CN115532226B - Efficient adsorption remover for cadmium ions and preparation method and application thereof - Google Patents
Efficient adsorption remover for cadmium ions and preparation method and application thereof Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 84
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000197 pyrolysis Methods 0.000 claims abstract description 24
- 239000010802 sludge Substances 0.000 claims abstract description 23
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000004043 dyeing Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 abstract description 57
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- -1 sulfide ions Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004383 yellowing Methods 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
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a high-efficiency adsorption remover for cadmium ions, and a preparation method and application thereof. The invention collects the dyeing sludge for drying treatment; taking the dried printing and dyeing sludge and melamine for oxygen-limited pyrolysis; uniformly mixing carbon disulfide and sodium hydroxide, reacting with the product obtained by oxygen limiting pyrolysis, magnetically stirring, and finally drying and sieving to obtain the adsorbent. The adsorbent of the invention can rapidly and efficiently adsorb heavy metals, and can adsorb heavy metals in the initial Cd 2+ The maximum removal rate can reach almost 100% under the conditions of 50, 80 and 100mg/L concentration; even at the initial Cd 2+ When the concentration is up to 200mg/L, the maximum adsorption capacity can reach 164.75mg/g. The invention has the advantages of simple preparation, high efficiency, high speed, low cost and the like, provides a new way for recycling the printing and dyeing sludge, and has wide application prospect in the treatment of heavy metal polluted water.
Description
Technical Field
The invention belongs to the technical field of environmental heavy metal pollution treatment, relates to an adsorbent for removing cadmium ions in the environment, and in particular relates to a high-efficiency adsorption remover for removing cadmium ions, and a preparation method and application thereof.
Background
More and more industrial wastewater containing heavy metal ions is discharged without reaching standards, so that serious pollution is caused to the ecological environment, and the human health is threatened. In the field of water heavy metal pollution treatment, common adsorbents mainly comprise inorganic active carbon, organic materials and the like, but have the problems of complex preparation process, high cost, secondary pollution and the like. Therefore, a heavy metal adsorbent with good adsorption performance, simple preparation process, low cost and environmental protection needs to be explored.
According to incomplete statistics, the sludge treatment scale of China is approximately 1000 ten thousand tons/year, and the sludge treatment problems are more and more widely emphasized. The traditional sludge treatment method mainly comprises landfill, incineration and recycling, wherein the most used landfill occupies a large amount of land and is easy to cause secondary pollution. Along with the development of technology, the incineration technology process is mature gradually, but the investment cost is high, and the atmospheric pollution is easy to cause. In the aspect of recycling technology, researchers can fully play the residual value of sludge by preparing biochar from sludge through pyrolysis, and the method is considered as one of effective ways for realizing both economy and environmental win-win. Although the pyrolysis process is simple and convenient to operate and the sludge biochar is cheap and easy to obtain, the adsorption removal effect is still to be improved in the aspect of water heavy metal ion pollution treatment. Therefore, the research and development of the adsorption material with simple preparation, abundant raw material sources and strong adsorption performance has important application value in the aspect of water heavy metal ion pollution control.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the primary purpose of the invention is to provide a preparation method of an efficient adsorption remover for cadmium ions. The raw material adopted by the method is printing and dyeing sludge, and has the characteristics of abundant quantity, low price and the like.
Another object of the present invention is to provide a highly efficient adsorption remover of cadmium ions obtained by the above-mentioned preparation method.
It is still another object of the present invention to provide an application of the above-mentioned high-efficiency adsorption remover for cadmium ions.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the efficient adsorption remover for cadmium ions comprises the following steps:
(1) Drying and grinding treatment is carried out after the printing and dyeing sludge is collected;
(2) Mixing the ground printing and dyeing sludge with melamine, performing oxygen-limited pyrolysis, taking out, cooling, pickling an oxygen-limited pyrolysis product, and drying;
(3) And (3) uniformly mixing the acid-washed and dried product with a product M obtained by uniformly mixing and reacting carbon disulfide and sodium hydroxide, extracting the product, and grinding and sieving to obtain powder, namely the efficient adsorption remover for cadmium ions.
Preferably, in the step (1), the drying refers to drying until the water content is lower than 5%.
Preferably, in the step (1), the temperature of the drying is set to be 60-100 ℃ and the time is 36-96 hours; preferably, the temperature is set at 80℃for 48 hours. If the moisture of the raw material of the printing and dyeing sludge is too high, the drying temperature or the drying time is correspondingly increased.
Preferably, in the step (2), the specific arrangement of oxygen limiting pyrolysis is as follows: uniformly mixing the ground printing and dyeing sludge and melamine according to the mass ratio of 1:1-1:3, placing the mixture in a pyrolysis furnace, introducing nitrogen for 20-40 min, heating to 700-900 ℃ at the heating rate of 300-600 ℃/h, carbonizing at constant temperature for 2-4 h, cooling to room temperature, and taking out.
Further preferably, in the step (2), the specific arrangement of oxygen limiting pyrolysis is as follows: uniformly mixing the printing and dyeing sludge after grinding treatment with melamine according to the mass ratio of 1:1, placing the mixture in a pyrolysis furnace, introducing nitrogen for 25min, heating to 900 ℃ at the heating rate of 300 ℃/h, carbonizing at constant temperature for 2h, cooling to room temperature, and taking out.
Preferably, the specific arrangement of the pickling in the step (2) is as follows: leaching the limited oxygen pyrolysis product by hydrochloric acid with the concentration of 0.1-2.0 mol/L for 1-10 minutes, and setting the drying temperature to 60-100 ℃ and the drying time to 36-96 hours.
Further preferably, the specific arrangement of the pickling in the step (2) is as follows: leaching the limited oxygen pyrolysis product by hydrochloric acid with the concentration of 1.0mol/L for 5 minutes, and setting the drying temperature to 80 ℃ for 48 hours.
Preferably, in the step (3), the specific setting of the uniformly mixing reaction of the carbon disulfide and the sodium hydroxide is as follows: mixing the carbon disulfide and sodium hydroxide solution according to the volume ratio of 1:1-1:3, magnetically stirring for 2-6 h, performing ultrasonic treatment for 0.5-2 h, drying, grinding and sieving.
Further preferably, in the step (3), the specific setting of the uniformly mixing reaction of the carbon disulfide and the sodium hydroxide is as follows: the volume ratio of the carbon disulfide to the sodium hydroxide solution is 2:3, mixing, magnetically stirring for 4 hours, performing ultrasonic treatment for 1 hour, drying, grinding and sieving.
Further preferably, the concentration of the sodium hydroxide solution is 0.4mol/L.
Preferably, in the step (3), the specific arrangement of the reaction between the acid washing and drying product and the product M is as follows: the mass ratio of the pickling and drying product to the product M is 5:1 to 10:1, and magnetically stirring for 12-20 h.
Further preferably, in the step (3), the specific arrangement of the reaction between the oxygen-limited pyrolysis product and the product M is as follows: oxygen limited pyrolysis product and product M are mixed according to mass ratio of 8:1, mixing and magnetically stirring for 16h.
Preferably, in the step (3), the powder obtained by grinding the powder through a sieve having a particle size of 0.3mm is smaller than 0.3mm.
The efficient adsorption remover for cadmium ions is prepared by the preparation method.
The high-efficiency adsorption remover for cadmium ions is applied to removing heavy metal cadmium ions in the environment.
Such environments include, but are not limited to, aqueous environments, soil environments.
In addition, the invention also provides a treatment method of the heavy metal polluted water body, which comprises the following steps: the high-efficiency adsorption remover for cadmium ions is added into a water body containing heavy metal cadmium ions, and the water body is fully contacted and reacted to remove the cadmium ions in the water body. Experiments prove that the adsorbent can rapidly and efficiently remove Cd in water 2+ Good treatment effect is obtained.
Preferably, the dosage of the high-efficiency adsorption remover for cadmium ions is 0.5-2 g/L; further preferably 1g/L.
Preferably, the initial pH of the water body is 1.0-7.0; further preferably 6.0.
Preferably, the initial concentration of heavy metal cadmium ions in the water body is 10-300 mg/L; further preferably 20 to 200mg/L.
Preferably, the reaction conditions are 10-50 ℃ and 6-24 h. Stirring or shaking may be performed in order to bring the cadmium ions into sufficient contact with the adsorbent.
The technical principle of the invention is as follows: based on the characteristic that the volatility of organic matters at high temperature obviously increases the specific surface area, the biochar with high specific surface area is prepared by pyrolysis from the perspective of recycling melamine waste, and the negative divalent sulfide ions and Cd of the water body are combined 2+ The method has very firm precipitation characteristics, and the biological carbon is further chemically modified through the yellowing reaction of the disulfide carbon and the sodium hydroxide solution, so that the heavy metal efficient adsorption remover is prepared.
Compared with the prior art, the invention has the following advantages and effects:
(1) The adsorbent provided by the invention has the advantages of simple preparation process and low cost, and provides a new way for recycling the printing and dyeing sludge. The concrete implementation is as follows: in the preparation process, the operation is simple, no catalyst (such as pyridine) or auxiliary solvent (such as dimethylformamide) is used, and the raw materials are cheap and easy to obtain and have large annual production quantity.
(2) The adsorbent disclosed by the invention can be used for adsorbing heavy metals rapidly and efficiently. The concrete implementation is as follows: at the initial Cd 2+ The adsorbents reach equilibrium in the reaction time of 45min, 240min and 720min under the conditions of 50mg/L, 80mg/L and 100mg/L, and the maximum removal rate can reach almost 100 percent.
(3) The adsorbent of the invention is used for Cd in environment 2+ Has rapid and efficient adsorption performance even in the initial Cd state 2+ When the concentration is up to 200mg/L, the maximum adsorption capacity can reach 164.75mg/g. The invention has the advantages of simple preparation, high efficiency, high speed, low cost and the like, and has wide application prospect in the treatment of heavy metal polluted water bodies.
Drawings
FIG. 1 is a schematic diagram of the preparation and implementation of the method of the invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of adsorbents A and B in example 1; wherein A is adsorbent A and B is adsorbent B.
FIG. 3 is the effect on adsorption at different initial pH in example 2.
FIG. 4 is a graph of the initial Cd at different temperatures in example 3 2+ A research result diagram of the influence of concentration on the adsorption effect; wherein A is 20deg.C, B is 30deg.C, and C is 40deg.C.
FIG. 5 is a different initial Cd in example 4 2+ A research result diagram of the influence of different adsorption time under concentration on the adsorption effect; wherein A is 50mg/L and B is 80mg/L.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. For process parameters not specifically noted, this is done according to conventional techniques.
A schematic diagram of the method of the invention is shown in FIG. 1.
The printing and dyeing sludge used in the invention is industrial wastewater generated in the process of producing textile printing and dyeing in textile printing and dyeing factories and domestic wastewater discharged from living areas in factories, and is a mixed solid waste which is separated after being treated by a physical and chemical method in the sewage treatment plants, and the water content is higher, and is generally 80% -99%; the printing sludge used in the examples below was collected from a wastewater treatment plant of the Dongguan printing mill.
Example 1: preparation of adsorbents
And (3) placing the collected printing and dyeing sludge in a baking oven (80 ℃ for 48 hours), then adopting an oxygen-limited heating pyrolysis method, placing the dried raw materials in the pyrolysis oven, introducing nitrogen for 25min, heating to 900 ℃ at a heating rate of 300 ℃/h, carbonizing at a constant temperature for 2 hours, cooling to room temperature, grinding and sieving (0.30 mm) to obtain the adsorbent A.
Placing the collected printing and dyeing sludge in a baking oven (80 ℃ for 48 h), uniformly mixing the dried product and melamine according to a mass ratio of 1:1, placing the mixture in a pyrolysis furnace, introducing nitrogen for 25min, heating to 900 ℃ at a heating rate of 300 ℃/h, keeping the temperature constant for 2h, cooling to room temperature, leaching with hydrochloric acid (1.0 mol/L) for 5min, drying (80 ℃ for 48 h), grinding and sieving (0.30 mm) to obtain a product a. Then, the carbon disulfide and NaOH solutions (0.4 mol/L) were mixed in a volume ratio of 2: and 3, magnetically stirring for 4 hours and carrying out ultrasonic treatment for 1 hour to obtain a product b. The mass ratio of the final product a to the final product b is 8:1, magnetically stirring for 16 hours, and carrying out suction filtration and drying through a 0.45um water-based filter membrane to obtain the adsorbent B.
As shown in fig. 2 and table 1, the surface of the adsorbent B contains a large amount of particulate matter enrichment, and the specific surface area thereof is greatly increased.
TABLE 1 specific surface area of adsorbents
Adsorbent and process for producing the same | Specific surface area (m) 2 /g) |
A | 77.78 |
B | 119.93 |
Example 2: influence on adsorption Effect at different initial pH
0.02g of two adsorbents (adsorbent A and adsorbent B prepared in example 1) were weighed accurately and respectively at different pH values (1, 2, 3, 4, 5, 6, 7) and Cd content 2+ In 20mL solution with the concentration of 100mg/L, the oscillation adsorption test is carried out for 24 hours at 150r/min under normal temperature operation, and then the atomic absorption spectrophotometer is adopted to measure Cd in the supernatant 2+ Concentration and calculate Cd at different pH 2+ Is used as the adsorption amount of the catalyst.
As can be seen from FIG. 3, when the pH is increased from 1 to 7, the adsorption amounts of the two adsorbents are rapidly increased, the balance is achieved in the pH range of 5 to 7, the adsorption amount and the removal rate of the adsorbent B are far greater than those of the adsorbent A, the maximum adsorption amount of the adsorbent B is 99.75mg/g, the removal rate is 99.75%, the maximum adsorption amount of the adsorbent A is 48.62mg/g, and the removal rate is 48.62%. When the pH is 7, the adsorption capacity is slightly reduced, but the adsorption capacity and the removal rate of the adsorbent B are still far greater than those of the adsorbent A, the adsorption capacity of the adsorbent B is 98.85mg/g, and the removal rate is 98.85%.
This example illustrates that adsorbent B is specific to Cd in water 2+ The adsorption removal effect of the water treatment agent is good, and a foundation is provided for the practical application of the water treatment agent in water environments with different pH values.
Example 3: different initial Cd at different temperatures 2+ Influence of concentration on adsorption Effect
0.02g of three adsorbents (adsorbent A and adsorbent B prepared in example 1) were added to different initial Cd, respectively 2+ In 20mL solution with the concentration (20, 40, 60, 80, 100, 120, 140, 160, 180, 200 mg/L) and pH of 6, shaking at 150r/min at 20 ℃, 30 ℃ and 40 ℃ for 24 hours respectively, centrifuging to obtain supernatant (10000 rpm,15 min) and measuring Cd 2+ Concentration.
At 20 ℃, along with the initial Cd 2+ The increase in concentration increases the adsorption capacity of both adsorbents, with the adsorption capacity of adsorbent B increasing the fastest; when (when)Initial Cd 2+ When the concentration is 160-200 mg/L, the adsorption quantity of the two adsorbents tends to be balanced, and when the Cd is initially started 2+ At a concentration of 200mg/L, the maximum adsorption amounts of the two adsorbents A and B were 28.84mg/g and 92.97mg/g (a in FIG. 4), respectively; at 30 ℃ (b in FIG. 4), along with Cd 2+ Concentration increase the adsorption capacity of both adsorbents increases rapidly, when Cd is initially 2+ When the concentration is 160-200 mg/L, the adsorption quantity of the two materials tends to be balanced, and the Cd is the initial Cd 2+ When the concentration is 200mg/L, the maximum adsorption capacity of the two adsorbents A and B is 40.11mg/g and 98.61mg/g respectively; at 40 ℃ (c in fig. 4), along with the initial Cd 2+ The concentration is increased, and the adsorption quantity is rapidly increased; in Cd 2+ When the concentration is 180-200 mg/L, the adsorption amounts of the two adsorbents tend to be balanced, and when the Cd is initially started 2+ At a concentration of 200mg/L, the two adsorbents reached maximum adsorption amounts of 58.20mg/g and 164.75mg/g, respectively.
This example illustrates that adsorbent B is specific to Cd in water 2+ The adsorption capacity of (C) is very strong and far greater than that of adsorbent A, even at 200mg/L of high concentration Cd 2+ Under the condition, the adsorption capacity still reaches 164.75mg/g, thereby providing guarantee for the practical application of the catalyst under the condition of different heavy metal pollution degrees.
Example 4: different initial Cd 2+ Influence of different adsorption time under concentration on adsorption effect
0.02g of two adsorbents (adsorbent A and adsorbent B prepared in example 1) were added to the catalyst containing 50, 80 and 100mg/L Cd, respectively 2+ In 20mL of solution with pH of 6, the experiment is carried out at normal temperature, shaking at 150r/min, centrifuging for different time (5, 10, 15, 20, 30, 45, 90, 150, 240, 360, 720, 1440 min) to obtain supernatant (10000 rpm,15 min), and determining Cd therein 2+ Concentration.
As can be seen from FIG. 5, when Cd is initially present 2+ At a concentration of 50mg/L (a in FIG. 5), the adsorption amounts were rapidly increased with the increase of time, and after 30 to 45 minutes of adsorption, the adsorption amounts were gradually retarded and tended to be balanced, the adsorption equilibrium of 40.16mg/g was reached by the adsorbent A at 45 minutes, the adsorption equilibrium of 47.92mg/g was reached by the adsorbent B at 45 minutes, and the removal rate was 95.84%The method comprises the steps of carrying out a first treatment on the surface of the At the initial Cd 2+ At a concentration of 80mg/L (B in FIG. 5), the adsorption amount increases rapidly with increasing adsorption time, and after 45min of adsorption, the adsorption amount gradually becomes slow and tends to balance, the adsorbent A reaches adsorption balance at 240min, the equilibrium adsorption amount is 51.15mg/g, the adsorbent B reaches adsorption balance at 240min, the equilibrium adsorption amount is 74.24mg/g, and the removal rate is 92.80%; at the initial Cd 2+ When the concentration is 100mg/L (c in FIG. 5), the adsorption amount is rapidly increased along with the increase of time, the adsorption amount is gradually slowed down and approaches equilibrium after 240-720 min, the adsorption equilibrium of the adsorbent A reaches 49.35mg/g at 720min, the removal rate is 49.35%, the adsorption equilibrium of the adsorbent B reaches 81.99mg/g during 720min, and the removal rate is 81.99%.
The experimental results show that the adsorbent B is used for preparing three different initial Cds 2+ The adsorption equilibrium time is 45min, 240min and 720min respectively under the concentration, and the water Cd 2+ The maximum removal rate of (a) is close to 100%.
This example illustrates that adsorbent A is specific to Cd in a body of water 2+ The adsorption removal rate is highest, and technical guarantee is provided for rapidly and efficiently treating heavy metal pollution of water body.
Example 5: adsorption thermodynamic parameter study
According to example 3, initial Cd at different temperatures 2+ The data of the effect of concentration on adsorption is used to calculate the adsorption thermodynamic parameters, see Table 2, where ΔG 0 (kJ mol -1 ) Is Gibbs free energy, deltaH 0 (kJ mol -1 ) Is the enthalpy change, deltaS 0 (kJ mol -1 K -1 ) Is entropy change.
TABLE 2 thermodynamic parameters of adsorption
Table 2 shows that two types of suctionΔG of the attachment agent 0 The values are negative numbers, indicating that adsorption is a spontaneous process; ΔH 0 >0, then the adsorption is an endothermic reaction; ΔS 0 >0 shows that as the temperature increases, the degree of confusion of the system increases, facilitating the occurrence of adsorption.
This example illustrates that adsorbent B is specific to Cd in water 2+ The adsorption is spontaneous endothermic reaction, is favorable for adsorption, and provides a theoretical basis for practical application.
The above is a preferred embodiment of the present invention, and those skilled in the art may make various modifications and optimization without departing from the scope of the technical idea of the present invention. And all such modifications and optimization are intended to be included within the scope of this invention as defined in the following claims without departing from the spirit and scope of the invention in accordance with the following claims.
Claims (7)
1. The application of the high-efficiency adsorption remover for cadmium ions in removing heavy metal cadmium ions in the environment is characterized in that: the efficient adsorption remover for cadmium ions is prepared by a method comprising the following steps:
(1) Drying and grinding treatment is carried out after the printing and dyeing sludge is collected;
(2) Uniformly mixing the ground printing and dyeing sludge and melamine according to the mass ratio of 1:1-1:3, placing the mixture in a pyrolysis furnace for oxygen-limited pyrolysis, introducing nitrogen for 20-40 min, heating to 700-900 ℃ at the heating rate of 300-600 ℃/h, carbonizing at constant temperature for 2-4 h, cooling to room temperature, taking out, pickling, and drying to obtain a pickling and drying product;
(3) Mixing carbon disulfide and sodium hydroxide solution according to a volume ratio of 1:1-1:3, magnetically stirring 2-6 h, and then performing ultrasonic treatment for 0.5-2 h to obtain a product M; the acid washing and drying product and the product M are mixed according to the mass ratio of 5:1 to 10:1, mixing, magnetically stirring 12-20 and h, extracting the product, and grinding and sieving to obtain powder, namely the efficient adsorption remover for cadmium ions.
2. The use according to claim 1, characterized in that:
in the step (1), the drying is that the water content is lower than 5%, the drying temperature is set to be 60-100 ℃ and the time is 36-96 h;
the specific arrangement of the pickling in the step (2) is as follows: leaching the limited oxygen pyrolysis product by hydrochloric acid with the concentration of 0.1-2.0 mol/L for 1-10 minutes, and setting the drying temperature to 60-100 ℃ and the drying time to 36-96 h.
3. The use according to claim 2, characterized in that:
in the step (1), the temperature of drying is set to 80 ℃ and the time is 48 h;
in the step (2), the specific setting of oxygen limiting pyrolysis is as follows: uniformly mixing the printing and dyeing sludge after grinding treatment and melamine according to the mass ratio of 1:1, placing the mixture in a pyrolysis furnace, introducing nitrogen for 25min, heating to 900 ℃ at the heating rate of 300 ℃/h, carbonizing at constant temperature for 2h, cooling to room temperature, and taking out;
the specific arrangement of the pickling in the step (2) is as follows: leaching the limited oxygen pyrolysis product by hydrochloric acid with the concentration of 1.0mol/L for 5 minutes, and setting the drying temperature to 80 ℃ and the drying time to 48h.
4. A use according to any one of claims 1-3, characterized in that:
in the step (3), the concrete steps of uniformly mixing and reacting the carbon disulfide and the sodium hydroxide are as follows: carbon disulfide and sodium hydroxide solution in volume ratio of 2:3, mixing, magnetically stirring 4, h, then carrying out ultrasonic treatment on the mixture for 1, h, drying, grinding and sieving;
in the step (3), the specific arrangement of the reaction between the pickling and drying product and the product M is as follows: acid washing and drying a product and a product M according to a mass ratio of 8:1, mixing, and magnetically stirring 16 h;
in the step (3), the concentration of the sodium hydroxide solution is 0.4 mol/L;
in the step (3), the powder is ground and then passes through a sieve with the particle size of 0.3 and mm, and the particle size of the obtained powder is smaller than 0.3 and mm.
5. The use according to claim 1, characterized in that:
the environment is water environment or soil environment.
6. The use according to claim 1, characterized in that: the method comprises the following steps: and adding the high-efficiency adsorption remover for cadmium ions into a water body containing heavy metal cadmium ions, and fully contacting and reacting to remove the cadmium ions in the water body.
7. The use according to claim 6, characterized in that:
the dosage of the high-efficiency adsorption remover for cadmium ions is 0.5-2 g/L;
the initial pH of the water body is 1.0-7.0;
the initial concentration of the heavy metal cadmium ions in the water body is 10-200 mg/L;
the reaction conditions are 10-50 ℃ and 6-24 h.
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