CN117839639B - Adsorption material and preparation method and application thereof - Google Patents
Adsorption material and preparation method and application thereof Download PDFInfo
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- CN117839639B CN117839639B CN202410136257.3A CN202410136257A CN117839639B CN 117839639 B CN117839639 B CN 117839639B CN 202410136257 A CN202410136257 A CN 202410136257A CN 117839639 B CN117839639 B CN 117839639B
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 95
- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920002148 Gellan gum Polymers 0.000 claims abstract description 63
- 239000000216 gellan gum Substances 0.000 claims abstract description 62
- 235000010492 gellan gum Nutrition 0.000 claims abstract description 55
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 51
- 239000011574 phosphorus Substances 0.000 claims abstract description 51
- 239000010802 sludge Substances 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- -1 iron ion Chemical class 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000008055 phosphate buffer solution Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 239000002686 phosphate fertilizer Substances 0.000 abstract description 2
- 239000004794 expanded polystyrene Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002351 wastewater Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 230000028327 secretion Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J20/22—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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides an adsorption material, a preparation method and application thereof, wherein the preparation method of the adsorption material comprises the following steps: and (3) polymerizing the sludge extracellular polymer and gellan gum, and then soaking the sludge extracellular polymer and gellan gum in an iron ion solution to obtain the adsorption material. The adsorption material not only can greatly improve the phosphorus adsorption capacity, is suitable for the environment with pH value of 3-10, has higher phosphorus adsorption capacity in acidic, alkaline and neutral environments, but also is easy to recycle, and the recycled adsorption material can be reused for phosphorus adsorption after releasing phosphorus in alkaline solution, so that the recycling of the adsorption material is realized; meanwhile, the desorbed solution can be used for preparing phosphate fertilizer and the like, so that the phosphorus can be recycled.
Description
Technical Field
The invention relates to the technical field of environmental pollution treatment, in particular to an adsorption material, a preparation method and application thereof.
Background
Phosphorus is a non-renewable resource, on one hand, exhaustion crisis exists in the global scope, and on the other hand, phosphorus-rich wastewater discharged by human activities such as aquaculture, agricultural production and the like brings serious problems to natural water ecological systems, such as eutrophication and the like. Adsorption is the preferred technology for recovering phosphorus from water, and has higher practicability by virtue of the advantages of easiness in operation, high treatment efficiency, low running cost and the like. In recent years, various adsorption materials have been developed for adsorbing and recovering phosphorus in water bodies, such as metal-based oxides, natural ores, activated carbon, etc., but all of the above adsorption materials have disadvantages of small particle size, high cost, weak phosphorus adsorption capacity, etc., affecting popularization, and thus it is necessary to develop novel phosphorus adsorption materials having high adsorption capacity and low cost.
Chinese patent CN107312127a discloses a method for preparing chemically modified gellan gum, which comprises the following steps: the graft copolymer is prepared by taking potassium persulfate as an initiator, acrylamide as a grafting monomer and trimethylolpropane triglycidyl ether as a cross-linking agent. The obtained modified gellan gum has enhanced water absorption, and can obtain high grafting rate under the condition of lower gellan gum and acrylamide ratio, so that the gellan gum has wider application prospect. The invention has simple operation and lower cost; the prepared modified gellan gum can be used as an adsorbent to play a great role in industrial wastewater, and is also applied to the fields of drug controlled release, biomedical engineering, filling conduction and the like, but has poor phosphorus adsorptivity.
Chinese patent CN113929195A discloses a method for preparing sludge extracellular polymeric compound nano zero-valent iron. The method comprises the following steps: standing and precipitating the activated sludge, heating in a water bath, adding anhydrous NaCO 3, centrifuging to obtain a sludge extracellular polymer, adding FeCl 3·6H2 O, adding NaBH 4 aqueous solution, stirring under the protection of nitrogen, and separating a solid product by using a magnet. The invention takes nano zero-valent iron and surplus sludge as the basis, and the prepared sludge extracellular secretion composite nano zero-valent iron not only maintains the advantages of high efficiency of microorganism extracellular secretion, suitability for treating heavy metal wastewater and the like, but also has the characteristic of magnetic separation and high reduction adsorption peculiar to nano zero-valent iron, is easy to recycle, has high flocculation efficiency and high reduction adsorption efficiency, avoids secondary pollution of sludge, and has the phosphorus adsorption property to be improved.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide an adsorbent material, a method for preparing the same, and a use thereof for further improving phosphorus adsorption.
To achieve the above and other related objects, the present invention is achieved by the following technical means.
The invention provides a preparation method of an adsorption material, which comprises the following steps: and (3) polymerizing the sludge extracellular polymer and gellan gum, and then soaking the sludge extracellular polymer and gellan gum in an iron ion solution to obtain the adsorption material.
Preferably, the gellan gum is selected from one or both of a high acyl gellan gum and a low acyl gellan gum.
Preferably, the sludge extracellular polymer is obtained by extracting sludge.
More preferably, the sludge is municipal sludge and/or river and lake sediment.
More preferably, the preparation method of the sludge extracellular polymer comprises the following steps: and (3) carrying out solid-liquid separation on the sludge to obtain a solid, extracting and purifying the solid to obtain the sludge extracellular polymer.
Further preferably, the solid-liquid separation is performed by centrifugation.
Still more preferably, the centrifugal rotational speed is 1000 to 1500r/min.
Still more preferably, the centrifugation time is 5 to 20 minutes.
Further preferably, microfiltration is used for purification.
Further preferably, the extraction method is as follows: adding phosphate buffer solution to make up the volume, and extracting by one or more of heating, ultrasonic and centrifuging.
Still more preferably, the heating temperature is 75 to 85 ℃.
Still more preferably, the heating time is 20 to 40 minutes.
Still more preferably, the ultrasonic frequency is 15 to 30kHz.
Still more preferably, the time of the ultrasound is 3 to 5 minutes.
Still more preferably, the centrifugal speed is 5500-6500 r/min.
Still more preferably, the centrifugation time is 25 to 40 minutes.
Still more preferably, the pH of the phosphate buffer is 5.5 to 8.5.
Preferably, the polymerization reaction further comprises a reaction medium, the reaction medium being water.
Preferably, the mass ratio of the sludge Extracellular Polymer (EPS) to the gellan gum is (0.5-10): 1. the mass ratio of EPS to gellan gum may be: (0.5-1): 1. (1-2): 1. (2-3): 1. (3-4): 1. (4-5): 1. (5-10): 1. the more EPS is used, the less gellan gum is used and the higher the phosphorus adsorption performance of the adsorbent material, but if the amount of gellan gum is too small, the phosphorus adsorption performance of the adsorbent material is reduced.
Preferably, the polymerization reaction further comprises an initiator selected from one or both of ammonium persulfate and potassium persulfate.
More preferably, the mass ratio of the gellan gum to the initiator is (0.1-10): 1.
The mass ratio of the gellan gum to the initiator may be (0.1-0.4): 1. (0.4-1): 1. (1-2): 1. (2-3): 1. (3-4): 1. (4-5): 1.
Preferably, the concentration of the sludge extracellular polymer in the polymerization reaction solution is 10-60 g/L. The dosage of the sludge extracellular polymer is 10-20 g/L, 20-30 g/L, 30-40 g/L, 40-50 g/L and 50-60 g/L. Too high or too low a concentration of the sludge extracellular polymer reduces the phosphorus adsorption effect.
Preferably, the sludge extracellular polymer and the gellan gum are further subjected to a mixing treatment prior to the polymerization reaction.
Preferably, the polymerization temperature is 75 to 95 ℃. For example, the temperature may be 75 to 80 ℃, 80 to 85 ℃, 85 to 90 ℃, or 90 to 95 ℃.
More preferably, the rate of rise of the polymerization temperature is 0.5 to 1.5 ℃/min. For example, it may be 0.5 to 0.7℃per minute, 0.7 to 1℃per minute, 1 to 1.2℃per minute, or 1.2 to 1.5℃per minute.
More preferably, the polymerization time is from 5 to 7 hours.
Preferably, the sludge extracellular polymer and the gellan gum are subjected to a cooling treatment after the polymerization reaction.
More preferably, the cooling temperature is 20 to 30 ℃ and the cooling time is 22 to 26 hours.
The cooling temperature may be 20 to 22 ℃, 22 to 24 ℃, 24 to 26 ℃, 26 to 28 ℃ and 28 to 30 ℃. The cooling time can be 22-23 h, 23-24 h, 24-25 h or 25-26 h.
Preferably, the ferric ion solution is selected from one or more of ferric chloride solution, ferric sulfate solution and ferric nitrate solution. The solvent of the solution is water.
Preferably, the concentration of iron ions in the iron ion solution is 0.2-2.2 mol/L. For example, the concentration of iron ions in the iron ion solution may be 0.2 to 0.6mol/L, 0.6 to 1mol/L, 1 to 1.4mol/L, 1.4 to 1.8mol/L, or 1.8 to 2.2mol/L. The higher the concentration of iron ions in the iron ion solution, the higher the phosphorus removal rate, but when the concentration of iron ions is too high, the phosphorus removal rate does not increase any more.
Preferably, the soaking time is 18-28 h. For example, the soaking time can be 18-20, 20-22, 22-24, 24-26 or 26-28 h.
Preferably, the soaking treatment is also subjected to a washing and/or drying treatment.
More preferably, the washing is water washing.
More preferably, the drying is in the shade.
The invention also discloses the adsorption material prepared by the preparation method.
The invention also discloses application of the adsorption material to adsorption of phosphorus in water environment.
The invention also discloses a method for removing phosphorus in water environment, which comprises the following specific steps: and adding the adsorption material into the water body.
Preferably, the addition amount of the adsorption material is 10-30 g/L. For example, the concentration of the catalyst may be 10 to 15g/L, 15 to 20g/L, 20 to 25g/L or 25 to 30g/L.
The invention discloses an adsorption material, a preparation method and application thereof, wherein hydroxyl groups on a gellan gum molecular chain in the adsorption material are physically crosslinked through hydrogen bonds to form a three-dimensional spiral structure, EPS is grafted on the gellan gum molecular chain, and iron ions are combined through complexation. The adsorption material has the following beneficial effects:
(1) Greatly improves the phosphorus adsorption capacity;
(2) Is suitable for the environment with pH value of 3-10, and has higher phosphorus adsorption capacity in acidic, alkaline and neutral environments;
(3) The method is easy to recycle, and the recycled adsorption material can be used for adsorbing phosphorus again after releasing phosphorus in alkaline solution, so that the recycling of the adsorption material is realized; meanwhile, the desorbed solution can be used for preparing phosphate fertilizer and the like, so that the phosphorus can be recycled;
(4) In the phosphate adsorption process, the influence of coexisting anions in the environment is small;
(5) The invention takes the sludge as the raw material, thereby realizing the resource utilization of the waste; meanwhile, the preparation conditions are mild, the preparation process is simple, and the method is suitable for large-scale industrial production and can be widely used for water environment treatment.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention may be used to practice the present invention according to the knowledge of one skilled in the art and the description of the present invention.
Example 1
The embodiment provides a specific adsorption material, and the specific preparation method comprises the following steps:
(1) Preparation of EPS: taking municipal sludge samples, centrifuging for 5min at the rotating speed of 1000r/min, discarding supernatant, adding phosphate buffer to supplement the original volume, heating for 20min at the water bath of 75 ℃, centrifuging for 25min at the rotating speed of 5500r/min, and filtering by a 0.45 mu m filter membrane to obtain EPS.
(2) Preparing an adsorption material: 0.6g of high acyl gellan gum is added to 100mL of deionized water, 3g of EPS and 0.6g of ammonium persulfate are added, and the mixture is continuously stirred for 15min to be uniformly mixed. Heating to 80 ℃ at a heating rate of 1 ℃/min, and stirring at constant temperature for 6 hours to obtain a mixed solution. The mixed solution was cooled to room temperature (24 ℃) and stirred for 24 hours to obtain an EPS-gellan gum mixed material. Soaking the EPS-gellan gum mixed material in ferric chloride solution with the concentration of Fe 3+ of 1.4mol/L for 20h, filtering, and cleaning with distilled water to obtain the adsorption material.
In the polymerization reaction solution, the concentration of EPS is 30g/L, and the mass ratio of EPS, gellan gum and initiator is 5:1:1.
The mass of EPS is 0.71g and the mass of gellan gum is 0.14g in the raw materials for preparing the adsorption material per gram.
Example 2
The embodiment provides a specific adsorption material, and the preparation method comprises the following steps:
(1) Preparation of EPS: taking municipal sludge samples, centrifuging for 15min at a rotating speed of 1500r/min, discarding supernatant, adding a phosphate buffer solution to supplement the original volume, putting the obtained products into an ultrasonic reactor (KQ 3200E, kunshanshumei) for ultrasonic treatment at 20kHz for 5min, centrifuging for 30min at a rotating speed of 6500r/min, and filtering by a 0.45 mu m filter membrane to obtain EPS.
(2) Preparing an adsorption material: 4g of high acyl gellan gum is added to 100mL of deionized water, 4gEPS and 1g of ammonium persulfate are added, and the mixture is continuously stirred for 15min to be uniformly mixed. Heating to 90 ℃ at a heating rate of 0.7 ℃/min, and stirring at constant temperature for 6 hours to obtain a mixed solution. And cooling the mixed solution to room temperature (24 ℃) and carrying out polymerization for 22 hours to obtain the EPS-gellan gum mixed material. Soaking the EPS-gellan gum mixed material in ferric sulfate solution with the concentration of Fe 3+ of 2.0mol/L for 25h, filtering, and cleaning with distilled water to obtain the adsorption material.
In the polymerization reaction solution, the concentration of EPS is 40g/L, and the mass ratio of EPS, gellan gum and initiator is 4:4:1.
The mass of EPS is 0.44g and the mass of gellan gum is 0.44g in the raw materials for preparing the adsorption material per gram.
Example 3
The embodiment provides a specific adsorption material, and the preparation method comprises the following steps:
(1) Preparation of EPS: taking a river and lake sludge sample, centrifuging for 20min at a rotating speed of 1500r/min, removing supernatant, adding a phosphate buffer solution to supplement the original volume, heating for 40min at a water bath of 85 ℃, centrifuging for 40min at a rotating speed of 6500r/min, and filtering by a 0.45 mu m filter membrane to obtain EPS.
(2) Preparing an adsorption material: 1g of low acyl gellan gum is added to 100mL of deionized water, 3gEPS g of ammonium persulfate and 0.2g of ammonium persulfate are added, and the mixture is continuously stirred for 15min to be uniformly mixed. Heating to 95 ℃ at a heating rate of 1.5 ℃/min, and stirring at constant temperature for 6 hours to obtain a mixed solution. The mixed solution is cooled to room temperature (24 ℃) and polymerized for 28 hours, and the EPS-gellan gum mixed material is obtained. Soaking the EPS-gellan gum mixed material in ferric nitrate solution with the concentration of Fe 3+ of 0.5mol/L for 24 hours, filtering, and cleaning with distilled water to obtain the adsorption material.
In the polymerization reaction solution, the concentration of EPS is 30g/L, and the mass ratio of EPS to gellan gum is 3:1, the mass ratio of the gellan gum to the initiator is 5:1.
The mass of EPS is 0.71g and the mass of gellan gum is 0.24g in the raw materials for preparing the adsorption material per gram.
Example 4
This example provides a specific adsorbent material, which is prepared in substantially the same manner as in example 1, and differs from example 1 only in that: in the step (2), the consumption of gellan gum in the adsorption material is 1.2g. In the polymerization reaction solution, the mass ratio of EPS, gellan gum and initiator is 5:2:1. the mass of EPS is 0.63g and the mass of gellan gum is 0.25g in the raw materials for preparing the adsorption material per gram.
Example 5
This example provides a specific adsorbent material, which is prepared in substantially the same manner as in example 1, and differs from example 1 only in that: in the step (2), the amount of EPS added was 6g. In the polymerization reaction solution, the concentration of EPS is 60g/L, and the mass ratio of EPS to gellan gum is 10:1. the mass of EPS is 0.83g and the mass of gellan gum is 0.08g in the raw materials for preparing the adsorption material per gram.
Comparative example 1
This comparative example is a comparative example of example 1, and differs from example 1 in that: EPS-Fe 3+ as an adsorption material, and the preparation method comprises the following steps: and (3) the EPS prepared in the step (1) is not grafted on the gellan gum to form an EPS-gellan gum mixed material, and the EPS is directly added into ferric chloride solution, stirred, filtered and cleaned by distilled water to obtain the adsorption material.
Comparative example 2
This comparative example is a comparative example of example 1, and differs from example 1 only in that: the gellan gum is used as an adsorption material and the preparation method comprises the following steps: adding the gellan gum into deionized water, heating for dissolving, and cooling to form gel state. Gellan gum is not grafted with EPS and is not immersed in ferric chloride solution.
Comparative example 3
This comparative example is a comparative example of example 1, and differs from example 1 in that: gellan gum-Fe 3+ as adsorption material, and its preparation method comprises: adding 0.6g of high acyl gellan gum into 100mL of deionized water, continuously stirring for 15min, uniformly mixing, heating to 80 ℃ at a heating rate of 1 ℃/min, heating for dissolution, and cooling to room temperature to form gel state. Soaking gellan gum in ferric chloride solution with Fe 3+ concentration of 1.4mol/L for 20h, filtering, and cleaning with distilled water to obtain the adsorbent material.
Comparative example 4
This comparative example is a comparative example of example 1, and differs from example 1 in that: EPS prepared in the step (1) is used as an adsorption material.
Comparative example 5
This comparative example is a comparative example of example 1, and differs from example 1 only in that: in the step (2), the amount of EPS added was 9g. In the polymerization reaction solution, the concentration of EPS is 90g/L, and the mass ratio of EPS, gellan gum and initiator is 15:1:1.
The adsorption materials prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to phosphorus adsorption performance test, and the adsorption material prepared in example 1 was subjected to tests for applicable environment, recovery adsorption effect, and co-existence of anion influence. The test results are shown in tables 1 to 4.
The test method is as follows:
phosphorus adsorption performance: and adding an adsorption material into the phosphorus-containing wastewater serving as a treatment object to perform a phosphorus adsorption test, wherein the adsorption time is 6 hours, and the phosphorus content in the phosphorus-containing wastewater is tested before and after adsorption. The pH of the phosphorus wastewater was 7.
Standard for testing phosphorus content in wastewater: GB11893-89 is digested with potassium persulfate.
The application environment is as follows: taking phosphorus-containing wastewater as a treatment object, dividing the wastewater into 3 parts, marking each part as a sample 1, a sample 2 and a sample 3 respectively, adding trace concentrated hydrochloric acid and trace sodium hydroxide concentrated solutions into the sample 1 and the sample 3 respectively, adding 30g of the adsorption material prepared in the example 1 into the sample 1, the sample 2 and the sample 3 respectively, wherein the pH is 5, 7 and 9, respectively, the adsorption time is 6 hours, and testing the phosphorus content in the phosphorus-containing wastewater before and after adsorption.
Recovery adsorption effect: taking phosphorus-containing wastewater as a treatment object, dividing the phosphorus-containing wastewater into 10 parts averagely, adding the adsorption material prepared in the embodiment 1 into the phosphorus-containing wastewater, wherein the adding amount of the adsorption material is 25g/L, the adsorption time is 6 hours, and testing the phosphorus content in the phosphorus-containing wastewater before and after adsorption; recovering the adsorption material, immersing the adsorption material in a sodium hydroxide solution (pH of 11) for 6 hours, filtering and flushing to obtain a recovered adsorption material, adding the recovered adsorption material into another part of phosphorus-containing wastewater, and testing the phosphorus content in the phosphorus-containing wastewater before and after adsorption for 6 hours; repeating the adsorption and recovery operations, and testing the phosphorus content in the phosphorus-containing wastewater before and after adsorption.
TABLE 1 adsorption Performance test results
Table 2 results of applicable environmental test
TABLE 3 recovery adsorption Effect test results
As can be seen from tables 1, 3:
In the embodiment 1, the adsorption material 25g contains 17.75g EPS and 3.5g gellan gum, and compared with the comparative examples 1 and 2, the EPS, the gellan gum and the Fe 3+ have synergistic effect, so that the phosphorus adsorption performance of the adsorption material is further improved, and the recycling of the adsorption material is promoted.
As can be seen from Table 1, in example 5, the amount of gellan gum used was smaller (mass ratio of EPS to gellan gum 10:1) than in example 1, and a complete network structure could not be formed, resulting in a decrease in phosphorus removal rate.
As can be seen from table 2, the adsorption material prepared according to the technical scheme of the application is suitable for acidic, neutral and alkaline environments and has wide application prospects.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The preparation method of the adsorption material is characterized by comprising the following steps: the method comprises the steps of (1) polymerizing a sludge extracellular polymer and gellan gum, and then soaking the sludge extracellular polymer and gellan gum in an iron ion solution to obtain an adsorption material; the mass ratio of the sludge extracellular polymer to the gellan gum is (0.5-10): 1, a step of; in the polymerization reaction solution, the concentration of the sludge extracellular polymer is 10-60 g/L; the concentration of iron ions in the iron ion solution is 0.2-2.2 mol/L; the polymerization temperature is 75-95 ℃.
2. The method of claim 1, wherein the gellan gum is selected from one or both of a high acyl gellan gum and a low acyl gellan gum; and/or, the sludge extracellular polymeric substance is obtained by extracting sludge.
3. The method according to claim 2, wherein the sludge is municipal sludge and/or river and lake sediment;
and/or, the preparation method of the sludge extracellular polymer comprises the following steps: and (3) carrying out solid-liquid separation on the sludge to obtain a solid, extracting and purifying the solid to obtain the sludge extracellular polymer.
4. A method of preparation according to claim 3, characterized in that the extraction method is: adding phosphate buffer solution to make up the volume, and extracting by one or more of heating, ultrasonic and centrifuging.
5. The method according to claim 4, wherein the heating temperature is 75 to 85 ℃; and/or the ultrasonic frequency is 15-30 kHz; and/or the centrifugal rotating speed is 5500-6500 r/min; and/or the pH of the phosphate buffer solution is 5.5-8.5.
6. The method of manufacturing according to claim 1, comprising one or more of the following features:
the polymerization reaction also includes a reaction medium;
the polymerization reaction also includes an initiator;
The iron ion solution is selected from one or more of ferric chloride solution, ferric sulfate solution and ferric nitrate solution;
the soaking time is 18-28 h.
7. The method of manufacturing according to claim 6, comprising one or more of the following features:
The reaction medium is water;
the initiator is one or two selected from ammonium persulfate and potassium persulfate;
the mass ratio of the gellan gum to the initiator is (0.1-10): 1.
8. An adsorbent material prepared by the method of any one of claims 1 to 7.
9. Use of the adsorption material of claim 8 for adsorbing phosphorus in an aqueous environment.
10. A method for removing phosphorus from an aqueous environment, comprising the steps of: the adsorption material of claim 8 is added into a water body.
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