℃for 2 hours under an atmosphere to obtain a product, which was designated as N-PC.
Comparative example 2
0.1282g of 2-methylthiophene and 0.7692g of Ca (OH) were weighed out 2 1.2820g of ZnCl 2 Ball milling is carried out for 2 hours at the rotating speed of 380r/min, and the mixed powder is prepared; placing the mixed powder in a quartz boat, at N 2 Heating to 800 ℃ in a tube furnace under the protection of (30 mL/min) and preserving heat for 12 hours to obtain black powder; washing the black powder with 30% hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for 3 times; drying the washed powder in a vacuum drying oven at 80deg.C for 6 hr, and finally using N in a tube furnace 2 (30 mL/min) was kept at 200℃for 2 hours under an atmosphere to obtain a product, designated as S-PC.
Comparative example 3
0.1282g of coke and 1.2820g of ZnCl are weighed out 2 Ball milling is carried out for 2 hours at the rotating speed of 380r/min, and the mixed powder is prepared; placing the mixed powder in a quartz boat, at N 2 (30mL/min), heating to 800 ℃ in a tube furnace under the protection of the powder, and preserving heat for 12 hours to obtain black powder; washing the black powder with 30% hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for 3 times; drying the washed powder in a vacuum drying oven at 80deg.C for 6 hr, and finally using N in a tube furnace 2 And (30 mL/min) was kept at 200℃for 2 hours under an atmosphere to obtain a product, designated as C.
Comparative example 4
0.1282g of coke and 0.7692g of Ca (OH) were weighed out 2 1.2820g of ZnCl 2 Ball milling is carried out for 2 hours at the rotating speed of 380r/min, and the mixed powder is prepared; placing the mixed powder in a quartz boat, at N 2 Heating to 800 ℃ in a tube furnace under the protection of (30 mL/min) and preserving heat for 12 hours to obtain black powder; washing the black powder with 30% hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for 3 times; drying the washed powder in a vacuum drying oven at 80deg.C for 6 hr, and finally using N in a tube furnace 2 The mixture was kept at 200℃for 2 hours under an atmosphere of (30 mL/min), and the product was obtained and designated as PC.
Adsorption performance test experiments were performed on the above-prepared examples 1 to 3 and comparative examples 1 to 4.
100mL of Au (S) having a concentration of 200ppm was prepared 2 O 3 ) 2 3- The pH value of the solution (adsorption solution) is regulated to 10, 0.5g of the adsorption materials prepared in the examples and the comparative examples are added into the adsorption solution, and the adsorption is carried out for 36 hours at the constant temperature of 30 ℃, and the results are shown in the table 1, so that the invention takes 2-aminothiazole as a raw material, and under the action of a template agent and an activator, the nitrogen-sulfur doped porous carbon material is obtained through high-temperature calcination, the adsorption capacity of the carbon material can be improved through the porous structure constructed by the template method, and the adsorption capacity of gold ions can be improved through doping nitrogen and sulfur elements.
In addition, 100mL of AgNO with a concentration of 200ppm was prepared 3 The solution is tried to absorb silver ions, and the result is shown in table 2, so that the nitrogen-sulfur doped porous carbon material has better absorbing capability to silver ions.
Table 1 shows the results of adsorption efficiency of carbon material on gold thiosulfate
| Sample of | NSPC1 | NSPC2 | NSPC3 | N-PC | S-PC | C | PC |
| Adsorption rate of | 89.7％ | 95.6％ | 91.1％ | 85.5％ | 87.3％ | 45.2％ | 53.7％ |
Table 2 shows the adsorption efficiency of the carbon material to silver ions
| Sample of | NSPC1 | NSPC2 | NSPC3 | N-PC | S-PC | C | PC |
| Adsorption rate of | 43.9％ | 55.6％ | 48.2％ | 35.1％ | 41.6％ | 13.7％ | 33.7％ |
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. An application of a porous carbon material based on nitrogen-sulfur doping in gold thiosulfate ion adsorption is characterized in that: the carbon material has a micro porous structure, and nitrogen and sulfur elements are doped on the surface of the carbon material;
the raw materials of the carbon material comprise a carbon source, a template agent and an activating agent;
the carbon source is 2-aminothiazole;
the mass of the template agent is 2-10 times of that of the carbon source, and the template agent is calcium hydroxide;
the mass of the activator is 5-30 times of that of the carbon source, and the activator is ZnCl 2 。
2. Use of a porous carbon material based on nitrogen-sulfur doping for gold thiosulfate ion adsorption according to claim 1, characterized by comprising the steps of:
(1) Weighing 2-aminothiazole, a template agent and an activating agent with certain mass, and performing ball milling and mixing uniformly to obtain mixed powder;
(2) Placing the mixed powder obtained in the step (1) in a quartz boat, and adding N 2 Heating to 600-900 deg.c in a tubular furnace under protection for 6-20 hr to obtain black powder;
(3) Washing the black powder obtained in the step (2) with hydrochloric acid to remove residual template agent and activator, and washing with deionized water and ethanol for multiple times;
(4) Drying the powder washed in the step (3) in a vacuum drying oven, and finally, placing the dried powder in a tube furnace in N 2 And (5) keeping the temperature of 200 ℃ for 2 hours under the atmosphere to obtain the product.
3. Use of a porous carbon material based on nitrogen-sulfur doping for gold thiosulfate ion adsorption according to claim 2, characterized in that: the rotational speed of ball milling in the step (1) is 380r/min.
4. Use of a porous carbon material based on nitrogen-sulfur doping for gold thiosulfate ion adsorption according to claim 2, characterized in that: the ball milling time in the step (1) is 2 hours.
5. Use of a porous carbon material based on nitrogen-sulfur doping for gold thiosulfate ion adsorption according to claim 2, characterized in that: the concentration of hydrochloric acid in the step (3) is 30 percent.
6. Use of a porous carbon material based on nitrogen-sulfur doping for gold thiosulfate ion adsorption according to claim 2, characterized in that: and (3) washing with deionized water and ethanol for 3 times in the step (3).
7. Use of a porous carbon material based on nitrogen-sulfur doping for gold thiosulfate ion adsorption according to claim 2, characterized in that: the drying temperature in the step (4) is 70-90 ℃.
8. Use of a porous carbon material based on nitrogen-sulfur doping for gold thiosulfate ion adsorption according to claim 2, characterized in that: the drying time in the step (4) is 5-7h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006636A (en) * | 2016-05-19 | 2016-10-12 | 中国科学院青岛生物能源与过程研究所 | Biomass-based nitrogen-doped porous carbon material, and preparation method and application thereof |
| CN110451509A (en) * | 2019-08-20 | 2019-11-15 | 江西省科学院应用化学研究所 | A method of nitrogen-doped porous carbon material is prepared by activator of zinc nitrate |
| CN111943199A (en) * | 2020-08-21 | 2020-11-17 | 江西省科学院应用化学研究所 | Method for preparing sulfur-nitrogen co-doped porous carbon material by using potassium hydroquinone sulfate as activating agent |
| CN111992180A (en) * | 2020-07-22 | 2020-11-27 | 复旦大学 | Preparation method of biomass-based carbon material and application of biomass-based carbon material in adsorption and recovery of precious metal gold |
| CN112206800A (en) * | 2020-08-31 | 2021-01-12 | 浙江工业大学 | Nitrogen-sulfur doped carbon material supported palladium catalyst, preparation method thereof and application thereof in tetrahydrophthalic anhydride hydrogenation reaction |
-
2021
- 2021-10-14 CN CN202111200874.8A patent/CN113893821B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006636A (en) * | 2016-05-19 | 2016-10-12 | 中国科学院青岛生物能源与过程研究所 | Biomass-based nitrogen-doped porous carbon material, and preparation method and application thereof |
| CN110451509A (en) * | 2019-08-20 | 2019-11-15 | 江西省科学院应用化学研究所 | A method of nitrogen-doped porous carbon material is prepared by activator of zinc nitrate |
| CN111992180A (en) * | 2020-07-22 | 2020-11-27 | 复旦大学 | Preparation method of biomass-based carbon material and application of biomass-based carbon material in adsorption and recovery of precious metal gold |
| CN111943199A (en) * | 2020-08-21 | 2020-11-17 | 江西省科学院应用化学研究所 | Method for preparing sulfur-nitrogen co-doped porous carbon material by using potassium hydroquinone sulfate as activating agent |
| CN112206800A (en) * | 2020-08-31 | 2021-01-12 | 浙江工业大学 | Nitrogen-sulfur doped carbon material supported palladium catalyst, preparation method thereof and application thereof in tetrahydrophthalic anhydride hydrogenation reaction |
Non-Patent Citations (2)
| Title |
|---|
| Efficient carbon dioxide capture by nitrogen and sulfur dual-doped mesoporous carbon spheres from polybenzoxazines synthesized by a simple strategy;Raneesh Konnola;《Journal of Environmental Chemical Engineering》;103614 * |
| 杂原子修饰的多孔材料设计合成和催化性能研究;柏家奇;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》;B014-285 * |
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