CN113289580A - Preparation method of heavy metal adsorption type carbon membrane filter element, product obtained by preparation method and application of product - Google Patents
Preparation method of heavy metal adsorption type carbon membrane filter element, product obtained by preparation method and application of product Download PDFInfo
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- CN113289580A CN113289580A CN202110595142.7A CN202110595142A CN113289580A CN 113289580 A CN113289580 A CN 113289580A CN 202110595142 A CN202110595142 A CN 202110595142A CN 113289580 A CN113289580 A CN 113289580A
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- filter element
- activated carbon
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- heavy metal
- edta
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 34
- 239000012528 membrane Substances 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 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 claims abstract description 28
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 28
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 18
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 18
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920000297 Rayon Polymers 0.000 claims description 4
- 230000003385 bacteriostatic effect Effects 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 229920002522 Wood fibre Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000002025 wood fiber Substances 0.000 claims description 2
- 229920000591 gum Polymers 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000004745 nonwoven fabric Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000010866 blackwater Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 229960001484 edetic acid Drugs 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- DNHVXYDGZKWYNU-UHFFFAOYSA-N lead;hydrate Chemical compound O.[Pb] DNHVXYDGZKWYNU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- BHKKSKOHRFHHIN-MRVPVSSYSA-N 1-[[2-[(1R)-1-aminoethyl]-4-chlorophenyl]methyl]-2-sulfanylidene-5H-pyrrolo[3,2-d]pyrimidin-4-one Chemical compound N[C@H](C)C1=C(CN2C(NC(C3=C2C=CN3)=O)=S)C=CC(=C1)Cl BHKKSKOHRFHHIN-MRVPVSSYSA-N 0.000 description 1
- 229910052695 Americium Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
-
- 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
Abstract
The invention relates to a preparation method of a heavy metal adsorption type carbon membrane filter element, a product obtained by the preparation method and application of the product. The preparation method of the invention takes activated carbon fiber blanket powder as a raw material, the activated carbon fiber blanket powder is modified by acid solution and then mixed with zinc-aluminum hydrotalcite intercalated by EDTA and a binder, and the filter element is prepared by a conventional process. The heavy metal adsorption type carbon membrane filter element can be applied to household water purification equipment, has the adsorption effect of modified activated carbon, further avoids the problem of black water generation frequently occurring in the use of the existing activated carbon filter element by selecting the binder and coating the surface of the filter element with non-woven fabric, and has positive significance in further improving the adsorption efficiency of the carbon filter element on heavy metal ions by doping the composite material of the intercalated hydrotalcite.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a water treatment technology, in particular to a preparation method of a heavy metal adsorption type carbon membrane filter element, and also relates to the filter element prepared by the method and application thereof in water treatment.
[ background of the invention ]
Heavy metals have many different definitions. Can be divided into three main categories: toxic metals (Hg, Cr, Pb, Zn, Cu, Ni, Cd, As, Co, Sn, etc.), radioactive metals (U, Th, Ra, Am, etc.) and precious metals (Pd, Pt, Ag, Au, Ru, etc.). According to the survey millions of tons of heavy metals are discharged into the environment every year. A large amount of untreated urban domestic garbage, industrial and domestic sewage, atmospheric sediment and the like are continuously discharged into water, and the pollution sources contain a large amount of heavy metals, which is the main reason for causing the heavy metal pollution of the water in China. The ecological safety and the human health of China are seriously threatened. According to statistics, at present, hundreds of sudden environmental events and frequent water pollution events occur in China every year, and the safety of urban water supply is seriously influenced. Meanwhile, when tap water is transported to a user's home from a water plant, heavy metals such as lead (Pb) are dissolved out in a pipeline, and if the heavy metals cannot be removed in a subsequent water purification step, the heavy metal pollutants are gradually accumulated in a human body, so that the health of the user is greatly damaged.
At present, membrane separation technologies taking a reverse osmosis membrane, a nanofiltration membrane and an ultrafiltration membrane as cores are applied more in the field of household water purification, wherein the reverse osmosis membrane is most widely applied. Although the reverse osmosis membrane can effectively separate and remove heavy metal ions in water, the wastewater ratio is high in the filtering process, and water resource waste is caused. Although the ultrafiltration membrane has no wastewater problem, the interception precision is poor, and heavy metal ions cannot be effectively removed.
The Chinese patent application CN 201610167686.2 discloses a method for reducing the heavy metal content in river water by using nitric acid oxidation modified activated carbon, 1) firstly, carrying out nitric acid oxidation modification treatment on the activated carbon indoors, then putting the shell activated carbon into a nitric acid solution for soaking and stirring, then cleaning the soaked activated carbon with distilled water, and drying; (2) adjusting the pH value of the sedimentation tank, and collecting the sewage into the sedimentation tank; (3) and putting the activated carbon activated by the nitric acid into river sewage for adsorption so as to reduce the content of heavy metals in the river water. However, the scheme is not suitable for water purification equipment, particularly for the field of household or medium-small commercial water purification equipment, and the modified activated carbon cannot be directly put into a water purification waterway under the requirement of drinking water safety when the heavy metal adsorption problem is solved.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provide a new generation of carbon film filter element so as to have the adsorption effect on heavy metals, particularly lead ions in wastewater.
The idea of the invention is that starting from activated carbon and starting from a chemical mechanism, functional groups such as carboxyl, hydroxyl, quinonyl, phenolic hydroxyl, acid anhydride, lactone group and the like exist on the surface of the activated carbon, and the functional groups can perform ion exchange with heavy metal ions with positive charges in water or form a polyatomic structure complex with the heavy metal, so as to achieve the purpose of adsorbing the heavy metal; meanwhile, in terms of physical characteristics, activated carbon materials, particularly activated carbon fibers, are developed due to surface adsorption pores, and if the number of functional groups on the surface of the activated carbon materials is increased, the adsorption effect on heavy metal ions can be enhanced. Based on the chemical and physical characteristics of the activated carbon material, intercalated hydrotalcite is further doped in the activated carbon material to construct a composite material activated carbon filter element, and through the strong ion exchange capacity of the intercalated hydrotalcite material, organic anions are expected to be inserted into hydrotalcite layers by adopting a certain treatment means to form metal chelates with metal ions, so that the capacity of the activated carbon filter element for adsorbing heavy metal ions is further improved, and the capacity of the activated carbon filter element for adsorbing heavy metal ions is further improved.
Based on the above thought, the invention provides a preparation method of a heavy metal adsorption type carbon membrane filter element, which comprises the following steps:
(1) pulverizing activated carbon fiber blanket to 70-200 mesh, washing, filtering, and drying to obtain raw material powder;
(2) putting the raw material powder in the step (1) into an acid solution, stirring for 2-12h at 60-80 ℃, filtering, taking a solid phase, washing with water to be neutral, and drying for later use;
(3) adding carbonate type zinc-aluminum hydrotalcite into an EDTA solution, adjusting the pH value to 7-9 by using a NaOH solution, wherein the mass ratio of the carbonate type zinc-aluminum hydrotalcite to the EDTA is 4-6: 1, stirring for 12-24 hours at 90-120 ℃ by introducing nitrogen for carrying out ion exchange reaction, filtering to obtain a solid phase after the reaction, and washing and drying to obtain the EDTA-intercalated zinc-aluminum hydrotalcite;
(4) 11-13 parts by volume: 5-6: 1, mixing the product obtained in the step (2), the zinc-aluminum hydrotalcite intercalated by the EDTA and the binder, carrying out negative pressure suction molding at the rotation speed of 200-.
In the present invention, the activated carbon fiber blanket is a commercially available product, such as a product sold by Xinran company under model 1200, 1500. Preferably, the viscose-based activated carbon fiber blanket with the fiber diameter of 5-15 mu m is adopted.
In order to ensure the adsorption capacity of the carbon membrane filter element, the BET specific surface area is preferably 1300-1800 m2The activated carbon fiber blanket is 1500-1800 m2The activated carbon fiber blanket is used for producing the activated carbon fiber blanket.
In the invention, the effect of putting the raw material powder into the acid solution in the step (2) is to wash away ash of the activated carbon fiber, increase surface acid groups of the activated carbon fiber and enhance the adsorption force on heavy metals, wherein the acid solution is selected from dilute nitric acid with the concentration of 1-4mol/L, concentrated nitric acid with the concentration of 13-15.5mol/L, dilute sulfuric acid with the concentration of 1-3mol/L, concentrated sulfuric acid with the concentration of 16.5-18.4 or glacial acetic acid with the concentration of 17.5 mol/L. When dilute sulfuric acid or dilute nitric acid is used, the reaction system is heated to a high temperature and stirred for a long time, for example, at 80 ℃ for 12 hours to sufficiently react. When concentrated sulfuric acid, concentrated nitric acid or glacial acetic acid is used, the temperature of the system can be appropriately lowered and the reaction time can be shortened, for example, the reaction is completed by soaking at 60 ℃ for 2h, and then the solid phase is obtained by filtration and washing.
According to a preferred embodiment, the carbonate-type hydrotalcite contains Zn2+:Al3+2: 1. The hydrotalcite material has symmetrical crystal form and good structure, and can easily cause hydrotalcite interlayer intercalation to other functional anions through some ion exchange reactions.
The zinc-aluminium hydrotalcite can be obtained commercially by the person skilled in the art or prepared according to the methods described in the prior art. An alternative preparation process is as follows: (1) preparing mixed salt solution of zinc nitrate and aluminum nitrate, wherein the molar ratio of Zn to Al is2: 1; (2) preparing mixed alkali solution of sodium hydroxide and sodium carbonate, wherein NaOH/Na2CO3The molar ratio is 2: 1; (3) and pouring the mixed salt solution and the mixed alkali solution into a colloid mill simultaneously for high-speed stirring crystallization, taking out the slurry after the mixed salt solution and the mixed alkali solution are fully mixed, placing the slurry into a high-pressure reaction kettle for crystallization for 24 hours, and then filtering, washing and drying to obtain the carbonate type zinc-aluminum hydrotalcite.
Optionally, in step (3), NaOH is added to avoid dissolution of the carbonate-type zinc-aluminum hydrotalcite in an acidic environment. The concentration of the NaOH solution and the EDTA solution used to adjust the pH of the system was 1:3 on a molar basis.
In the invention, the binder is selected from one or more of wood fiber, paper pulp fiber, PVA (polyvinyl acetate) glue, VAE (polyvinyl acetate) glue, acrylic glue, carboxymethyl cellulose, guar gum and sodium alginate.
According to the invention, by selecting a proper binder and coating the non-woven fabric on the outer surface of the filter element in the step (4), the possible defect of the existing granular carbon filter element is avoided, namely the problem of black water caused by flushing out of part of black powder along with water flow in the use process due to the fact that the crushed slag is formed by uneven particle size distribution or water flow impact crushing in the use process.
In the invention, in order to improve the antibacterial performance of the product, the step (4) also contains antibacterial materials, such as silver-loaded activated carbon fibers, and preferably, the activated carbon fibers are also crushed to 70-200 meshes. The volume ratio of the product obtained in the step (2), the zinc-aluminum hydrotalcite intercalated by the EDTA, the bacteriostatic material and the binder is 11-13: 5-6: 1-3: 1.
in the present invention, after the materials in step (4) are mixed, the materials are subjected to negative pressure suction molding by a wet process to prepare a carbon membrane filter element, which belongs to the prior art in the field of filter element preparation.
The invention also provides application of the carbon membrane filter element prepared by the preparation method in water treatment.
The carbon film filter element is particularly suitable for removing heavy metal ions Pb in water2+、Cd2+、Cu2+、Ag+And (3) heavy metal ions. Experiments prove that the carbon film filter element can realize 97.8% removal rate for wastewater with the heavy metal ion content of 50ppb, which is obviously higher than that of the prior art.
The invention takes the activated carbon fiber felt as the raw material, and the modified composite intercalation hydrotalcite material is prepared into the filter element by wet process molding, and the filter element can be applied to household water purification equipment. The composite material has the adsorption effect of modified activated carbon, the non-woven fabric is coated on the surface of the filter element through the selection of the binder, the problem of black water generation frequently occurring when the existing activated carbon filter element is used is further avoided, and in addition, the adsorption efficiency of the carbon filter element on heavy metal ions is further improved through the composite material doped with the intercalated hydrotalcite, so that the composite material has a remarkable effect.
[ detailed description ] embodiments
The following examples serve to illustrate the technical solution of the present invention without limiting it.
Example 1:
the BET specific surface area is 1800m2The viscose-based activated carbon fiber felt is crushed into 80 meshes, the obtained powder is soaked and cleaned in boiling water, filtered and dried, and then the obtained powder is put into a dilute sulfuric acid solution of 2mol/L, the active carbon powder is completely immersed in the dilute sulfuric acid solution, and the obtained solution is soaked and stirred for 12 hours at the temperature of 80 ℃ for reaction. And after the reaction is finished, filtering to obtain a solid phase, washing the solid phase to be neutral by using pure water, and drying to obtain the modified activated carbon material.
Adding carbonate type zinc-aluminum hydrotalcite into an EDTA solution according to the mass ratio of 5:1, adding a sodium bicarbonate solution to adjust the pH value of the system to 7-9, heating to 90 ℃, continuously stirring for 24 hours at the temperature to perform ion exchange reaction, and protecting the reaction system by using nitrogen to eliminate other influences. And filtering to obtain a product after the reaction is finished, and washing and drying to obtain the zinc-aluminum hydrotalcite intercalated by the EDTA.
And (3) in volume ratio, 11: 5: 3: 1, uniformly mixing an activated carbon material, EDTA (ethylene diamine tetraacetic acid) intercalated zinc-aluminum hydrotalcite, silver-loaded activated carbon fiber and a binder, preparing the carbon membrane filter element by negative pressure suction molding through a conventional wet process, drying the carbon membrane filter element at 100 ℃ through a conventional process, and coating non-woven fabrics to obtain the carbon membrane filter element with the heavy metal adsorption characteristic, wherein the sample is marked as sample No. AC 1.
Example 2
The same procedure as in example 1 was carried out, except that dilute sulfuric acid was replaced with 2mol/L of dilute nitric acid.
The resulting filter element is designated sample No. AC2
Example 3
The same procedure as in example 1 was carried out, except that 17.5mol/L glacial acetic acid was used instead of dilute sulfuric acid and the reaction temperature was adjusted downward to 60 ℃ to shorten the reaction time to 2 h. The resulting filter element is designated sample No. AC3
Example 4
The procedure is as in example 3, except that glacial acetic acid is replaced by 18.4mol/L concentrated sulfuric acid. The resulting filter element is designated sample No. AC4
Example 5
The procedure is as in example 3, except that glacial acetic acid is replaced by 15.5mol/L concentrated nitric acid. The resulting filter element is designated sample No. AC5
Example 6
The BET specific surface area is 1800m2The viscose-based activated carbon fiber felt is crushed into 80 meshes, the obtained powder is soaked and cleaned in boiling water, filtered and dried, and then the weight ratio of the obtained powder to the volume ratio of 15: 1 and a binder, preparing the carbon membrane filter element by a conventional wet process negative pressure suction molding, and then drying and coating non-woven fabric at 100 ℃ by a conventional process to obtain the conventional carbon membrane filter element marked as sample No. AC 0.
Preparing a pure water solution with a lead ion concentration of 50ppb, respectively passing through the filter element samples of examples 1 to 6 at 4L/min under 0.2MPa, measuring the lead content in the produced water of the filter element by an atomic fluorescence method, and calculating the lead removal rate in the water according to the following formula:
the removal rate is (raw water lead ion concentration-water-producing lead ion concentration) ÷ raw water lead ion concentration × 100%
The removal rates for lead ions from water for the cartridge samples of examples 1-6 are shown in the following table.
TABLE 1 adsorption efficiency of activated carbon fiber filter element on Pb
| Sample (I) | Raw Water/ppb | Water production/ppb | Removal rate/%) |
| AC0 | 49.887 | 26.277 | 47.33 |
| AC1 | 46.032 | 9.126 | 80.175 |
| AC2 | 40.827 | 10.856 | 73.410 |
| AC3 | 45.659 | 13.338 | 70.788 |
| AC4 | 42.077 | 7.283 | 82.691 |
| AC5 | 47.803 | 1.041 | 97.822 |
The results show that the performance of the filter element of the invention in removing heavy metal ions in water is obviously superior to that of a common activated carbon filter element, wherein the filter element modified by concentrated nitric acid and added with hydrotalcite has the best interception effect on lead ions, and the interception effect reaches 97.822%.
Claims (10)
1. The preparation method of the heavy metal adsorption type carbon membrane filter element comprises the following steps:
(1) pulverizing activated carbon fiber blanket to 70-200 mesh, washing, filtering, and drying to obtain raw material powder;
(2) putting the raw material powder in the step (1) into an acid solution, stirring for 2-12h at 60-80 ℃, filtering, taking a solid phase, washing with water to be neutral, and drying for later use;
(3) adding carbonate type zinc-aluminum hydrotalcite into an EDTA solution, adjusting the pH value to 7-9 by using a NaOH solution, wherein the mass ratio of the carbonate type zinc-aluminum hydrotalcite to the EDTA is 4-6: 1, stirring for 12-24 hours at 90-120 ℃ by introducing nitrogen for carrying out ion exchange reaction, filtering to obtain a solid phase after the reaction, and washing and drying to obtain the EDTA-intercalated zinc-aluminum hydrotalcite;
(4) 11-13 parts by volume: 5-6: 1, mixing the product obtained in the step (2), the zinc-aluminum hydrotalcite intercalated by the EDTA and the binder, carrying out negative pressure suction molding at the rotation speed of 200-.
2. The method according to claim 1, wherein the activated carbon fiber blanket is a viscose-based activated carbon fiber blanket having a fiber diameter of 5 to 15 μm.
3. The method of claim 1The method is characterized in that the BET specific surface area of the activated carbon fiber blanket is 1300-1800 m2/g。
4. The method according to claim 1, wherein the acid solution is selected from dilute nitric acid having a concentration of 1 to 4mol/L, concentrated nitric acid having a concentration of 13 to 15.5mol/L, dilute sulfuric acid having a concentration of 1 to 3mol/L, concentrated sulfuric acid having a concentration of 16.5 to 18.4mol/L, and glacial acetic acid having a concentration of 17.5 mol/L.
5. The method according to claim 1, wherein the acid solution is concentrated nitric acid of 13 to 15.5 mol/L.
6. The process according to claim 1, wherein Zn is contained in the carbonate-type zinc-aluminum hydrotalcite in a molar ratio2+:Al3+＝2:1。
7. The method according to claim 1, wherein the binder is selected from one or more of wood fiber, pulp fiber, PVA gum, VAE gum, acrylic gum, carboxymethyl cellulose, guar gum, and sodium alginate.
8. The preparation method according to claim 1, characterized in that step (4) further comprises bacteriostatic materials, and the volume ratio of the product of step (2), the EDTA-intercalated zinc-aluminum hydrotalcite, the bacteriostatic materials and the binder is 11-13: 5-6: 1-3: 1.
9. the preparation method according to claim 8, wherein the bacteriostatic material is silver-loaded activated carbon fiber powder with an average mesh size of 70-200 meshes.
10. Use of a carbon membrane filter element prepared by the method of any one of claims 1 to 9 in water treatment.
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