CN117550675A - Preparation method of modified activated carbon capable of effectively removing phosphorus in glyphosate waste salt - Google Patents
Preparation method of modified activated carbon capable of effectively removing phosphorus in glyphosate waste salt Download PDFInfo
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- CN117550675A CN117550675A CN202311851127.XA CN202311851127A CN117550675A CN 117550675 A CN117550675 A CN 117550675A CN 202311851127 A CN202311851127 A CN 202311851127A CN 117550675 A CN117550675 A CN 117550675A
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- activated carbon
- modified activated
- carbon
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- glyphosate
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 43
- 239000011574 phosphorus Substances 0.000 title claims abstract description 43
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 16
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 16
- 150000003839 salts Chemical class 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 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 abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 19
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 19
- 239000000661 sodium alginate Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003607 modifier Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 150000002603 lanthanum Chemical class 0.000 claims description 5
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 4
- 229960001927 cetylpyridinium chloride Drugs 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 230000001788 irregular Effects 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 241000143432 Daldinia concentrica Species 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000007630 basic procedure Methods 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- PDYXIVPKOMYDOK-UHFFFAOYSA-N Glyphosate-monoammonium Chemical compound [NH4+].OC(=O)CNCP(O)([O-])=O PDYXIVPKOMYDOK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZEKANFGSDXODPD-UHFFFAOYSA-O carboxymethyl(phosphonomethyl)azanium;propan-2-amine Chemical compound CC(C)[NH3+].OC(=O)CNCP(O)(O)=O ZEKANFGSDXODPD-UHFFFAOYSA-O 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000874 microwave-assisted extraction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- LIOPHZNMBKHGAV-UHFFFAOYSA-M potassium;2-(phosphonomethylamino)acetate Chemical compound [K+].OC(=O)CNCP(O)([O-])=O LIOPHZNMBKHGAV-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- YWICANUUQPYHOW-UHFFFAOYSA-M sodium;2-(phosphonomethylamino)acetate Chemical compound [Na+].OP(O)(=O)CNCC([O-])=O YWICANUUQPYHOW-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
Classifications
-
- 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
- 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
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
-
- 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
- B01J20/22—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
-
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- 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
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
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- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a preparation method of modified activated carbon capable of effectively removing phosphorus in glyphosate waste salt, which comprises the steps of firstly mixing activated carbon and lanthanum nitrate, preparing a mixed solution, regulating the pH value of the aqueous solution to 6-7, preparing preliminary modified activated carbon, adding the preliminary modified activated carbon into sodium alginate solution, stirring and reacting to prepare carbon spheres, finally adding the carbon spheres into metal salt solution, stirring, soaking and drying to prepare the modified activated carbon. According to the invention, the three-step method is adopted to modify the activated carbon, so that lanthanum can be uniformly loaded on the surface of the activated carbon, the precipitation efficiency of phosphate ions is improved, the phosphorus removal rate reaches more than 99%, and the stability of lanthanum loading can be improved; the phosphorus removal rate of the regenerated modified activated carbon can still reach 86 percent.
Description
Technical Field
The invention belongs to the field of preparation of modified activated carbon, and particularly relates to a preparation method of modified activated carbon capable of effectively removing phosphorus in glyphosate waste salt.
Background
Glyphosate, also known as noda, and its molecular formula is C 3 H 8 NO 3 P is an organophosphorus pesticide, and is one of the widely used herbicides in the world due to its characteristics of high efficiency, low toxicity, broad spectrum and low cost. The glyphosate is white crystal powder, and mainly comprises ammonium glyphosate, diammonium glyphosate, isopropylammonium glyphosate, potassium glyphosate, sodium glyphosate and other salts. Has been successfully developed by Mengshan in 1971, and is widely used in the field of transgenic crops. Glyphosate is a persistent and accumulating contaminant with a significant environmental impact due to its long half-life.
At present, the treatment methods for the wastewater produced by the glyphosate are various and mainly divided into three categories, namely a physical method, a chemical method and a biological method. Physical methods include adsorption, membrane separation, microwave-assisted extraction, and the like. The chemical method is to utilize a certain chemical reagent to form a precipitate with phosphate so as to achieve the purpose of removing phosphorus in the solution. The biological method is to use glyphosate as the only nitrogen source and phosphorus source, so that the phosphorus element can be metabolically degraded, and the aim of removing the phosphorus element is achieved. The adsorption method in the physical method is to add an adsorbent into the phosphorus-containing wastewater so that phosphorus can have a bonding effect with the adsorbent, and the phosphorus can be enriched on the adsorbent, so that phosphorus impurities in the wastewater are removed. The adsorption method has the advantages of low running cost, simple operation and high efficiency.
Currently, many adsorbents are used, such as activated carbon, biomass, metal oxides, clay minerals, and the like. For example, the invention patent with the application number of CN202110779504.8, named as a preparation method and application of a zeolite type phosphorus remover for high-salt waste liquid, discloses a preparation method of a zeolite type phosphorus remover for high-salt waste liquid, which has low raw material cost, simple operation and high phosphorus removal rate, but has lower adsorption capacity.
The invention patent with the application number of CN202111183335.8 and the name of 'high-salt byproduct waste salt phosphorus removal and impurity removal system and process of glyphosate' discloses a modified activated carbon for wastewater phosphorus removal and a preparation method thereof, wherein the modified activated carbon is used for thoroughly removing phosphorus-containing substances in wastewater, so that the wastewater meets the standard requirements.
Based on the above, the invention is based on the modification of the activated carbon, and can efficiently remove the phosphorus in the waste glyphosate salt.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for preparing modified activated carbon, which can efficiently remove phosphorus in waste glyphosate salt, and the removal rate can reach more than 99%.
The technical scheme is as follows: the invention relates to a preparation method of modified activated carbon capable of effectively removing phosphorus in glyphosate waste salt, which comprises the following steps:
(1) Mixing active carbon and a modifier, preparing into an aqueous solution, stirring in an oil bath, adjusting the pH value of the aqueous solution to 6-7, performing ultrasonic treatment, filtering, washing to be neutral, drying, and grinding to obtain primary modified active carbon; wherein the modifier comprises lanthanum salt and cationic surfactant in a mass ratio of (1-1.5): 1;
(2) Adding the preliminary modified activated carbon prepared in the step (1) into sodium alginate solution, and stirring for reaction to obtain carbon spheres;
(3) And (3) adding the carbon spheres prepared in the step (2) into a metal salt solution, stirring, soaking, and drying to obtain the modified activated carbon.
The invention adopts a three-step method to modify the activated carbon, thereby improving the removal rate of the modified activated carbon to the phosphorus in the glyphosate waste salt and enabling the removal rate to reach more than 99 percent. The preparation method comprises the steps of firstly adopting a modifier aqueous solution prepared from lanthanum salt and a cationic surfactant, carrying out preliminary modification on the modifier aqueous solution under the conditions of ultrasonic treatment and pH value of 6-7, opening an internal gap channel of an adsorption carrier under the acidic condition, increasing the specific surface area, and loading the modified active carbon on the active carbon carrier more superior to lanthanum metal salt, so as to prepare preliminary modified active carbon; secondly, stirring reaction is carried out on the preliminary modified activated carbon through sodium alginate, soaking reaction is carried out on the preliminary modified activated carbon and the metal salt solution after the reaction, the introduction of the sodium alginate not only can stabilize the preliminary modified activated carbon system and improve the stability of lanthanum metal salt preliminarily loaded on an activated carbon carrier, but also can lead metal ions introduced later to form complexation with the sodium alginate based on the addition of the sodium alginate to form a three-dimensional reticular structure, so that the metal ions introduced later reach atomic-level uniform mixing and can not be dissociated in water, and the dephosphorization effect of the finally prepared modified activity is improved.
Further, when the modified activated carbon prepared by the method is regenerated, the used modified activated carbon is put into sodium hydroxide solution to be stirred for 5-10 hours, soaked, filtered and dried, and the regenerated activated carbon is prepared. Preferably, the concentration of NaOH employed may be in the range of 0.1 to 0.2mol/L.
Further, in the step (1) of the preparation method, the mass ratio of the active carbon to the modifier is 1 (1-2); the concentration of the modifier and the activated carbon in the aqueous solution is 10-30mmol/L.
Further, in the step (1) of the preparation method of the invention, the cationic surfactant is cetyl trimethyl ammonium bromide or cetyl pyridinium chloride; the lanthanum salt is lanthanum nitrate.
Further, in the step (1) of the preparation method, the temperature of the oil bath is 60-90 ℃, and the oil bath is stirred for 10-12 hours; the ultrasonic time is 20-40min.
Further, in the step (2) of the preparation method, the mass ratio of the sodium alginate to the primary activated carbon is 1 (1-2), and the concentration of the sodium alginate solution is 5-10g/L.
Further, in the step (3) of the preparation method of the invention, the metal salt solution is LaCl 3 The concentration of the solution is 20-30mmol/L, and the mass ratio of the metal salt to the carbon spheres is (1-2): 1.
The beneficial effects are that: compared with the prior art, the invention has the remarkable advantages that: the modified activated carbon is modified by adopting a three-step method, so that lanthanum can be uniformly loaded on the surface of the activated carbon, the precipitation efficiency of phosphate ions is improved, the stability of lanthanum loading can be improved, and the phosphorus removal rate can reach more than 99%.
Drawings
FIG. 1 is a graph showing the effect of the amount of the modified activated carbon prepared in example 1 of the present invention on the removal rate of phosphorus.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings.
The raw materials used in the present invention are commercially available. The treated water sample adopted by the invention is prepared from waste salt containing phosphorus after high Wen Lin oxygen pyrolysis of glyphosate byproduct salt produced in limited production of Hubei Xingfu chemical group stock, and the total phosphorus content of the water sample is 15mg/L.
Example 1
The preparation method of the modified activated carbon in the embodiment 1 comprises the following steps:
(1) La (NO) 3 ) 3 ·6H 2 O and hexadecyl trimethyl ammonium bromide are uniformly mixed according to the mass ratio of 1.22:1 to prepare a modifier;
(2) Mixing the modifier with active carbon according to a mass ratio of 1:1, adding distilled water according to a concentration of 20mmol/L, stirring and reacting for 11 hours at an oil bath temperature of 80 ℃, adjusting the pH value to 7, performing ultrasonic reaction for 30 minutes, filtering, washing until the mixture is neutral, drying for 12 hours at a temperature of 72 ℃, and grinding to obtain the primary modified active carbon;
(3) Adding the preliminary modified activated carbon prepared in the step (1) into sodium alginate solution with the concentration of 8g/L, and rapidly stirring to prepare irregular carbon spheres; wherein the mass ratio of the preliminary modified activated carbon to the sodium alginate is 1:1;
(4) Adding the irregular carbon balls prepared in the step (3) into a lanthanum chloride solution with the concentration of 25mmol/L, stirring for 10min, and soaking for 12h, wherein the mass ratio of the lanthanum chloride to the irregular carbon balls is 1:1, so as to prepare the final modified activated carbon.
Comparative example 1
The basic procedure is the same as in example 1, except that step (3) and step (4) of example 1 are omitted. The method comprises the following steps:
(1) La (NO) 3 ) 3 ·6H 2 O and hexadecyl trimethyl ammonium bromide are uniformly mixed according to the mass ratio of 1.22:1 to prepare a modifier;
(2) Mixing the modifier with active carbon according to the mass ratio of 1:1, adding distilled water according to the concentration of 20mmol/L, stirring and reacting for 11 hours at the temperature of 80 ℃ of an oil bath, adjusting the pH value to 7, carrying out ultrasonic reaction for 30 minutes, filtering, washing until the mixture is neutral, drying for 12 hours at the temperature of 72 ℃, and grinding to obtain the primary modified active carbon.
Comparative example 2
The basic procedure is the same as in example 1, except that step (4) of example 1 is omitted. The method comprises the following steps:
(1) La (NO) 3 ) 3 ·6H 2 O and hexadecyl trimethyl ammonium bromide are uniformly mixed according to the mass ratio of 1.22:1 to prepare a modifier;
(2) Mixing the modifier with active carbon according to a mass ratio of 1:1, adding distilled water according to a concentration of 20mmol/L, stirring and reacting for 11 hours at an oil bath temperature of 80 ℃, adjusting the pH value to 7, performing ultrasonic reaction for 30 minutes, filtering, washing until the mixture is neutral, drying for 12 hours at a temperature of 72 ℃, and grinding to obtain the primary modified active carbon;
(3) Adding the preliminary modified activated carbon prepared in the step (1) into sodium alginate solution with the concentration of 8g/L, and rapidly stirring to prepare irregular carbon spheres; wherein the mass ratio of the preliminary modified activated carbon to the sodium alginate is 1:1.
And (3) performance detection: dephosphorization effect measurement
The modified activated carbon prepared in example 1 and comparative examples 1 and 2 was added to the waste water sample used in the present invention in an amount of 0.2g/50mL, and mixed in a magnetic stirrer for 3 hours, and dephosphorization results are shown in table 1 below.
Table 1 dephosphorization effect table of example 1 and comparative example 1
As can be seen from Table 1, the total phosphorus removal rate of the modified activated carbon prepared by the modification method can reach 99.6%, the adsorption capacity is 3.74mg/g, and the modified activated carbon has a higher phosphorus removal rate.
Meanwhile, the modified activated carbon prepared in example 1 was subjected to phosphorus removal effect detection using different addition amounts, and the obtained results are shown in fig. 1 below. As is clear from FIG. 1, the modified activated carbon of the present invention has an increased phosphorus removal rate with an increase in the amount of the modified activated carbon added to 0.2g/50mL or less, but has a smooth phosphorus removal rate with an increase in the amount of the modified activated carbon added to 0.25g/50mL or more.
EXAMPLE 2 modified activated carbon regeneration
The modified activated carbon obtained after the dephosphorization test in the embodiment 1 is dried and collected, added into a sodium hydroxide solution with the concentration of 0.1mol/L, stirred, filtered, washed until the solution is neutral, and dried in an oven.
The dephosphorization effect of the regenerated modified activated carbon was measured, and the obtained results are shown in table 2 below.
Table 2 dephosphorization effect tables of example 1 and example 2
As is clear from Table 2, the phosphorus removal rate of the activated carbon prepared by the invention after regeneration can also reach 86%, the adsorption capacity can reach 3.2mg/g, and the regeneration effect is excellent.
Example 3
The preparation method of the modified activated carbon in the embodiment 3 comprises the following steps:
(1) La (NO) 3 ) 3 ·6H 2 Uniformly mixing O and cetylpyridinium chloride according to the mass ratio of 1:1 to prepare a modifier;
(2) Mixing the modifier with active carbon according to a mass ratio of 1.5:1, adding distilled water according to a concentration of 10mmol/L, stirring and reacting for 12 hours at an oil bath temperature of 60 ℃, adjusting the pH value to 6.5, carrying out ultrasonic reaction for 40 minutes, filtering, washing until the mixture is neutral, drying for 12 hours at a temperature of 72 ℃, and grinding to obtain the primary modified active carbon;
(3) Adding the preliminary modified activated carbon prepared in the step (1) into sodium alginate solution with the concentration of 5g/L, and rapidly stirring to prepare irregular carbon spheres; wherein the mass ratio of the preliminary modified activated carbon to the sodium alginate is 1.5:1;
(4) Adding the irregular carbon balls prepared in the step (3) into a lanthanum chloride solution with the concentration of 20mmol/L, stirring for 10min, and soaking for 12h, wherein the mass ratio of the lanthanum chloride to the irregular carbon balls is 1.5:1, so as to prepare the final modified activated carbon.
Example 4
The preparation method of the modified activated carbon in the embodiment 4 comprises the following steps:
(1) La (NO) 3 ) 3 ·6H 2 Uniformly mixing O and cetylpyridinium chloride according to the mass ratio of 1.5:1 to prepare a modifier;
(2) Mixing the modifier with active carbon according to a mass ratio of 2:1, adding distilled water according to a concentration of 30mmol/L, stirring and reacting for 10 hours at an oil bath temperature of 90 ℃, adjusting the pH value to 6, carrying out ultrasonic reaction for 20 minutes, filtering, washing until the mixture is neutral, drying for 12 hours at a temperature of 72 ℃, and grinding to obtain the primary modified active carbon;
(3) Adding the preliminary modified activated carbon prepared in the step (1) into sodium alginate solution with the concentration of 10g/L, and rapidly stirring to prepare irregular carbon spheres; wherein the mass ratio of the preliminary modified activated carbon to the sodium alginate is 2:1;
(4) Adding the irregular carbon spheres prepared in the step (3) into a lanthanum chloride solution with the concentration of 30mmol/L, stirring for 10min, and soaking for 12h, wherein the mass ratio of the lanthanum chloride to the irregular carbon spheres is 2:1, so as to prepare the final modified activated carbon.
And (3) performance detection: dephosphorization effect measurement
The modified activated carbon prepared in example 3 and example 4 was added to the waste water sample used in the present invention in an amount of 0.2g/50mL, and mixed in a magnetic stirrer for 3 hours, and dephosphorization results are shown in table 3 below.
Table 3 dephosphorization effect table of example 3 and example 4
As can be seen from Table 3, the modified activated carbon prepared by the modification method of the invention has a total phosphorus removal rate of more than 99%, an adsorption capacity of more than 3.57mg/g and a higher phosphorus removal rate.
Claims (7)
1. The preparation method of the modified activated carbon capable of effectively removing phosphorus in the glyphosate waste salt is characterized by comprising the following steps of:
(1) Mixing active carbon and a modifier, preparing into an aqueous solution, stirring in an oil bath, adjusting the pH value of the aqueous solution to 6-7, performing ultrasonic treatment, filtering, washing to be neutral, drying, and grinding to obtain primary modified active carbon; wherein the modifier comprises lanthanum salt and cationic surfactant in a mass ratio of (1-1.5): 1;
(2) Adding the preliminary modified activated carbon prepared in the step (1) into sodium alginate solution, and stirring for reaction to obtain carbon spheres;
(3) Adding the carbon spheres prepared in the step (2) into a metal salt solution, stirring, soaking and drying to obtain the modified activated carbon.
2. The method for preparing modified activated carbon capable of effectively removing phosphorus in waste glyphosate salt according to claim 1, wherein when the modified activated carbon is regenerated, the used modified activated carbon is put into sodium hydroxide solution with the concentration of 0.1-0.2mol/L to be stirred for 5-10h, soaked, filtered and dried, and the regenerated activated carbon is prepared.
3. The method for preparing modified activated carbon capable of effectively removing phosphorus in waste glyphosate salt according to claim 1, wherein in the step (1), the mass ratio of the activated carbon to the modifier is 1 (1-2), and the concentration of the modifier and the activated carbon in the aqueous solution is 10-30mmol/L.
4. The method for preparing modified activated carbon effective in removing phosphorus from waste glyphosate salt according to claim 1, wherein in step (1), the cationic surfactant is cetyl trimethylammonium bromide or cetyl pyridinium chloride; the lanthanum salt is lanthanum nitrate.
5. The method for preparing modified activated carbon capable of effectively removing phosphorus in waste glyphosate salt according to claim 1, wherein in the step (1), the temperature of the oil bath is 60-90 ℃, and the oil bath is stirred for 10-12 hours; the ultrasonic time is 20-40min.
6. The method for preparing modified activated carbon capable of effectively removing phosphorus in glyphosate waste salt according to claim 1, wherein in the step (2), the mass ratio of sodium alginate to primary activated carbon is 1 (1-2), and the concentration of sodium alginate solution is 5-10g/L.
7. The method for preparing modified activated carbon effective in removing phosphorus from waste glyphosate salt as claimed in claim 1, wherein in step (3), the metal salt solution is LaCl 3 The concentration of the solution is 20-30mmol/L, and the mass ratio of the metal salt to the carbon sphere is (1-2): 1.
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