CN116408053A - Papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent and preparation method and application thereof - Google Patents
Papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent and preparation method and application thereof Download PDFInfo
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- CN116408053A CN116408053A CN202310407417.9A CN202310407417A CN116408053A CN 116408053 A CN116408053 A CN 116408053A CN 202310407417 A CN202310407417 A CN 202310407417A CN 116408053 A CN116408053 A CN 116408053A
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 235000002906 tartaric acid Nutrition 0.000 title claims abstract description 100
- 239000011975 tartaric acid Substances 0.000 title claims abstract description 100
- 239000003463 adsorbent Substances 0.000 title claims abstract description 70
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 54
- 238000009830 intercalation Methods 0.000 claims abstract description 54
- 230000002687 intercalation Effects 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 44
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 19
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 18
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 17
- 239000001433 sodium tartrate Substances 0.000 claims description 17
- 229960002167 sodium tartrate Drugs 0.000 claims description 17
- 235000011004 sodium tartrates Nutrition 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 37
- 239000000463 material Substances 0.000 abstract description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001431 copper ion Inorganic materials 0.000 abstract description 8
- 239000011777 magnesium Substances 0.000 description 85
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 74
- 230000000052 comparative effect Effects 0.000 description 26
- 229920002678 cellulose Polymers 0.000 description 25
- 239000001913 cellulose Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229910021645 metal ion Inorganic materials 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000010893 paper waste Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229960001545 hydrotalcite Drugs 0.000 description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010814 metallic waste 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
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- -1 tartrate ions Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- B01J20/22—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent and a preparation method and application thereof, and belongs to the technical field of adsorption materials. The adsorbent is prepared by the following method: firstly, tartaric acid is adopted to carry out intercalation on Mg/Al-LDHs to obtain tartaric acid intercalation Mg/Al-LDHs, a papermaking waste pulp precipitate is taken as a raw material to prepare a granular fiber compound, and then the fiber compound is grafted with the tartaric acid intercalation Mg/Al-LDHs through a crosslinking agent to obtain the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent. The papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent prepared by the invention has excellent adsorption capacity on copper ions.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a papermaking waste pulp grafted tartaric acid intercalated magnesium aluminum-based layered double hydroxide (Mg/Al-LDHs) adsorbent, and a preparation method and application thereof.
Background
The water pollution in China mainly takes serious pollution sources such as metal ions, organic matters and the like as main. The pollutants enter the water body in the nature and exceed the pollution caused by the self-cleaning capability of the water body, so that the physical, chemical, biological and other aspects of the water body are changed, and the water quality is deteriorated. These contaminants enter the human body through the drinking water or food chain and can cause various degrees of damage to the health of the human body. How to reduce the concentration of metal ions in waste liquid and improve the water quality, thereby improving the water recycling efficiency and reducing the pollution to environmental water is one of the most important directions and purposes of numerous researchers for the research of adsorbents. Among the existing sewage treatment methods, the adsorption method is one of the most widely used methods. Many scientific researchers at home and abroad have been devoted to the research and application of adsorbents for a long time. The defects of high cost, limited adsorption capacity, difficult regeneration and the like limit the wide use of the existing adsorption material, and promote the scientific research of people on the novel adsorption material with high economic benefit and adsorption capacity.
Chinese patent CN103638905B discloses a method for adsorbing heavy metals using tartaric acid intercalated hydrotalcite, the method comprising: (1) PreparingMagnesium nitrate, a salt solution of aluminum nitrate and a sodium hydroxide alkali solution are prepared into carbonic acid hydrotalcite by adopting a coprecipitation method; (2) preparing tartaric acid solution; (3) And (3) putting the carbonic acid hydrotalcite into tartaric acid solution, carrying out ion exchange for 12 hours at 120 ℃, and then filtering, washing and drying to obtain the hydrotalcite. The tartaric acid intercalated hydrotalcite prepared by the invention can rapidly adsorb Cu in water 2+ Ions. However, after tartrate ions are intercalated between Layered Double Hydroxides (LDHs) as organic acid radicals, the hydrophilicity of the LDHs is reduced compared with that of LDHs which are not intercalated, and the problem that LDHs is easy to agglomerate in water cannot be effectively solved, so that the LDHs is not beneficial to the adsorption of metal ions in wastewater.
On the other hand, the explosive development of the paper industry causes serious pollution and destruction of the environment and the global ecological system, and even if the most modern and efficient operation technology is adopted, the production of one ton of paper generates at least 50 cubic meters of waste pulp, and if the waste pulp is directly discharged, great pollution is likely to be caused to our environment. In order to effectively solve the serious pollution problem in China, realize sustainable development of the papermaking industry and the country, recycle waste liquid and apply to other fields, has great significance to green economy. In order to reasonably utilize papermaking waste pulp, chinese patent CN101396649A utilizes a penetrating agent to modify a fiber compound prepared from papermaking waste pulp sediment, so as to prepare a liquid pollutant adsorbent; the method fully utilizes the effective components of the waste paper pulp sediment, opens up a new way for treating the waste paper pulp sediment and reduces environmental pollution. Although cellulose contains a large number of hydroxyl groups, most of the hydroxyl groups form cellulose with high crystallinity in a multi-level coiling mode due to strong hydrogen bonding action between the hydroxyl groups, and only partial free hydroxyl groups can be used for adsorbing metal ions. Thus, cellulose is not strong in its ability to adsorb metals. In addition, the cellulose content in the waste paper pulp is not so high that the metal ion adsorption capacity of the waste paper pulp is weaker.
Aiming at the problems, a novel adsorption material is developed, so that the papermaking waste pulp can be reasonably utilized, and an adsorbent with high-efficiency adsorption performance on metal ions can be provided, and the adsorption material has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent and a preparation method thereof, which can simultaneously solve the problems of low cellulose reaction activity and easy agglomeration of organic intercalated LDHs in the papermaking waste pulp, and prepare the adsorbent with excellent adsorption performance on heavy metal ions; meanwhile, the waste papermaking pulp can be reasonably utilized, and the pollution problem of the waste papermaking pulp is solved.
The aim of the invention is achieved by the following technical scheme.
The papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent is prepared by the following method: firstly, tartaric acid is adopted to carry out intercalation on Mg/Al-LDHs to obtain tartaric acid intercalation Mg/Al-LDHs, a papermaking waste pulp precipitate is taken as a raw material to prepare a granular fiber compound, and then the fiber compound is grafted with the tartaric acid intercalation Mg/Al-LDHs through a crosslinking agent to obtain the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent.
Preferably, the crosslinking agent is N, N-methylenebisacrylamide.
Preferably, the mass ratio of the fiber composite to the tartaric acid intercalated Mg/Al-LDHs is 1 (0.3-3.5).
The preparation method of the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent comprises the following steps:
s1, preparing a granular fiber compound by taking a papermaking waste pulp precipitate as a raw material;
s2, adding sodium tartrate to remove CO 2 Fully stirring the solution in the deionized water to obtain tartaric acid solution; then adding pretreated Mg/Al-LDHs into the tartaric acid solution, regulating the pH value of the mixed solution to 10-11, stirring and refluxing at 50-70 ℃ for reaction for 24-36 h, filtering, washing and drying to obtain tartaric acid intercalation Mg/Al-LDHs;
s3, dissolving lithium chloride in N, N-dimethylacetamide, adding the fiber compound obtained in the step S1 after ultrasonic dispersion, and stirring for 2-3 hours at 90-110 ℃ in a protective gas atmosphere to obtain a solution A; dissolving tartaric acid intercalation Mg/Al-LDHs obtained in the step S2 in acetic acid solution, and performing ultrasonic dispersion to obtain solution B;
s4, mixing the solution A obtained in the step S3 with the solution B, uniformly stirring, adding N, N-methylene bisacrylamide, stirring for 1-2 hours at 30-50 ℃, adjusting the pH value of the solution to 9-10, stirring for 1-2 hours at 60-80 ℃, filtering, washing, drying and grinding to obtain the papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent.
The invention takes papermaking waste pulp sediment as a raw material to prepare a fiber compound, prepares tartaric acid intercalation Mg/Al-LDHs by an anion exchange method, and finally grafts the tartaric acid intercalation Mg/Al-LDHs with the fiber compound by a crosslinking reaction to obtain the cellulose grafted tartaric acid intercalation Mg/Al-LDHs adsorbent. On one hand, the fiber compound contains a large amount of hydroxyl groups, the hydrophilicity of the adsorbent can be obviously improved after grafting, and on the other hand, the adsorbent with a huge rigid structure can be obtained after grafting, so that the dispersing and dissolving capacity of the adsorbent material in wastewater can be improved from the two aspects, the possibility of contact with metal ions can be increased, and the problem that the hydrophilicity of the adsorbent material is reduced due to tartaric acid intercalation can be solved; meanwhile, more adsorption groups in the fiber composite and tartaric acid intercalation Mg/Al-LDHs can be exposed through grafting, so that the possibility of contact with metal ions is increased, and the capability of adsorbing the metal ions is further enhanced. Under the synergistic effect of the fiber compound, the tartaric acid intercalation Mg/Al-LDHs and the N, N-methylene bisacrylamide, the dispersion capacity of the adsorbent in water can be improved, the metal ion adsorption capacity of the adsorbent can be improved, and meanwhile, the problems that cellulose in waste papermaking pulp is low in reactivity and the tartaric acid intercalation LDHs is easy to agglomerate are solved, so that the adsorption capacity of the prepared cellulose grafted tartaric acid intercalation Mg/Al-LDHs adsorbent is remarkably improved.
Preferably, the method of preparing the particulate fibrous composite of step S1 is as follows: repeatedly washing the papermaking waste pulp precipitate with deionized water and absolute ethyl alcohol for 3-5 times, drying at 80-100 ℃, crushing and sieving with a 200-mesh sieve to obtain the granular fiber compound.
Preferably, in the step S2, the mass ratio of the sodium tartrate to the Mg/Al-LDHs is (8-10): 25.
Preferably, in step S2, the method for pretreatment of Mg/Al-LDHs is as follows: and (3) calcining the Mg/Al-LDHs at 450-550 ℃ for 3-5 h. The pretreatment is to remove CO between LDHs layers 3 2- 。
Preferably, in the step S3, the mass ratio of the fiber composite to the lithium chloride to the N, N-dimethylacetamide is (4-6): (6-9): (85-90), and the mass ratio of the tartaric acid intercalation Mg/Al-LDHs to the acetic acid solution is 1 (45-55). The crystal areas formed by the intramolecular and intermolecular hydrogen bonds of the cellulose prevent the solvent from contacting with the cellulose molecules, and the effect of the lithium chloride is mainly to perform activation pretreatment on the cellulose; the partial hydrogen bonds of the cellulose after the activation pretreatment are broken, the molecular chains obtain a looser configuration, and the closely arranged crystal areas are easier to contact with the solvent, so that the cellulose is dissolved more rapidly.
Preferably, in the step S4, the mass ratio of the solution A to the solution B is 1 (1-7), and the mass ratio of the solution A to the N, N-methylenebisacrylamide is 1 (0.2-2.2).
The invention also provides application of the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent in wastewater treatment.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the fiber composite is grafted onto the tartaric acid intercalation Mg/Al-LDHs, so that not only is the capability of the tartaric acid intercalation Mg/Al-LDHs for adsorbing copper ions reserved, but also the hydroxyl in the fiber composite is added as a binding site of the copper ions, and the adsorption capability of the prepared adsorbent for metal ions is obviously improved under the combined action of the tartaric acid intercalation Mg/Al-LDHs.
2. Tartaric acid is not effective in inhibiting aggregation of LDHs after intercalation of LDHs. In the invention, N-methylene bisacrylamide is selected as a connecting agent to graft the fiber compound and tartaric acid intercalation Mg/Al-LDHs. N, N-methylene bisacrylamide is used as a dialdehyde linking agent, and the polar structure of carbonyl enables the dialdehyde linking agent to easily generate nucleophilic reaction with polar groups, so that the fiber composite grafted tartaric acid intercalated Mg/Al-LDHs adsorbent has a huge rigid structure, and therefore, the fiber composite grafted tartaric acid intercalated Mg/Al-LDHs adsorbent has better dispersibility in water than a matrix LDHs. By grafting N, N-methylene bisacrylamide, more adsorption groups in the fiber compound and tartaric acid intercalation Mg/Al-LDHs can be exposed, and the possibility of contact with metal ions is increased. In addition, N, N-methylene bisacrylamide has amino groups, so that the adsorption capacity to copper ions can be further enhanced. Under the synergistic effect of the fiber compound, the tartaric acid intercalation Mg/Al-LDHs and the N, N-methylene bisacrylamide, the dispersion capacity of the adsorbent in wastewater can be improved, and the metal ion adsorption capacity of the adsorbent can be enhanced, so that the adsorbent with excellent adsorption capacity is obtained.
3. The preparation method of the invention not only can solve the problem of heavy metal ion adsorption in industrial wastewater, but also can reduce the cost of wastewater adsorbent, and simultaneously solves the problem of pollution treatment of papermaking waste pulp, thereby finally realizing sustainable development.
4. The equilibrium adsorption capacity of the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent prepared by the invention to copper ions can reach 60.5Mg/g.
Drawings
FIG. 1 is an infrared spectrum of cellulose and paper mill pulp precipitate;
figure 2 is an XRD pattern of cellulose and paper mill sludge precipitate.
Detailed Description
The applicant will now make further details of the process of the present invention with reference to specific examples in order to enable a person skilled in the art to clearly understand the present invention. The following examples should not be construed in any way as limiting the scope of the invention as claimed.
In the following examples and comparative examples, the papermaking waste pulp precipitate was derived from the Vidada group, and FIG. 1 is an infrared spectrum of cellulose and papermaking waste pulp precipitate, from which it can be seen that the cellulose spectrum was 1040, 1400, 1700, 2950, 3400cm -1 Absorption peaks, C-O, C-H, C = O, C-H and O-H groups, respectively, exist at the left and right sides, from the paper mill pulp precipitateWe can find 1040, 1400, 1700, 2950, 3400cm from the pattern of (A) -1 The absorption peaks also exist at the left and right positions and correspond to the cellulose graph, but the intensity of the peaks is slightly lower than that of cellulose, so that the main material in the waste pulp sediment of papermaking can be judged to be cellulose. FIG. 2 is an XRD pattern of cellulose and paper mill sludge precipitate, from which it can be seen that cellulose has distinct characteristic peaks at 14, 16, 22 and 34℃and its peaks are sharp, indicating good crystallinity; the waste paper pulp sediment also has weaker peak shapes at 14, 16, 22 and 34 degrees, which further indicates that the main material in the waste paper pulp sediment is cellulose based on infrared spectrum on one hand, and on the other hand, the waste paper pulp sediment has weaker crystallinity relative to cellulose, so that more hydroxyl groups can be exposed, and the capability of adsorbing metal ions in waste water is enhanced relative to natural cellulose.
Sodium tartrate, magnalium-based layered double hydroxide, dilute hydrochloric acid, anhydrous lithium chloride, N-dimethylacetamide and N, N-methylene bisacrylamide are purchased from Shanghai Ala Latin Biochemical technology Co., ltd, and all raw materials are common raw materials in the market.
Example 1
The embodiment discloses a preparation method of a papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent, which comprises the following steps:
s1, taking a papermaking waste pulp precipitate as a raw material, repeatedly washing with distilled water and absolute ethyl alcohol for three times respectively, drying at 80 ℃ until the water content is 10%, crushing, and sieving with a 200-mesh sieve to obtain a fine granular fiber compound;
s2, adding sodium tartrate into the mixture at the temperature of 80 ℃ to remove CO 2 Sodium tartrate and CO removal in deionized water 2 The mass ratio of the deionized water is 1:90, and tartaric acid solution is obtained after full stirring and dissolution; then placing the Mg/Al-LDHs in a muffle furnace, heating to 450 ℃ and roasting for 5h to remove CO between the Mg/Al-LDHs layers 3 2- The method comprises the steps of carrying out a first treatment on the surface of the Finally, after the temperature of the muffle furnace is reduced to 200 ℃, rapidly taking out the Mg/Al-LDHs, adding the Mg/Al-LDHs into a three-neck flask placed in a water bath kettle, and adding and preparing the Mg/Al-LDHs according to the mass ratio of sodium tartrate to Mg/Al-LDHs of 8:25The mixed solution is stirred uniformly and then is adjusted to have a pH value of 10 by dilute hydrochloric acid, then is stirred and refluxed at 50 ℃ for reaction for 36 hours, is cooled to room temperature, is filtered by suction, is washed by deionized water for three times, and is dried at 90 ℃ for 12 hours to obtain tartaric acid intercalation Mg/Al-LDHs;
s3, adding anhydrous lithium chloride and N, N-dimethylacetamide into the flask, ultrasonically oscillating to enable the anhydrous lithium chloride to be dissolved in the N, N-dimethylacetamide, and then adding the fiber compound obtained in the step S1, wherein the mass ratio of the fiber compound to the anhydrous lithium chloride to the N, N-dimethylacetamide is 6:9:85; then uniformly stirring for 3 hours at 90 ℃ under the protection of nitrogen, and standing to room temperature to obtain a solution A; mixing the tartaric acid intercalation Mg/Al-LDHs obtained in the step S2 with acetic acid solution (2 wt%) according to a mass ratio of 1:45, and carrying out ultrasonic oscillation for dispersion and dissolution to obtain solution B;
s4, mixing the solution A and the solution B according to the mass ratio of 1:6.8 under the protection of nitrogen, uniformly stirring for 1h at room temperature, adding N, N-methylene bisacrylamide, continuously stirring for 2h at 30 ℃, regulating the pH value of the solution to 9 by using 1mol/L NaOH, stirring for 1h at 80 ℃, finally carrying out suction filtration, respectively washing for three times by using absolute ethyl alcohol and deionized water, drying for 12h at 90 ℃, grinding, and sieving by a 200-mesh sieve to obtain the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent.
Example 2
The embodiment discloses a preparation method of a papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent, which comprises the following steps:
s1, taking a papermaking waste pulp precipitate as a raw material, repeatedly washing with distilled water and absolute ethyl alcohol for three times respectively, drying at 100 ℃ until the water content is 10%, crushing, and sieving with a 200-mesh sieve to obtain a fine granular fiber compound;
s2, adding sodium tartrate into the mixture at the temperature of 80 ℃ to remove CO 2 Sodium tartrate and CO removal in deionized water 2 The mass ratio of the deionized water is 1:90, and tartaric acid solution is obtained after full stirring and dissolution; then placing the Mg/Al-LDHs in a muffle furnace, heating to 500 ℃ and roasting for 4 hours to remove CO between the Mg/Al-LDHs layers 3 2- The method comprises the steps of carrying out a first treatment on the surface of the Finally, after the temperature of the muffle furnace is reduced to 200 ℃, rapidly taking out Mg/Al-LDHs, adding the Mg/Al-LDHs into a three-neck flask placed in a water bath kettle, adding the prepared tartaric acid solution according to the mass ratio of sodium tartrate to Mg/Al-LDHs of 9:25, regulating the pH value of the mixed solution to 10 by using dilute hydrochloric acid after uniformly stirring, then stirring and refluxing the mixed solution at 60 ℃ for reaction for 24 hours, cooling to room temperature, carrying out suction filtration, washing with deionized water for three times, and drying at 80 ℃ for 12 hours to obtain tartaric acid intercalation Mg/Al-LDHs;
s3, adding anhydrous lithium chloride and N, N-dimethylacetamide into the flask, ultrasonically oscillating to enable the anhydrous lithium chloride to be dissolved in the N, N-dimethylacetamide, and then adding the fiber compound obtained in the step S1, wherein the mass ratio of the fiber compound to the anhydrous lithium chloride to the N, N-dimethylacetamide is 5:7:88; then uniformly stirring for 2 hours at 100 ℃ under the protection of nitrogen, and standing to room temperature to obtain a solution A; mixing the tartaric acid intercalation Mg/Al-LDHs obtained in the step S2 with acetic acid solution (2 wt%) according to a mass ratio of 1:50, and carrying out ultrasonic oscillation for dispersion and dissolution to obtain solution B;
s4, mixing the solution A and the solution B according to the mass ratio of 1:3.3 under the protection of nitrogen, uniformly stirring for 1h at room temperature, adding N, N-methylene bisacrylamide, continuously stirring for 1.5h at 40 ℃, regulating the pH value of the solution to 9 by using 1mol/L NaOH, stirring for 1h at 70 ℃, finally carrying out suction filtration, respectively washing for three times by using absolute ethyl alcohol and deionized water, drying for 12h at 80 ℃, grinding, and sieving by a 200-mesh sieve to obtain the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent.
Example 3
The embodiment discloses a preparation method of a papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent, which comprises the following steps:
s1, taking a papermaking waste pulp precipitate as a raw material, repeatedly washing with distilled water and absolute ethyl alcohol for three times respectively, drying at 100 ℃ until the water content is 10%, crushing, and sieving with a 200-mesh sieve to obtain a fine granular fiber compound;
s2, adding sodium tartrate into the mixture at the temperature of 80 ℃ to remove CO 2 In the deionized water of (2),sodium tartrate and CO removal 2 The mass ratio of the deionized water is 1:90, and tartaric acid solution is obtained after full stirring and dissolution; then placing the Mg/Al-LDHs in a muffle furnace, heating to 550 ℃, and roasting for 3h to remove CO between the Mg/Al-LDHs layers 3 2- The method comprises the steps of carrying out a first treatment on the surface of the Finally, after the temperature of the muffle furnace is reduced to 100 ℃, rapidly taking out Mg/Al-LDHs, adding the Mg/Al-LDHs into a three-neck flask placed in a water bath kettle, adding the prepared tartaric acid solution according to the mass ratio of sodium tartrate to Mg/Al-LDHs of 10:25, regulating the pH value of the mixed solution to 10 by using dilute hydrochloric acid after uniformly stirring, then stirring and refluxing the mixed solution at 70 ℃ for reaction for 24 hours, cooling to room temperature, carrying out suction filtration, washing with deionized water for three times, and drying at 80 ℃ for 12 hours to obtain tartaric acid intercalation Mg/Al-LDHs;
s3, adding anhydrous lithium chloride and N, N-dimethylacetamide into the flask, ultrasonically oscillating to enable the anhydrous lithium chloride to be dissolved in the N, N-dimethylacetamide, and then adding the fiber compound obtained in the step S1, wherein the mass ratio of the fiber compound to the anhydrous lithium chloride to the N, N-dimethylacetamide is 4:6:90; then uniformly stirring for 2 hours at 110 ℃ under the protection of nitrogen, and standing to room temperature to obtain a solution A; mixing the tartaric acid intercalation Mg/Al-LDHs obtained in the step S2 with acetic acid solution (2 wt%) according to a mass ratio of 1:55, and carrying out ultrasonic oscillation for dispersion and dissolution to obtain solution B;
s4, mixing the solution A and the solution B according to the mass ratio of 1:1.7 under the protection of nitrogen, uniformly stirring at room temperature for 2.5 hours, adding N, N-methylene bisacrylamide, continuously stirring at 50 ℃ for 1 hour, regulating the pH value of the solution to 9 by using 1mol/L NaOH, stirring at 60 ℃ for 2 hours, finally carrying out suction filtration, respectively washing with absolute ethyl alcohol and deionized water for three times, drying at 90 ℃ for 12 hours, grinding, and sieving with a 200-mesh sieve to obtain the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent.
Example 4
This embodiment is substantially the same as embodiment 2 except that: in the step S4, the mass ratio of the solution A to the solution B is 1:1, and the mass ratio of the solution A to the N, N-methylene bisacrylamide is 1:0.3.
Comparative example 1
The comparative example provides a method for preparing a fiber composite adsorbent, comprising the following steps:
s1, taking a papermaking waste pulp precipitate as a raw material, repeatedly washing with distilled water and absolute ethyl alcohol for three times respectively, drying at 100 ℃ until the water content is 10%, crushing, and sieving with a 200-mesh sieve to obtain a fine granular fiber compound;
s2, adding anhydrous lithium chloride and N, N-dimethylacetamide into a flask, ultrasonically oscillating to dissolve the anhydrous lithium chloride in the N, N-dimethylacetamide, and then adding the fiber compound obtained in the step S1, wherein the mass ratio of the fiber compound to the anhydrous lithium chloride to the N, N-dimethylacetamide is 5:7:88; then uniformly stirring for 2 hours at 100 ℃ under the protection of nitrogen, and standing to room temperature to obtain a solution A;
s3, stirring the solution A obtained in the step S2 at a uniform speed for 2.5 hours at room temperature under the protection of nitrogen, regulating the pH value of the solution to 9 by using 1mol/L NaOH, stirring for 1 hour at 70 ℃, carrying out suction filtration, respectively washing three times by using absolute ethyl alcohol and deionized water, drying for 12 hours at 80 ℃, grinding, and sieving by using a 200-mesh sieve to obtain the fiber composite adsorbent.
Comparative example 2
The comparative example provides a preparation method of tartaric acid intercalated Mg/Al-LDHs adsorbent, which comprises the following steps:
s1, adding sodium tartrate into the mixture at the temperature of 80 ℃ to remove CO 2 Sodium tartrate and CO removal in deionized water 2 The mass ratio of the deionized water is 1:90, and tartaric acid solution is obtained after full stirring and dissolution; then placing the Mg/Al-LDHs in a muffle furnace, heating to 500 ℃ and roasting for 4 hours to remove CO between the Mg/Al-LDHs layers 3 2- The method comprises the steps of carrying out a first treatment on the surface of the Finally, after the temperature of the muffle furnace is reduced to 200 ℃, rapidly taking out Mg/Al-LDHs, adding the Mg/Al-LDHs into a three-neck flask placed in a water bath kettle, adding the prepared tartaric acid solution according to the mass ratio of sodium tartrate to Mg/Al-LDHs of 9:25, regulating the pH value of the mixed solution to 10 by using dilute hydrochloric acid after uniformly stirring, then stirring and refluxing the mixed solution at 60 ℃ for reaction for 24 hours, cooling to room temperature, carrying out suction filtration, washing with deionized water for three times, and drying at 80 ℃ for 12 hours to obtain tartaric acid intercalation Mg/Al-LDHs;
s2, mixing the tartaric acid intercalation Mg/Al-LDHs obtained in the step S1 with acetic acid solution (2 wt%) according to a mass ratio of 1:50, and carrying out ultrasonic oscillation for dispersion and dissolution to obtain a solution B;
s3, stirring the solution B obtained in the step S2 at a uniform speed for 2.5 hours at room temperature under the protection of nitrogen, regulating the pH value of the solution to 9 by using 1mol/L NaOH, stirring for 1 hour at 70 ℃, carrying out suction filtration, washing three times by using absolute ethyl alcohol and deionized water respectively, drying for 12 hours at 80 ℃, grinding, and sieving by a 200-mesh sieve to obtain the tartaric acid intercalated Mg/Al-LDHs adsorbent.
Comparative example 3
This comparative example is substantially the same as example 2 except that: and in the step S4, a cross-linking agent N, N-methylene bisacrylamide is not added, and the fiber composite and tartaric acid intercalation Mg/Al-LDHs blending material is obtained.
Comparative example 4
The comparative example discloses a preparation method of a papermaking waste pulp grafted Mg/Al-LDHs adsorbent, which comprises the following steps:
s1, taking a papermaking waste pulp precipitate as a raw material, repeatedly washing with distilled water and absolute ethyl alcohol for three times respectively, drying at 100 ℃ until the water content is 10%, crushing, and sieving with a 200-mesh sieve to obtain a fine granular fiber compound;
s3, adding anhydrous lithium chloride and N, N-dimethylacetamide into the flask, ultrasonically oscillating to enable the anhydrous lithium chloride to be dissolved in the N, N-dimethylacetamide, and then adding the fiber compound obtained in the step S1, wherein the mass ratio of the fiber compound to the anhydrous lithium chloride to the N, N-dimethylacetamide is 5:7:88; then uniformly stirring for 2 hours at 100 ℃ under the protection of nitrogen, and standing to room temperature to obtain a solution A; mixing Mg/Al-LDHs and acetic acid solution (2 wt%) according to a mass ratio of 1:50, and carrying out ultrasonic oscillation to disperse and dissolve so as to obtain solution B;
s4, mixing the solution A and the solution B according to the mass ratio of 1:3.3 under the protection of nitrogen, uniformly stirring for 1h at room temperature, adding N, N-methylene bisacrylamide, continuously stirring for 1.5h at 40 ℃, regulating the pH value of the solution to 9 by using 1mol/L NaOH, stirring for 1h at 70 ℃, finally carrying out suction filtration, respectively washing for three times by using absolute ethyl alcohol and deionized water, drying for 12h at 80 ℃, grinding, and sieving by using a 200-mesh sieve to obtain the papermaking waste pulp grafted Mg/Al-LDHs adsorbent.
That is, in comparison with example 2, the present comparative example does not use tartaric acid to intercalate Mg/Al-LDHs.
Comparative example 5
This comparative example is substantially the same as example 2 except that: in the step S4, the mass ratio of the solution A to the solution B is 1:0.02.
Application example
Reagent grade Cu (NO) 3 )·3H 2 O is added into deionized water to prepare 1L of Cu with initial concentration of 200mg/L 2 + Weighing 1g of the solution, adding Cu to the adsorbents prepared in examples 1-4 and comparative examples 1-5 2+ Stirring at 25deg.C for 3 hr, and measuring Cu by atomic absorption spectrophotometry 2+ Concentration.
And the equilibrium adsorption amount is calculated according to the following calculation formula:
wherein q is e The unit is mg/g for equilibrium adsorption quantity; c (C) o The unit is recorded as mg/L for the initial concentration of metal ions in the waste liquid before adsorption; c (C) e The unit is recorded as mg/L for the equilibrium concentration of metal ions in the residual waste liquid after adsorption; m is the mass of the adsorbent, V is the volume of the metal waste liquid, and the test results are shown in Table 1.
Table 1 adsorption of Cu by adsorbents prepared in examples and comparative examples 2+ Results of Performance test
| Adsorbent and process for producing the same | Balance adsorption quantity (mg/g) |
| Example 1 | 53.4 |
| Example 2 | 60.5 |
| Example 3 | 56.3 |
| Example 4 | 42.9 |
| Comparative example 1 | 25.2 |
| Comparative example 2 | 33.1 |
| Comparative example 3 | 32.3 |
| Comparative example 4 | 38.9 |
| Comparative example 5 | 28.1 |
From the data in Table 1, it can be seen that the waste papermaking pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent prepared by the invention has excellent adsorption performance on copper ions. Comparative example 2 and comparative examples 1 to 3 can find that the equilibrium adsorption amount is significantly reduced in comparative example 1 directly using the fiber composite as the adsorbent and in comparative example 2 directly using tartaric acid intercalated Mg/Al-LDHs as the adsorbent. In comparative example 3, no crosslinking agent was added, no grafting reaction occurred between the fiber composite and tartaric acid intercalated Mg/Al-LDHs, but simple compounding, poor dispersibility of the adsorbent, and significant decrease in equilibrium adsorption capacity. This demonstrates that grafting the fiber composite with tartaric acid intercalated Mg/Al-LDHs can enhance the adsorption capacity of the adsorbent for copper ions compared to using the fiber composite, tartaric acid intercalated Mg/Al-LDHs alone, or simply compounding the two. This is probably because by grafting the fiber composite onto the tartaric acid intercalation Mg/Al-LDHs, the adsorption capacity of the adsorbent can be improved and the dispersion capacity of the adsorbent in wastewater can be improved under the interaction of the fiber composite and the tartaric acid intercalation Mg/Al-LDHs, so that on one hand, the problems of closed hydroxyl and low reaction activity in the fiber composite can be solved, and on the other hand, the problem of easy agglomeration of the tartaric acid intercalation Mg/Al-LDHs can be solved, and further, the adsorption capacity of the prepared adsorbent on copper ions can be remarkably improved. In comparative example 4, mg/Al-LDHs were not intercalated with tartaric acid, and in comparative example 5, the proportion of tartaric acid intercalated Mg/Al-LDHs was very small, compared with example 2, and the adsorption capacity of the adsorbent was significantly reduced.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent is characterized by being prepared by the following method: firstly, tartaric acid is adopted to carry out intercalation on Mg/Al-LDHs to obtain tartaric acid intercalation Mg/Al-LDHs, a papermaking waste pulp precipitate is taken as a raw material to prepare a granular fiber compound, and then the fiber compound is grafted with the tartaric acid intercalation Mg/Al-LDHs through a crosslinking agent to obtain the papermaking waste pulp grafted tartaric acid intercalation Mg/Al-LDHs adsorbent.
2. The papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent of claim 1, wherein the cross-linking agent is N, N-methylene bisacrylamide.
3. The method for preparing the papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent as claimed in claim 1 or 2, which is characterized by comprising the following steps:
s1, preparing a granular fiber compound by taking a papermaking waste pulp precipitate as a raw material;
s2, adding sodium tartrate to remove CO 2 Fully stirring the solution in the deionized water to obtain tartaric acid solution; then adding pretreated Mg/Al-LDHs into the tartaric acid solution, regulating the pH value of the mixed solution to 10-11, stirring and refluxing at 50-70 ℃ for 24-36 h, filtering, washing and drying to obtain tartaric acid intercalation Mg/Al-LDHs;
s3, dissolving lithium chloride in N, N-dimethylacetamide, adding the fiber compound obtained in the step S1 after ultrasonic dispersion, and stirring for 2-3 hours at 90-110 ℃ in a protective gas atmosphere to obtain a solution A; dissolving tartaric acid intercalation Mg/Al-LDHs obtained in the step S2 in acetic acid solution, and performing ultrasonic dispersion to obtain solution B;
s4, mixing the solution A obtained in the step S3 with the solution B, uniformly stirring, adding N, N-methylene bisacrylamide, stirring for 1-2 hours at 30-50 ℃, adjusting the pH value of the solution to 9-10, stirring for 1-2 hours at 60-80 ℃, filtering, washing, drying and grinding to obtain the papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent.
4. The method for preparing a papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent according to claim 3, wherein the method for preparing the granular fiber composite in the step S1 is as follows: repeatedly washing the papermaking waste pulp precipitate with deionized water and absolute ethyl alcohol for 3-5 times, drying at 80-100 ℃, crushing and sieving with a 200-mesh sieve to obtain the granular fiber compound.
5. The method for preparing a paper making waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent according to claim 3, wherein in the step S2, the mass ratio of sodium tartrate to Mg/Al-LDHs is (8-10): 25.
6. The method for preparing the papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent, according to claim 3, wherein in the step S2, the method for preprocessing the Mg/Al-LDHs is as follows: and (3) calcining the Mg/Al-LDHs at 450-550 ℃ for 3-5 h.
7. The method for preparing the tartaric acid intercalated Mg/Al-LDHs adsorbent grafted by papermaking waste pulp according to claim 3, wherein in the step S3, the mass ratio of the fiber compound to the lithium chloride to the N, N-dimethylacetamide is (4-6): (6-9): (85-90), and the mass ratio of the tartaric acid intercalated Mg/Al-LDHs to the acetic acid solution is (1) - (45-55).
8. The method for preparing a paper making waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent according to claim 3, wherein in the step S4, the mass ratio of the solution A to the solution B is 1 (1-7), and the mass ratio of the solution A to the N, N-methylenebisacrylamide is 1 (0.2-2.2).
9. The use of the papermaking waste pulp grafted tartaric acid intercalated Mg/Al-LDHs adsorbent of claim 1 in wastewater treatment.
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