CN110064380B - Nitrogen/sulfur co-doped porous cellulose adsorbent and preparation method and application thereof - Google Patents
Nitrogen/sulfur co-doped porous cellulose adsorbent and preparation method and application thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 82
- 239000001913 cellulose Substances 0.000 title claims abstract description 82
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000003463 adsorbent Substances 0.000 title claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 21
- 239000011593 sulfur Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims abstract description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 22
- 239000011651 chromium Substances 0.000 claims abstract description 22
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 11
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229920000875 Dissolving pulp Polymers 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005342 ion exchange Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 229910001430 chromium ion Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000006722 reduction reaction Methods 0.000 description 2
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- 239000011358 absorbing material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000005067 remediation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a nitrogen/sulfur co-doped porous cellulose adsorbent for treating chromium-containing wastewater, and a preparation method and application thereof. The preparation method comprises the following steps: (1) polymerizing vinyl imidazole monomer to obtain polyvinyl imidazole; (2) cellulose and polyvinyl imidazole react in one step to obtain quaternary ammonium salt functionalized cellulose; (3) and performing ion exchange on the quaternary ammonium salt functionalized cellulose and an ammonium tetrathiomolybdate solution to obtain the nitrogen/sulfur co-doped cellulose adsorbent. The preparation method provided by the invention takes renewable resources as raw materials, has wide sources and low price, accords with the concept of green environmental protection, and the prepared nitrogen/sulfur co-doped porous cellulose adsorbent has excellent adsorption rate, adsorption capacity and affinity to hexavalent chromium, has large adsorption capacity, and can be applied to treatment of chromium-containing wastewater.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a nitrogen/sulfur co-doped porous cellulose adsorbent for treating chromium-containing wastewater, and a preparation method and application thereof.
Background
The rapid development of industry generates a large amount of wastewater, wherein heavy metal ion pollutants seriously restrict the development of economy and become a great problem influencing human health and ecological balance. Chromium has been widely used in the past decades in the industries of metallurgy, electroplating, metal working, steel making, electricity generation, tanning and textile. These applications result in the release of chromium ions into the natural environment. The chromium ions can directly destroy water quality to cause poisoning of aquatic organisms, and can also migrate into human bodies along with food chains to harm human health. Therefore, the world health organization recommends that the maximum allowable concentration of chromium in drinking water be 50ppb and the maximum emission standard of industrial wastewater be 100 ppb. In order to meet this emission standard, a number of remediation processes, such as precipitation, ion exchange, membrane filtration, chemical reduction, adsorption, biological, photocatalytic, electrochemical flocculation, etc., have been used to remove chromium ions from aqueous solutions. Among these methods, the adsorption method has attracted attention because of its characteristics of high efficiency, reliability, simple equipment, economical feasibility, and the like. The core of the adsorption method lies in the design and preparation of the adsorption material. At present, a plurality of adsorbing materials, such as activated carbon, molecular sieves, metal oxides, metal organic framework materials and the like, are applied to the adsorption and separation of hexavalent chromium ions. However, most of these adsorbents have problems of low adsorption efficiency, high price, and the like. Therefore, the development of low-cost and high-efficiency adsorbents is of great significance.
Cellulose is a renewable resource, has the characteristics of abundance, low price, easy obtaining and the like, and a large number of hydroxyl functional groups on the surface of the cellulose can be used for anchoring active adsorption sites and providing electrons for the reduction of hexavalent chromium ions, so the cellulose is a potential chromium-absorbing material. The cellulose-based adsorbent reported at present shows a certain adsorption effect on chromium ions, but the adsorption capacity, selectivity and affinity of the cellulose-based adsorbent on hexavalent chromium still need to be further improved.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a nitrogen/sulfur co-doped porous cellulose adsorbent.
The preparation method adopts a strategy of 'coordination to anions' and prepares the cellulose adsorbent containing organic nitrogen and inorganic sulfur codoped through three steps of polymerization, crosslinking and ion exchange, and the adsorbent has excellent adsorption rate, adsorption capacity and affinity to hexavalent chromium.
The invention also aims to provide the nitrogen/sulfur co-doped porous cellulose adsorbent prepared by the method.
The invention further aims to provide application of the nitrogen/sulfur co-doped porous cellulose adsorbent in treatment of chromium-containing wastewater.
The purpose of the invention is realized by the following scheme:
a preparation method of a nitrogen/sulfur co-doped porous cellulose adsorbent comprises the following steps: (1) polymerizing vinyl imidazole monomer to obtain polyvinyl imidazole; (2) cellulose and polyvinyl imidazole react in one step to obtain quaternary ammonium salt functionalized cellulose; (3) and performing ion exchange on the quaternary ammonium salt functionalized cellulose and an ammonium tetrathiomolybdate solution to obtain the nitrogen/sulfur co-doped cellulose adsorbent.
In the step (1), the polymerization condition is preferably polymerization reaction at 30-100 ℃ for 1-24 h; more preferably at 70 ℃ for 4 h. The product obtained in the reaction can be directly used in the next reaction.
The polymerization is preferably carried out under initiator initiation; the amount of the initiator used is a conventional amount, and is preferably 2% by mass of the vinylimidazole monomer.
The initiator may be a conventional monomer polymerization initiator such as Azobisisobutyronitrile (AIBN).
In the step (2), the reaction condition is preferably 40-100 ℃ for 0.5-24 h; more preferably 50-70 ℃ for 1-4 h.
The cellulose and the polyvinyl imidazole are preferably used in an amount of 1 to 4 parts by mass of the cellulose and 1 to 4 parts by mass of the polyvinyl imidazole.
The mass ratio of cellulose to polyvinylimidazole used is more preferably from 4:1 to 1: 1.
And (2) reacting the cellulose and the polyvinyl imidazole in an alkaline solution system environment under the action of a cross-linking agent to obtain the quaternary ammonium salt functionalized cellulose.
The crosslinking agent is conventional in the art, such as epichlorohydrin. The mass volume portion ratio of the cross-linking agent to the cellulose is g and mL, the mass portion ratio of the cellulose is 1-4, and the mass portion ratio of the cross-linking agent to the cellulose is 8-16.
After the cross-linking agent is added into the system, preferably, the mixture is stirred uniformly at low temperature and then heated for reaction; the low-temperature stirring is preferably carried out for 1 to 3 hours at the temperature of between 0 and 20 ℃;
preferably, cellulose and polyvinyl imidazole are respectively prepared into solution, then the solution is mixed and stirred evenly, and a cross-linking agent is added for reaction; the stirring time is preferably 1-24 h; more preferably 5-12 h.
More preferably, cellulose is dissolved in a mixed aqueous solution containing sodium hydroxide and urea to obtain a cellulose solution; the concentration of the cellulose solution is preferably 2-4 wt%; the content of urea in the mixed aqueous solution is preferably 9 to 15 wt%, more preferably 12 wt%; the sodium hydroxide is preferably 6 to 8 wt%, more preferably 7 wt%.
More preferably, polyvinylimidazole is dissolved in a urea solution; the concentration of the urea solution is preferably 16-37 wt%, more preferably 28 wt%.
In the step (3), the mass ratio of the quaternary ammonium salt functionalized cellulose to the ammonium tetrathiomolybdate is preferably 2:1-4: 1.
The concentration of the ammonium tetrathiomolybdate solution is preferably 0.1-10g/L, more preferably 0.25-1 g/L.
The ion exchange is preferably carried out at room temperature with stirring, preferably for 6 to 72h, more preferably for 24 to 48 h.
The method of the invention more particularly comprises the following steps:
(1) vinyl imidazole is polymerized for 1 to 24 hours at the temperature of between 30 and 100 ℃ to obtain polyvinyl imidazole;
(2) dissolving cellulose in a mixed aqueous solution containing sodium hydroxide and urea to obtain a cellulose solution; dissolving polyvinyl imidazole in a urea solution, mixing with a cellulose solution, and uniformly stirring;
(3) adding a cross-linking agent into the system obtained in the step (2), uniformly stirring at low temperature, heating to 40-100 ℃, and reacting for 0.5-24h to obtain quaternary ammonium salt functionalized cellulose;
(4) adding quaternary ammonium salt functionalized cellulose into an ammonium tetrathiomolybdate solution, and stirring for 6-72h at room temperature to obtain the nitrogen/sulfur co-doped porous cellulose adsorbent.
The preparation method of the invention takes renewable resources as raw materials, has wide sources and low price, and accords with the concept of green environmental protection.
The invention also provides the nitrogen/sulfur co-doped porous cellulose adsorbent prepared by the method, which has excellent adsorption rate, adsorption capacity and affinity to hexavalent chromium, has large adsorption capacity, and can be applied to chromium-containing wastewater treatment.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method takes renewable cellulose as a raw material, has wide sources and low cost, and accords with the concept of green environmental protection.
(2) The nitrogen/sulfur co-doped cellulose adsorbent disclosed by the invention has the advantages of excellent adsorption rate and adsorption capacity for hexavalent chromium, large adsorption capacity, strong anion interference resistance and high affinity.
Drawings
FIG. 1 is a reaction scheme of the preparation method of the present invention.
FIG. 2 is a scanning electron micrograph of the material prepared in example 5.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available. The using amount of each component is g and mL in parts by mass.
The reaction scheme of the preparation method of the invention is shown in figure 1.
Example 1
(1) Preparation of polyvinyl imidazole: 10 parts by volume of vinylimidazole, 0.2 part by mass of azobisisobutyronitrile and 55 parts by volume of toluene were reacted at 70 ℃ for 4 hours to obtain white polyvinylimidazole powder.
(2) 0.125 mass part of polyvinyl imidazole is added into 15 volume parts of 28 wt% urea solution to be dissolved, 13 mass parts of 4 wt% cellulose solution (7 wt% sodium hydroxide and 12 wt% urea) is added, and the mixture is stirred for 5 hours at room temperature and uniformly mixed.
(3) And (3) adding 2 parts by volume of epoxy chloropropane into the system in the step (2) to ensure that the mass-to-volume ratio of the cellulose to the polyvinyl imidazole to the epoxy chloropropane is 4:1:16, stirring for 1h at 0 ℃, placing the obtained transparent solution into an oven to react for 1h at 60 ℃, washing the obtained solid sample for several times by using deionized water and tert-butyl alcohol, and then freeze-drying.
(4) And (4) adding 0.1 part by mass of the solid sample obtained in the step (3) into 100 parts by volume of 0.25g/L ammonium tetrathiomolybdate solution, and stirring at room temperature for 24 hours. And after the reaction is finished, washing the obtained solid sample with deionized water for several times, and freeze-drying for 24 hours to obtain the cellulose composite material.
(5) Mixing the obtained cellulose composite material with a hexavalent chromium solution with the concentration of 20-200mg/L, placing the mixture into a constant-temperature oscillator for oscillation, and measuring the concentration of chromium in the solution after the balance is achieved. The maximum adsorption capacity of the adsorbent for chromium was 126 mg/g.
Example 2
(1) 0.330 part by mass of polyvinyl imidazole is added into 15 parts by volume of 28 wt% urea solution to be dissolved, 13 parts by mass of 4 wt% cellulose solution (7 wt% sodium hydroxide and 12 wt% urea) is added, and the mixture is stirred and mixed evenly for 12 hours at room temperature.
(2) And (2) adding 2 parts by volume of epoxy chloropropane into the system in the step (1) to ensure that the mass-to-volume ratio of the cellulose to the polyvinyl imidazole to the epoxy chloropropane is 3:4:12, stirring for 2 hours at 5 ℃, placing the obtained transparent solution into an oven to react for 2 hours at 50 ℃, washing the obtained solid sample for a plurality of times by using deionized water and tert-butyl alcohol, and then freeze-drying.
(3) And (3) adding 0.15 mass part of the solid sample obtained in the step (2) into 100 volume parts of 0.75g/L ammonium tetrathiomolybdate solution, and stirring at room temperature for 36 hours. And after the reaction is finished, washing the obtained solid sample by deionized water for a plurality of times, and drying for 24 hours in vacuum to obtain the cellulose composite material.
(4) Mixing the obtained cellulose composite material with a chromium solution with the concentration of 20-200mg/L, placing the mixture into a constant-temperature oscillator for oscillation, and measuring the concentration of chromium in the solution after the balance is achieved. The maximum adsorption capacity of the adsorbent for chromium was 163 mg/g.
Example 3
(1) 0.167 part by mass of polyvinyl imidazole is added into 15 parts by volume of 28 wt% urea solution to be dissolved, 25 parts by mass of 2 wt% cellulose solution (7 wt% sodium hydroxide, 12 wt% urea) is added, and the mixture is stirred and mixed evenly for 8 hours at room temperature.
(2) And (2) adding 2 parts by volume of epoxy chloropropane into the system in the step (1) to ensure that the mass volume ratio of the cellulose to the polyvinyl imidazole to the epoxy chloropropane is 3:2:12, stirring for 3 hours at 0 ℃, placing the obtained transparent solution into an oven to react for 4 hours at 70 ℃, washing the obtained solid sample for a plurality of times by using deionized water and tert-butyl alcohol, and then freeze-drying.
(3) And (3) adding 0.2 part by mass of the solid sample obtained in the step (2) into 100 parts by volume of 0.75g/L ammonium tetrathiomolybdate solution, and stirring at room temperature for 48 hours. And after the reaction is finished, washing the obtained solid sample with deionized water for several times, and freeze-drying for 24 hours to obtain the cellulose composite material.
(4) Mixing the obtained cellulose composite material with a chromium solution with the concentration of 20-200mg/L, placing the mixture into a constant-temperature oscillator for oscillation, and measuring the concentration of chromium in the solution after the balance is achieved. The maximum adsorption capacity of the adsorbent for chromium was 159 mg/g.
Example 4
(1) 0.25 part by mass of polyvinyl imidazole is added into 15 parts by volume of 28 wt% urea solution to be dissolved, 8.5 parts by mass of 3 wt% cellulose solution (7 wt% sodium hydroxide and 12 wt% urea) is added, and the mixture is stirred for 8 hours at room temperature and uniformly mixed.
(2) And (2) adding 3 parts by volume of epoxy chloropropane into the system in the step (1) to ensure that the mass-to-volume ratio of the cellulose to the polyvinyl imidazole to the epoxy chloropropane is 1:1:12, stirring for 2 hours at 10 ℃, placing the obtained transparent solution into an oven to react for 2 hours at 60 ℃, washing the obtained solid sample for a plurality of times by using deionized water and tert-butyl alcohol, and then freeze-drying.
(3) And (3) adding 0.2 mass part of the solid sample obtained in the step (2) into 100 volume parts of 1.0g/L ammonium tetrathiomolybdate solution, and stirring at room temperature for 48 hours. And after the reaction is finished, washing the obtained solid sample by deionized water for a plurality of times, and drying for 24 hours in vacuum to obtain the cellulose composite material.
(4) Mixing the obtained cellulose composite material with a chromium solution with the concentration of 20-200mg/L, placing the mixture into a constant-temperature oscillator for oscillation, and measuring the concentration of chromium in the solution after the balance is achieved. The maximum adsorption capacity of the adsorbent for chromium was 181 mg/g.
Example 5
(1) 0.5 part by mass of polyvinyl imidazole is added into 15 parts by volume of 28 wt% urea solution to be dissolved, 13 parts by mass of 4 wt% cellulose solution (7 wt% sodium hydroxide and 12 wt% urea) is added, and the mixture is stirred and mixed evenly for 12 hours at room temperature.
(2) Adding 4 parts by volume of epoxy chloropropane into the system in the step (1) to ensure that the mass volume ratio of the cellulose to the polyvinyl imidazole to the epoxy chloropropane is 1:1:8, stirring for 3h at 0 ℃, placing the obtained transparent solution into an oven to react for 2h at 60 ℃, washing the obtained solid sample for a plurality of times by using deionized water and tert-butyl alcohol, and then freeze-drying.
(3) And (3) adding 0.15 mass part of the solid sample obtained in the step (2) into 100 volume parts of 0.5g/L ammonium tetrathiomolybdate solution, and stirring at room temperature for 48 hours. After the reaction is finished, the obtained solid sample is washed by deionized water for a plurality of times, and then is dried in vacuum for 24 hours to obtain the cellulose composite material, and the cellulose composite material is observed by scanning an electron microscope, and the result is shown in figure 2.
(4) Mixing the obtained cellulose composite material with a chromium solution with the concentration of 20-200mg/L, placing the mixture into a constant-temperature oscillator for oscillation, and measuring the concentration of chromium in the solution after the balance is achieved. The maximum adsorption capacity of the adsorbent for chromium was 232 mg/g.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a nitrogen/sulfur co-doped porous cellulose adsorbent is characterized by comprising the following steps:
(1) vinyl imidazole is polymerized for 1 to 24 hours at the temperature of between 30 and 100 ℃ to obtain polyvinyl imidazole;
(2) dissolving cellulose in a mixed aqueous solution containing sodium hydroxide and urea to obtain a cellulose solution; dissolving polyvinyl imidazole in a urea solution, mixing with a cellulose solution, and uniformly stirring;
adding a cross-linking agent into the system, uniformly stirring at low temperature, heating to 40-100 ℃ and reacting for 0.5-24h to obtain quaternary ammonium salt functionalized cellulose;
(3) adding quaternary ammonium salt functionalized cellulose into an ammonium tetrathiomolybdate solution, and stirring for 6-72h at room temperature to obtain the nitrogen/sulfur co-doped porous cellulose adsorbent.
2. The method for preparing a nitrogen/sulfur co-doped porous cellulose adsorbent according to claim 1, characterized in that: the dosage of the cellulose and the polyvinyl imidazole is 1 to 4 parts by mass of the cellulose and 1 to 4 parts by mass of the polyvinyl imidazole; the mass ratio of the cellulose to the polyvinyl imidazole is 4:1-1: 1.
3. The method for preparing a nitrogen/sulfur co-doped porous cellulose adsorbent according to claim 1, characterized in that: the cross-linking agent is epichlorohydrin; the cross-linking agent and the cellulose are 1-4 parts by mass of the cellulose and 8-16 parts by volume of the cross-linking agent.
4. The method for preparing a nitrogen/sulfur co-doped porous cellulose adsorbent according to claim 1, characterized in that: in the step (3), the mass ratio of the quaternary ammonium salt functionalized cellulose to the ammonium tetrathiomolybdate is 2:1-4: 1; the concentration of the ammonium tetrathiomolybdate solution is 0.1-10 g/L.
5. A nitrogen/sulfur-codoped porous cellulose adsorbent, characterized by being obtained by the production method according to any one of claims 1 to 4.
6. Use of the nitrogen/sulfur co-doped porous cellulose adsorbent according to claim 5 in the treatment of chromium-containing wastewater.
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| Reaction mechanism of hexavalent chromium with cellulose;Shan-Li Wang等;《Chemical Engineering Journal》;20111015;第174卷(第1期);全文 * |
| Remarkable Acid Stability of Polypyrrole-MoS4: A Highly Selective and Efficient Scavenger of Heavy Metals Over a Wide pH Range;Linxia Xie等;《Adv. Funct. Mater.》;20180330;第28卷(第20期);1800502页第3-4节 * |
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