CN112915971A - Lignin grafted polyamino acid type heavy metal adsorbent and preparation method and application thereof - Google Patents
Lignin grafted polyamino acid type heavy metal adsorbent and preparation method and application thereof Download PDFInfo
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- CN112915971A CN112915971A CN202110075510.5A CN202110075510A CN112915971A CN 112915971 A CN112915971 A CN 112915971A CN 202110075510 A CN202110075510 A CN 202110075510A CN 112915971 A CN112915971 A CN 112915971A
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- lignin
- adsorbent
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- heavy metal
- polyamino acid
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 86
- 229920005610 lignin Polymers 0.000 title claims abstract description 86
- 239000002253 acid Substances 0.000 title claims abstract description 46
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 18
- -1 aldehyde compound Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 22
- 229910021645 metal ion Inorganic materials 0.000 description 21
- 238000001728 nano-filtration Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- 108010039918 Polylysine Proteins 0.000 description 12
- 229920000656 polylysine Polymers 0.000 description 12
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 229920000805 Polyaspartic acid Polymers 0.000 description 9
- 108010020346 Polyglutamic Acid Proteins 0.000 description 9
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
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- 229920002643 polyglutamic acid Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
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- 230000000694 effects Effects 0.000 description 7
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- 239000002699 waste material Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000006683 Mannich reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940009859 aluminum phosphate Drugs 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
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- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229960000587 glutaral Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229940118019 malondialdehyde Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a lignin grafted polyamino acid type heavy metal adsorbent, and a preparation method and application thereof.
Description
Technical Field
The invention relates to the field of natural polymer adsorbents, and particularly relates to a lignin-grafted polyamino acid type heavy metal adsorbent and a preparation method and application thereof.
Background
Environmental problems are very serious problems in recent years, and wastewater contaminated with heavy metals is one of industrial wastewater which is most serious in environmental pollution and most harmful to human beings and animals and plants. Water pollution has become a serious problem in the past decades due to the high toxicity, carcinogenicity and non-degradability of heavy metal ions. Toxic heavy metals such as lead, cadmium, chromium, arsenic, zinc, copper and nickel are harmful to aquatic organisms, and most of the heavy metal ions have carcinogenic, teratogenic and mutagenic effects, are easily concentrated in organisms and amplified by food chains to finally cause harm to human bodies, and cause various diseases and disorders when they are accumulated in human bodies through the food chains. The elimination of heavy metal pollution is more difficult, so that the natural polymer adsorbent is used for adsorbing heavy metal in wastewater, and the method is considered to be a promising method for eliminating heavy metal ions in water due to the characteristics of simple operation, wide application range, high removal efficiency, environmental friendliness, capability of recovering useful materials, reusability and the like.
During the past decades, lignins have received considerable attention in adsorbing different kinds of organic and inorganic contaminants in water due to their unique physicochemical properties, biocompatibility, low cost and abundant properties, as well as the presence of active sites in their molecules. The lignin molecule contains functional groups such as hydroxyl, carboxyl, carbonyl and the like, wherein an unshared electron pair exists on an oxygen atom, and can form a coordinate bond with a metal ion to generate chelation, so that a metal chelate of the lignin is generated. For example, the invention of ChinaApplication of CN 110479217 modified lignin based on metal doping for selective adsorption of As (V) anion HAsO in water4 2-However, this method is only suitable for adsorption of oxoanions and the adsorption conditions are only at pH 7, at which heavy metal cations cannot be adsorbed. In addition, the Chinese invention application CN109569528A utilizes sodium lignosulfonate and acid modified fly ash to carry out crosslinking to obtain a composite adsorbent for Cu in water2+The composite adsorbent prepared by the method is adsorbed, but the composite adsorbent prepared by the method is not desorbed and reused after adsorption is completed, so that the adsorbent prepared by the method is poor in repeated practicability, and resource waste is caused.
The polyamino acid copolymer is a novel biodegradable high molecular material, has a structure similar to a protein amido bond, and has the advantages of no toxicity, excellent biocompatibility, environmental friendliness, high performance and the like. The water-soluble polymer material has excellent water solubility, super-strong adsorbability and biodegradability, is an excellent environment-friendly polymer material, can be used as a water-retaining agent, a heavy metal ion adsorbent, a flocculating agent, a slow-release agent, a drug carrier and the like, and has great commercial value and social value in industries of cosmetics, environmental protection, food, medicine, agriculture, desert control and the like.
Therefore, research and development of a novel adsorbent which has strong adsorption capacity, no secondary pollution and environmental friendliness are necessary, and the produced natural polymer biological adsorbent is a novel green metal adsorbent with great development potential. Therefore, the invention develops the lignin grafted polyamino acid type heavy metal adsorbent and the preparation method and the application thereof.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing an adsorbent aiming at the defects of the prior art.
The technical problem to be solved by the invention is to provide a preparation method of the adsorbent.
The technical problem to be solved by the present invention is to provide the application of the above adsorbent.
The invention idea is as follows: the invention provides a preparation method for removing heavy metal ions in a water body by adsorbing alkali lignin modified by polyamino acid, wherein lignin molecular structural units contain a plurality of active groups, so that the lignin molecular structural units have potential adsorption capacity on certain inorganic metal ions and the like; in the structural unit of the lignin, hydrogen atoms on ortho-position and para-position of phenolic hydroxyl on a benzene ring and alpha-position of carbonyl on a side chain are more active so as to carry out chemical modification on the structure of the lignin, and the lignin is easy to carry out Mannich reaction with aldehyde and amine. The polyamino acid can be grafted on the lignin through a Mannich reaction, so that-NH-and COOH-which have the chelating effect are endowed to the alkali lignin, and functional groups with the chelating and adsorbing effects are introduced; meanwhile, the adsorption characteristic of the lignin is utilized, so that heavy metal ions in the wastewater can be adsorbed, and the application value of the lignin and the polyamino acid is improved.
In order to solve the first technical problem, the invention discloses an adsorbent which is a lignin grafted polyamino acid type adsorbent.
The lignin includes but is not limited to industrial lignin such as organic solvent type lignin, enzymatic hydrolysis lignin, alkali lignin and the like.
Wherein the weight average molecular weight of the polyamino acid is 500-1000000.
Wherein the polyamino acid includes, but is not limited to, polylysine, polyglutamic acid, polyglycine, polyhistidine, polyaspartic acid, polyarginine, or combinations thereof; preferably one or more of polylysine, polyaspartic acid, polyglutamic acid, polyarginine, polyhistidine and polyglycine.
The adsorbent takes polyamino acid as a skeleton structure and is grafted with lignin through-NH-.
Wherein, polyamino acid and lignin in the adsorbent are grafted by aldehyde compounds.
Wherein the adsorbent is a chain polymer consisting of monomers shown in a formula I;
wherein the chain polymer has a repeating unit structure as shown in formula II:
in order to solve the second technical problem, the invention discloses a preparation method of the lignin grafted polyamino acid type heavy metal adsorbent, which comprises the step of reacting lignin with polyamino acid and aldehyde compounds.
The aldehyde compounds include, but are not limited to, formaldehyde, acetaldehyde, glyoxal, malondialdehyde, glutaraldehyde, and the like.
Wherein the mass ratio of the lignin to the polyamino acid is 1: (0.5-2), preferably 1: 0.5.
wherein the mass ratio of the lignin to the aldehyde compound is 1: (0.1 to 0.5), preferably 1: (0.1 to 0.3), more preferably 1: 0.185.
preferably, polyamino acid and aldehyde compound are added into the medium lignin solution for reaction; further preferably, polyamino acid is added into the lignin solution, and the aldehyde compound is slowly added; still more preferably, the aldehyde compound is added dropwise or fed-batch; still more preferably within 20 min.
Wherein, in the lignin solution, the mass fraction of lignin is 10-40%.
The lignin solution includes, but is not limited to, an alkaline lignin aqueous solution, and may also be other lignin solutions, such as a lignin furan solution, and the like.
Wherein the pH value of the alkaline lignin aqueous solution is 9-12; preferably, the pH is adjusted with aqueous NaOH; more preferably, the concentration of the NaOH aqueous solution is 0.1-0.4 mol/L.
Wherein the aldehyde compound is added in the form of an aldehyde compound solution; preferably, the mass percent of the aldehyde compound solution is 37 wt%; further preferably, the mass ratio of the lignin to the aldehyde compound solution is 1: 0.5 to 2; still more preferably, the mass ratio of the lignin to the aldehyde compound solution is 1: 0.5.
wherein the reaction is a Mannich reaction.
Wherein the reaction temperature is 50-90 ℃, and preferably 70 ℃.
Wherein the reaction time is 2-4 h, preferably 3 h.
And after the reaction is finished, cooling the reaction liquid, performing nanofiltration and drying to obtain the lignin grafted polyamino acid type heavy metal adsorbent.
Wherein the nanofiltration is performed by adopting a nanofiltration membrane with the interception amount of 300-2000 Da, so as to obtain a concentrated solution which does not penetrate through the filtration membrane.
Wherein the pH value of the nanofiltration end point concentrated solution is 4-8.
Wherein, the drying includes but is not limited to spray drying or freeze drying.
Wherein the temperature of the spray drying is 100-140 ℃.
In order to solve the third technical problem, the invention discloses an application of the lignin grafted polyamino acid type heavy metal adsorbent in heavy metal adsorption.
Wherein the heavy metal includes but is not limited to metals in groups IA-VIIA, IB-VIIB, VIII, transition metals, lanthanide metals, actinide metals; preferably any one or a combination of more of Pb, Cd, Ni, Mn, Cu, Fe and Cr; further preferably heavy metal cations; more preferably Pb2+、Cu2+、Cd2+、Zn2+、Cr3+。
Preferably, heavy metal is adsorbed in the environment with the pH value of 2-6; preferably, the heavy metal is absorbed in the liquid containing the heavy metal and with the pH value of 2-6; further preferably, the heavy metal is adsorbed in a water body containing the heavy metal and having a pH of 2-6.
Wherein the mass ratio of the lignin grafted polyamino acid type heavy metal adsorbent to the heavy metal is 1 g: 40-500 mg.
Wherein the adsorption temperature is 20-55 ℃, and preferably 20-30 ℃.
Wherein the adsorption time is 1-10 h, preferably 2-6 h.
Wherein, after the adsorption is finished, the adsorbent adsorbed with the heavy metal is regenerated by acid; preferably, the adsorbent adsorbed with the heavy metal is fully contacted with acid to desorb the heavy metal, so that the regeneration of the adsorbent is realized; further preferably, the adsorbent adsorbed with the heavy metal is placed in acid, and is fully contacted with the acid to desorb the heavy metal, so that the regeneration of the adsorbent is realized.
Preferably, the acid is a strong acid, including but not limited to hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, or combinations thereof; further preferred is nitric acid.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the invention uses polyamino acid to modify lignin, compared with common amino acid, the common amino acid is mainly used as food and feed additive at present, the added value is lower, and the polyamino acid has a large amount of carboxyl and amino groups, has extremely strong adsorption capacity, can be used as a wastewater treatment agent, and has wide market application prospect.
2. The main raw materials of the lignin and the polyamino acid used in the invention belong to renewable resources and green chemicals; the synthesized polyamino acid modified lignin adsorbent has a large number of hydroxyl groups, carboxyl groups and amino groups, wherein lone electron pairs are arranged on N atoms on the amino groups, and can be subjected to compound coordination with metal ions, so that the adsorbent can show stronger chelating capacity, and the adsorption of heavy metal ions is greatly improved.
3. The method has mild adsorption treatment conditions for the water body, can treat the water body with a wider pH range of 2-6, has short removal time and high adsorption removal rate, and can greatly improve the water treatment efficiency.
4. The adsorbent provided by the invention has a stable structure, can be subjected to multiple adsorption-desorption, is beneficial to metal recovery and multiple reuse of the adsorbent, has the characteristics of safety, no toxicity, environmental friendliness and the like of lignin and polyamino acid, and has good economic and environmental benefits.
Drawings
The above and/or other advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings and the detailed description.
Fig. 1 is an infrared spectrum of polylysine and polyglutamic acid modified lignin provided in examples 1 and 3 of the present invention.
Fig. 2 is a bar graph of the adsorption capacity of polylysine-modified lignin to lead ions after adsorption-desorption for 8 times, which is provided in embodiment 1 of the present invention.
Fig. 3 is a bar chart of the polyglutamic acid modified lignin provided in example 3 of the present invention adsorbing various metal ions.
FIG. 4 is a graph showing that AL-PL and AL-PG synthesized in examples 1 and 3 according to the present invention adsorb various ions in examples 9 and 10.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the following examples, the polyglutamic acid, polylysine and polyaspartic acid were obtained from Shanghai Michelin Biotech, Inc.; polyhistidine, polyglycine, and polyarginine were purchased from Sigma-Aldrich.
In the following examples, the lignin was kraft lignin with a lignin particle size of 2.8 microns.
Characteristic infrared absorption peaks of polylysine-modified lignin (AL-PL) and polyglutamic acid-modified lignin (AL-PG) prepared in examples 1 and 3 below are shown in FIG. 1, and 3401cm is shown in the infrared spectrogram of polylysine and polyglutamic acid-modified lignin in addition to the characteristic peaks of lignin-1NH tensile vibration absorption peak at (1) and 3402cm Above Lignin (AL)-1The strong and wide O-H stretching vibration absorption peak parts are overlapped, the peak strength is higher, and the N-H band in the association state is sharper than the O-H absorption peak possibly due to the formation of hydrogen bonds between the grafted amine and other molecules; 1594. 1502 and 1456cm-1Can be attributed to the stretching vibration of the aromatic ring skeleton of lignin. In addition, due to NH2N of structureH flexural vibration at 1653cm-1A new peak appears. In addition, the non-conjugated CN tensile shock absorption peak appears at 1237cm-1(ii) a The C-O stretching vibration peak is 1380cm-1And the-OH tensile shock absorption peak is 3401cm-1The results indicate that the carboxyl groups have grafted onto the lignin structure.
Examples 1 to 2
Step 1: adding 5g of lignin powder into water to prepare an aqueous solution with the mass fraction of 30%, adding 0.2mol/L of NaOH aqueous solution to adjust the pH value to 12.0, and stirring to completely dissolve the lignin. Adding polylysine (2.5g, example 1) and polyaspartic acid (4g, example 2) into the round-bottom flask respectively, dripping 2.5g of 37 wt% formaldehyde solution within 20 minutes, and heating to 70 ℃ for reaction for 3 hours; and (3) after the reaction is finished, nanofiltration is carried out on the reaction liquid by adopting a nanofiltration membrane with the molecular weight cutoff of 1000Da, the pH value of the nanofiltration end point is 5-7, and the concentrated solution after nanofiltration is subjected to freeze drying to respectively obtain polylysine modified lignin (AL-PL) and polyaspartic acid modified lignin (AL-PC), wherein the N contents of the concentrated solution are respectively 10.24% and 8.76% according to an element analysis test. .
Step 2: and (3) respectively using the AL-PL and the AL-PC synthesized in the step (1) as adsorbents to respectively adsorb and treat the metal ions in the water body. The specific adsorption treatment process is as follows: respectively adding an AL-PL (aluminum-phosphate) adsorbent and an AL-PC (polycarbonate) adsorbent into a lead nitrate-containing water body with the pH value of 6, wherein the mass-volume ratio of the adsorbent to the lead nitrate-containing water body is 1g/L, the initial concentration of a lead nitrate solution is 50mg/L, the adsorption temperature is 20 ℃, the adsorption is carried out for 4 hours, filtering is carried out to obtain a filtrate, ICP-OES (inductively coupled plasma-optical emission system) is used for detecting lead ions in the filtrate, and the adsorption capacity of the lead ions is 48.13mg/g and 46.76mg/g respectively when the AL-PL or AL-PC is used as the adsorbent.
And step 3: and (3) respectively taking 0.1g of AL-PL and AL-PC adsorbed with lead ions in the step (2), adding the AL-PL and the AL-PC into 0.2M nitric acid, stirring for 30min, filtering, washing the obtained solid with deionized water for 3 times, and respectively recovering the AL-PL and the AL-PC.
And 4, step 4: and (3) performing an adsorption-desorption experiment on the lead ions again by using the AL-PL and the AL-PC recovered in the step (3) according to the method in the step (2), repeating the experiment for 8 times, detecting the lead ions in the filtrate after the last adsorption by using ICP-OES, and finding that the adsorption amounts of the AL-PL (shown in figure 2) or AL-PC adsorbent to the lead ions can reach 41.42mg/g and 39.25mg/g respectively, so that the two adsorbents can be recycled and have good effects.
Comparative example 1
And (3) adsorbing and treating the water body containing lead ions by using the lignin powder as an adsorbent. The adsorption conditions were the same as in step 2 of example 1, and the maximum adsorption capacity for lead ions was found to be 20.12 mg/g. Respectively carrying out desorption regeneration experiments on the lignin after adsorbing the metal ions, and finding that the metal ions begin to overflow from the solution after 5 experiments, so that the reusability is poor.
Comparative example 2
And respectively taking the polylysine and the polyaspartic acid in the embodiment 1 and the embodiment 2 as adsorbents to adsorb and treat the water body containing lead ions. The adsorption conditions were the same as in step 2 of example 1, and the maximum adsorption capacities of polylysine and polyaspartic acid to lead ions were found to be 22.56mg/g and 24.34mg/g, respectively. The polylysine and the polyaspartic acid which are adsorbed with the metal ions are respectively subjected to desorption regeneration experiments, and the results show that the two polyamino acids begin to decompose after 4 experiments, the adsorption effect is obviously deteriorated, the metal ions overflow, and the reusability is poor.
Comparative example 3
The lignin powder was mixed with polylysine from example 1 in a ratio of 1: the mixed mixture with the mass ratio of 0.5 is a first adsorbent; the lignin powder was mixed with polyaspartic acid from example 2 in a ratio of 1: the mixed mixture in a mass ratio of 0.8 is the second adsorbent.
The first adsorbent and the second adsorbent were used for treating a lead ion-containing water body by adsorption in the same manner as in example 1 under the same adsorption conditions as in step 2 of example 1, and the maximum adsorption capacities of the first adsorbent and the second adsorbent for lead ions were found to be 39.75mg/g and 42.48mg/g, respectively.
Comparative example 4
In the same manner as in example 1, polylysine was replaced with triethylenetetramine only, and the maximum adsorption capacities for lead ions were measured to be 30.72mg/g, respectively, according to step 2 of example 1, indicating that the adsorption capacity for heavy metal cations was poor. The desorption regeneration experiment is carried out on the triethylene tetramine modified lignin after the metal ions are adsorbed, and the modified lignin is found to have obviously poor adsorption effect and low reusability after 5 experiments.
Examples 3 to 4:
step 1: adding 5g of lignin powder into water to prepare an aqueous solution with the mass fraction of 25%, adding 0.1mol/L NaOH aqueous solution to adjust the pH value to 11.0, and stirring to completely dissolve the lignin. Respectively adding polyglutamic acid (5g, example 3) and polyarginine (7.5g, example 4) into a round-bottom flask, dropwise adding 2.5g of 37 wt% glyoxal solution within 20min, heating to 60 ℃ and reacting for 3 h; and (3) after the reaction is finished, nanofiltration is carried out on the reaction liquid by adopting a nanofiltration membrane with the molecular weight cutoff of 1000Da, the pH value of the nanofiltration end point is 5-7, and the concentrated solution after nanofiltration is freeze-dried to obtain polyglutamic acid modified lignin (AL-PG) and polyarginine modified lignin (AL-PS), wherein the N contents are respectively 6.21% and 8.32% according to elemental analysis tests.
Step 2: and (3) respectively using the AL-PG and the AL-PS synthesized in the step (1) as adsorbents to respectively adsorb and treat metal ions in the water body. The specific adsorption treatment process is as follows: respectively adding AL-PG and AL-PS adsorbents into a water body containing copper nitrate with the pH value of 3, wherein the mass-volume ratio of the adsorbents to the water body containing ions is 0.8g/L, the initial concentration of a copper nitrate solution is 50mg/L, the adsorption temperature is 25 ℃, the adsorption is carried out for 5 hours, filtering is carried out to obtain a filtrate, copper ions in the filtrate are detected by ICP-OES, and the adsorption capacity of AL-PG and AL-PS to the copper ions is respectively 46.45mg/g and 48.41 mg/g.
And step 3: and (3) respectively taking 0.1g of the AL-PG and AL-PS adsorbents which adsorb copper ions in the step (2), adding the adsorbents into 0.2M nitric acid, stirring for 30min, filtering, washing the obtained solid with deionized water for 3 times, and respectively recovering the AL-PG and the AL-PS.
And 4, step 4: and (3) performing an adsorption-desorption experiment on the Al-PG and the AL-PS recovered in the step (3) again according to the method in the step (2), repeating the experiment for 8 times, detecting the copper ions in the filtrate after the last adsorption by using ICP-OES, and finding that the adsorption amounts of the AL-PG and AL-PS adsorbents to the copper ions can reach 36.69mg/g and 40.71mg/g respectively, so that the adsorbents can be recycled and have a good effect.
Comparative example 5
And (3) adsorbing the copper ion-containing water body by using lignin powder as an adsorbent. The adsorption conditions were the same as in step 2 of example 3, and the adsorption capacity for copper ions was found to be 12.34 mg/g.
Comparative example 6
The polyglutamic acid and the polyarginine in the embodiment 3 and the embodiment 4 are respectively used as adsorbents to adsorb and treat the water body containing copper ions. Adsorption conditions as in step 2 of example 3, the adsorption capacities of polyglutamic acid or polyarginine to copper ions were found to be 25.76mg/g and 28.12mg/g, respectively.
Examples 5 to 6:
step 1: adding 5g of lignin powder into water to prepare an aqueous solution with the mass fraction of 20%, adding 0.4mol/L NaOH aqueous solution to adjust the pH value to 11.0, and stirring to completely dissolve the lignin. Then adding polyhistidine (6g, example 5) and polyglycine (3g, example 6) into a round-bottom flask respectively, finishing dropwise adding 37 wt% glutaraldehyde solution 2.5g within 20min, heating to 60 ℃ and reacting for 2 h; and (3) after the reaction is finished, nanofiltration is carried out on the reaction liquid by adopting a nanofiltration membrane with the molecular weight cutoff of 1000Da, the pH of the nanofiltration end point is 5-7, and the concentrated solution after nanofiltration is freeze-dried to obtain polyhistidine modified lignin (AL-PH) and polyglycine modified lignin (AL-PA), wherein the N content is respectively 16.10% and 9.65% by element analysis.
Step 2: and (3) respectively using the AL-PH or AL-PA synthesized in the step (1) as an adsorbent to adsorb and treat metal ions in the water body. The specific adsorption treatment process is as follows: respectively adding an AL-PH adsorbent and an AL-PA adsorbent into a water body containing chromium nitrate and having a pH value of 4, wherein the mass-volume ratio of the adsorbent to the water body containing cadmium ions is 1.1g/L, the initial concentration of a cadmium nitrate solution is 50mg/L, the adsorption temperature is 30 ℃, the adsorption is carried out for 4 hours, filtering is carried out to obtain a filtrate, cadmium ions in the filtrate are detected by ICP-OES, and the adsorption capacity of the AL-PH adsorbent or the AL-PA adsorbent to the cadmium ions is respectively 44.17mg/g and 42.98 mg/g.
And step 3: and (3) respectively taking 0.1g of the AL-PH and AL-PA adsorbents which adsorb cadmium ions in the step (2), adding the adsorbents into 0.2M nitric acid, stirring for 30min, filtering, washing the obtained solid with deionized water for 3 times, and respectively recovering the AL-PH and the AL-PA.
And 4, step 4: and (3) performing an adsorption-desorption experiment on the Al-PH and AL-PA recovered in the step (3) again according to the method in the step (2), repeating the experiment for 8 times, detecting the cadmium ions in the filtrate after the last adsorption by using ICP-OES, and finding that the adsorption amounts of the AL-PH and AL-PA adsorbents to the cadmium ions can reach 35.75mg/g and 37.27mg/g respectively, so that the adsorbents can be recycled and have a good effect.
Comparative example 7
The lignin powder is used as an adsorbent to adsorb and treat the water body containing cadmium ions. The adsorption conditions were the same as those in step 2 of example 5, and the adsorption capacity of cadmium ion was found to be 18.47 mg/g.
Comparative example 8
And (3) respectively taking the polyhistidine and the polyglycine in the embodiment 5 and the embodiment 5 as adsorbents to adsorb and treat the water body containing cadmium ions. The adsorption conditions were the same as in step 2 of example 5, and the adsorption capacities for cadmium ions were found to be 21.61mg/g and 20.36mg/g, respectively.
Examples 7 to 8
AL-PL and AL-PG synthesized in examples 1 and 3 were used as adsorbents to adsorb mixed metal ions in a treated water body. The specific adsorption treatment process is as follows: dissolving 8.0mg of lead nitrate, 14.76mg of copper nitrate, 10.52mg of cadmium nitrate, 12.35mg of zinc sulfate and 25.62mg of chromium trichloride hexahydrate in a water body with the pH value of 100 mL5 to prepare an aqueous solution with the metal concentration of 50mg/L, respectively adding AL-PL and AL-PG adsorbents into the prepared mixed metal ion solution, wherein the mass-volume ratio of the adsorbent to the mixed metal ion water body is 1g/L, the adsorption temperature is 25 ℃, adsorbing for 3 hours, filtering to obtain a filtrate, detecting metal ions in the filtrate by using ICP-OES, and the test result is shown in figure 3, wherein the AL-PL and AL-PG polyamino acid modified lignin have strong adsorption capacity on various metal ions.
Examples 9 to 10
A simulated waste acid solution is prepared by adsorbing and treating waste liquid components generated in a sulfuric acid washing section of a certain enterprise by using the AL-PL and the AL-PG synthesized in the embodiment 1 and the embodiment 3 as adsorbents respectively, wherein the waste acid solution contains mixed metal ions of Fe (II), Cr (III), Mn (II) and Ni (II), the metal ion contents are 0.2g/L, 0.05g/L, 0.1g/L and 0.05g/L respectively, and the pH value is 2-3. Respectively adding an AL-PL (alkaline-phosphate) adsorbent and an AL-PG (alkaline-phosphate) adsorbent into the simulated waste acid liquid, wherein the mass-volume ratio of the adsorbent to the simulated waste acid liquid is 1g/L, the adsorption temperature is 25 ℃, adsorbing for 3 hours, filtering to obtain a filtrate, detecting metal ions in the filtrate by using ICP-OES (inductively coupled plasma-optical emission spectrometry), and the test result is shown in figure 4, which shows that AL-PL and AL-PG polyamino acid modified lignin have strong adsorption capacity on various metal ions in the simulated waste acid liquid.
The present invention provides a method and a method for preparing the same, and a method and a device for preparing the same, which are many ways and are particularly suitable for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and embellishments can be made without departing from the principle of the present invention, and these modifications and embellishments should be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. An adsorbent is characterized in that the adsorbent is a lignin grafted polyamino acid type adsorbent.
2. The method for producing the adsorbent according to claim 1, wherein the lignin is reacted with the polyamino acid and the aldehyde compound.
3. The preparation method according to claim 2, wherein the mass ratio of the lignin to the polyamino acid is 1: (0.5-2).
4. The preparation method according to claim 2, wherein the mass ratio of the lignin to the aldehyde compound is 1: (0.1-0.5).
5. The method according to claim 2, wherein the reaction temperature is 50 to 90 ℃.
6. The application of the lignin grafted polyamino acid type heavy metal adsorbent in heavy metal adsorption according to claim 1.
7. The use according to claim 6, wherein the heavy metal is adsorbed in an environment having a pH of 2 to 6.
8. The use according to claim 6, wherein the mass ratio of the lignin-grafted polyamino acid-type heavy metal adsorbent to the heavy metal is 1 g: 40-500 mg.
9. The use according to claim 6, wherein the temperature of the adsorption is 20 to 55 ℃.
10. Use according to claim 6, characterized in that the adsorbent to which the heavy metal is adsorbed is regenerated with an acid after the adsorption has ended.
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Application publication date: 20210608 |