CN117244519B - Composite porous Si@Al adsorbent prepared by utilizing electric flocculation precipitation waste, method and application thereof - Google Patents
Composite porous Si@Al adsorbent prepared by utilizing electric flocculation precipitation waste, method and application thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000005189 flocculation Methods 0.000 title claims abstract description 26
- 230000016615 flocculation Effects 0.000 title claims abstract description 26
- 238000001556 precipitation Methods 0.000 title claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 46
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 28
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 17
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000356 contaminant Substances 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 12
- 239000003242 anti bacterial agent Substances 0.000 abstract description 11
- 229940088710 antibiotic agent Drugs 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- -1 organic matters Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000004098 Tetracycline Substances 0.000 description 10
- 229960002180 tetracycline Drugs 0.000 description 10
- 229930101283 tetracycline Natural products 0.000 description 10
- 235000019364 tetracycline Nutrition 0.000 description 10
- 150000003522 tetracyclines Chemical class 0.000 description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
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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
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/30—Organic compounds
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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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the field of materials, and discloses a method for preparing a composite porous Si@Al adsorbent by utilizing electric flocculation precipitation waste, and an application thereof, wherein the method comprises the following steps: the raw materials adopt the precipitation waste generated in the electric flocculation water treatment process; adding chlorella liquid into the precipitated waste; illuminating and vibrating; filtering, grinding and sieving; mixing with sodium silicate; calcining 2h to obtain the composite porous Si@Al adsorbent. The preparation method is simple and easy to implement, and the adsorbent can adsorb various pollutants such as organic matters, antibiotics, heavy metals and the like at the same time, so that the problems of high raw material cost and difficult adsorption of the existing adsorbent are successfully solved; the adsorbent has the advantages of strong adsorption performance, short adsorption time, wide applicable pH range and high repeated use rate, and realizes waste recycling. The test result can provide reference for the preparation of the low-cost adsorption material, and can also provide a new thought for recycling the electric flocculation precipitation waste.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a composite porous Si@Al adsorbent prepared by utilizing electric flocculation precipitation waste, a method and application thereof.
Background
Antibiotics and heavy metals are widely applied to agriculture, industry, medical industry and the like, so that the pollution of the antibiotics and the heavy metals in the environment, especially the water environment, is caused, and the fluidity and the solubility characteristics of the antibiotics and the heavy metals are further aggravated. Up to now, water pollution has become a considerable environmental concern.
The method for simultaneously removing the antibiotics and the heavy metals mainly comprises an adsorption method and a membrane separation method, and compared with the adsorption method, the adsorption method is a method for efficiently and simultaneously removing the antibiotics and the heavy metals due to low cost, simple operation and high removal rate. The adsorption materials commonly used in adsorption methods generally include carbon-based materials, metal-organic frameworks, mineral materials, mesoporous materials, and the like. Among them, metal-related materials perform well, but are generally expensive; the performance of minerals and carbon-based raw materials is limited, the removal effect of certain pollutants is poor, performance improvement is usually required to improve the efficiency, most of the current technologies pay attention to modified materials, however, various chemical agents are usually required to be added in the modification process for soaking or pickling, and even strong acid, strong alkali, heavy metal solution and the like are used for modification, so that the operation can greatly increase the cost, and a great deal of toxic and harmful waste liquid is worried about.
Therefore, the invention prepares the composite porous Si@Al adsorbent by using precipitated waste generated after the electric flocculation water treatment, doping a small amount of sodium silicate powder and simply calcining at 200 ℃. The preparation process has the advantages of low cost of raw materials, no use of toxic and harmful chemical substances, no generation of waste liquid, simple steps, great time saving and economic cost, environmental friendliness, excellent performance and wide adaptability, and can simultaneously remove organic matters, antibiotics and heavy metals in sewage.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for preparing a composite porous Si@Al adsorbent by utilizing electric flocculation precipitation waste, and application thereof.
The technical scheme adopted for solving the technical problems is as follows:
a method for preparing a composite porous Si@Al adsorbent by utilizing electroflocculation precipitation waste comprises the following steps:
(1) The raw materials adopt the precipitation waste generated in the electric flocculation water treatment process;
(2) Adding chlorella concentrate into the precipitate waste, wherein the final mass concentration of the chlorella concentrate is 0.5%, and placing the mixture in an illumination incubator at 26 ℃ for 3500lx illumination for 2 hours; simultaneously, vibrating the mixed solution at 120 rpm;
wherein the chlorella concentrate is a solid substance formed by filtering chlorella liquid, and polyethylene glycol is added for soaking for 10min, and the solid substance is: the mass of the polyethylene glycol is 1:1;
meanwhile, the algae cells are uniformly distributed on the colloid network structure, ca and Mg plasmas in the water body are easily combined to the surface on the surfaces of the microalgae cells, and 'hole points' are formed in the subsequent calcination.
(3) Filtering the mixed solution after shaking in the step (2), naturally air-drying the precipitate or drying the precipitate at 60 ℃, grinding the precipitate, and sieving the precipitate with a 60-mesh sieve to obtain uniform precipitate powder;
(4) Mixing the precipitate powder obtained in the step (3) with sodium silicate in a powder-powder mixing manner to obtain a mixture;
(5) Calcining the mixture in the step (4) for 2 hours at the temperature of 200 ℃ to obtain the composite porous Si@Al adsorbent.
Further, the precipitated waste in the step (1) is generated by industrial hydropower flocculation to remove silicon, and the initial concentration of the silicon is 10-60mg/L; the anode plate is an aluminum (Al) electrode and the cathode plate is a stainless steel electrode when the silicon is removed by electric flocculation;
the electric flocculation uses a direct current power supply, and the current density is 3.2mA/cm 2 The distance between the polar plates is 0.5cm, the water inflow rate is 0.25L/min, and the hydraulic retention time is 10s.
Moreover, unlike chemical substances having a crystal structure, the precipitate is Al which slowly separates out under the action of a weak electric field 3+ The polymer has good uniformity and dispersibility, huge specific surface area and more active sites with thin and interweaved reticular colloid formed by chemical bonds, such as O, H, si.
Further, the mixing of the precipitate powder in step (4) with sodium silicate is performed in air, and the addition of liquid affects the performance of the adsorbent.
The sodium silicate forms a 'cauliflower-shaped' composite hole with surrounding sediment during calcination, so that the specific surface area and the porosity of the adsorbent are further improved.
Further, the precipitate powder in step (4): the mass ratio of the sodium silicate is 1:1 to 6:1.
the composite porous Si@Al adsorbent prepared by the method is prepared.
The application method of the composite porous Si@Al adsorbent comprises the following steps:
and (3) weighing the composite porous Si@Al adsorbent, and directly putting the composite porous Si@Al adsorbent into a water body for adsorption operation.
The regeneration method of the composite porous Si@Al adsorbent comprises the following steps:
the regeneration method of the composite porous Si@Al adsorbent after use is solvent regeneration or calcination regeneration.
The use of a composite porous si@al adsorbent as described above for the simultaneous adsorption of a plurality of contaminants.
Further, the plurality of contaminants include organics, antibiotics, heavy metals.
The invention has the advantages and positive effects that:
1. the adsorbent of the invention does not need to be soaked or reacted by toxic and harmful chemical substances or washed by a large amount of water in the preparation process, so that toxic and harmful waste liquid is not generated. The chemical reagent used in the preparation process is only a small amount of sodium silicate, and the chemical reagent is directly mixed with powder, so that no waste liquid or secondary pollutant is generated, and the environmental ecological effect is better.
2. The preparation method of the invention has simple and easy preparation process and low cost. The adsorbent uses industrial waste as raw materials, and expensive heavy metals, chemicals and other expensive chemical substances are not used in the preparation process, so that the material cost is low. The calcination condition in the preparation process is 200 ℃ for 2 hours, and the aim can be achieved, which is lower than the temperature (450-800 ℃) and the treatment time (soaking and calcination are approximately 50 hours) commonly used in the prior art, so the energy consumption is low, and the time cost is low.
3. The adsorbent of the present invention is excellent in effect. The adsorbent has good adsorption performance on various pollutants with different properties (organic matters, antibiotics, heavy metals and the like); the adsorbent has short adsorption time (10-30 min) which is lower than a plurality of hours in the prior art; the adsorbent has high adsorption efficiency, wide applicable pH range (2.5-10) and high repeated use rate.
4. The adsorbent dissolves only a small amount of Al in the use process 3+ And silicate, can not dissolve out poisonous and harmful substances or ions such as heavy metal, etc., therefore, the adsorbent is safer and more effective in use.
5. The preparation method of the adsorbent disclosed by the invention uses waste to treat waste, does not generate secondary pollution, can provide a treatment route of changing waste into valuable, is green and efficient for water treatment, and accords with the green development concept.
Drawings
FIG. 1 is a graph showing the adsorption performance of adsorbents produced by different mass ratios of precipitated waste powder to sodium silicate in example 1 of the present invention;
FIG. 2 is a graph showing the adsorption performance of adsorbents produced at different muffle temperatures in example 1 of the present invention;
FIG. 3 is a graph showing the adsorption performance of the adsorbents prepared under different mixing conditions in example 1 of the present invention;
FIG. 4 is an XRD pattern of the adsorbent of example 1 of the present invention; wherein A is XRD pattern of Si@Al adsorbent, and B is XRD pattern of electric flocculation precipitation waste raw material;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the microstructure of the adsorbent of example 1 of the present invention;
FIG. 6 is a graph showing the adsorption effect of Si@Al adsorbents of different mass concentrations on methylene blue in example 2 of the present invention;
FIG. 7 is a graph showing the adsorption capacity of the adsorbent of example 2 of the present invention for methylene blue at various initial concentrations over time;
FIG. 8 is a graph showing the effect of Si@Al adsorbent in example 2 of the present invention on methylene blue adsorption at different pH values;
FIG. 9 is a graph showing the recycling of Si@Al adsorbent to methylene blue in example 2 of the present invention;
FIG. 10 is a graph showing the adsorption capacity of Si@Al adsorbent for tetracycline over time in example 3 of the present invention;
FIG. 11 is a graph showing the effect of Si@Al adsorbent in example 3 of the present invention on adsorption of tetracycline at different temperatures;
FIG. 12 shows the weight of the Si@Al adsorbent to heavy metal Cd in example 3 of the invention 2+ A plot of adsorption capacity over time;
FIG. 13 shows the comparison of Cd with Si@Al adsorbent in example 3 of the present invention at different temperatures 2+ Adsorption effect graph of (2).
Detailed Description
The invention will now be further illustrated by reference to the following examples, which are intended to be illustrative, not limiting, and are not intended to limit the scope of the invention.
The various experimental operations involved in the specific embodiments are conventional in the art, and are not specifically noted herein, and may be implemented by those skilled in the art with reference to various general specifications, technical literature or related specifications, manuals, etc. before the filing date of the present invention.
A method for preparing a composite porous Si@Al adsorbent by utilizing electroflocculation precipitation waste comprises the following steps:
(1) The raw materials adopt the precipitation waste generated in the electric flocculation water treatment process;
(2) Adding chlorella concentrate into the precipitate waste, wherein the final mass concentration of the chlorella concentrate is 0.5%, and placing the mixture in an illumination incubator at 26 ℃ for 3500lx illumination for 2 hours; simultaneously, vibrating the mixed solution at 120 rpm;
wherein the chlorella concentrate is a solid substance formed by filtering chlorella liquid, and polyethylene glycol is added for soaking for 10min, and the solid substance is: the mass of the polyethylene glycol is 1:1;
meanwhile, the algae cells are uniformly distributed on the colloid network structure, ca and Mg plasmas in the water body are easily combined to the surface on the surfaces of the microalgae cells, and 'hole points' are formed in the subsequent calcination.
(3) Filtering the mixed solution after shaking in the step (2), naturally air-drying the precipitate or drying the precipitate at 60 ℃, grinding the precipitate, and sieving the precipitate with a 60-mesh sieve to obtain uniform precipitate powder;
(4) Mixing the precipitate powder obtained in the step (3) with sodium silicate in a powder-powder mixing manner to obtain a mixture;
(5) Calcining the mixture in the step (4) for 2 hours at the temperature of 200 ℃ to obtain the composite porous Si@Al adsorbent.
Preferably, the precipitated waste in the step (1) is generated by industrial hydropower flocculation to remove silicon, and the initial concentration of the silicon is 10-60mg/L; the anode plate is an aluminum (Al) electrode and the cathode plate is a stainless steel electrode when the silicon is removed by electric flocculation;
the electric flocculation uses a direct current power supply, and the current density is 3.2mA/cm 2 The distance between the polar plates is 0.5cm, the water inflow rate is 0.25L/min, and the hydraulic retention time is 10s.
Moreover, unlike chemical substances having a crystal structure, the precipitate is Al which slowly separates out under the action of a weak electric field 3+ The polymer has good uniformity and dispersibility, huge specific surface area and more active sites with thin and interweaved reticular colloid formed by chemical bonds, such as O, H, si.
Preferably, the mixing of the precipitate powder in step (4) with sodium silicate is performed in air, and the addition of liquid affects the performance of the adsorbent.
The sodium silicate forms a 'cauliflower-shaped' composite hole with surrounding sediment during calcination, so that the specific surface area and the porosity of the adsorbent are further improved.
Preferably, the precipitate powder in step (4): the mass ratio of the sodium silicate is 1:1 to 6:1.
the composite porous Si@Al adsorbent prepared by the method is prepared.
The application method of the composite porous Si@Al adsorbent comprises the following steps:
and (3) weighing the composite porous Si@Al adsorbent, and directly putting the composite porous Si@Al adsorbent into a water body for adsorption operation.
The regeneration method of the composite porous Si@Al adsorbent comprises the following steps:
the regeneration method of the composite porous Si@Al adsorbent after use is solvent regeneration or calcination regeneration.
The use of a composite porous si@al adsorbent as described above for the simultaneous adsorption of a plurality of contaminants.
Preferably, the plurality of contaminants includes organics, antibiotics, heavy metals.
Specifically, the related preparation and detection are as follows:
example 1: preparation and characterization of Si@Al adsorbent under different conditions
Weighing naturally air-dried electric flocculation silicon removal sediment, wherein the sediment waste is generated by removing silicon through industrial hydropower flocculation, and the initial concentration of the silicon is 10-60mg/L; the anode plate is an aluminum (Al) electrode and the cathode plate is a stainless steel electrode when the silicon is removed by electric flocculation; the electric flocculation uses a direct current power supply, and the current density is 3.2mA/cm 2 The distance between the polar plates is 0.5cm, the water inflow rate is 0.25L/min, and the hydraulic retention time is 10s. Adding chlorella concentrate with the final mass concentration of 0.5% into the precipitate waste, and placing the mixture into an illumination incubator for illumination at 26 ℃ and 3500lx for 2 hours; simultaneously, vibrating the mixed solution at 120 rpm; the chlorella concentrate is a solid substance formed by filtering chlorella liquid, and polyethylene glycol is added for soaking for 10min, wherein the solid substance is: the mass of the polyethylene glycol is 1:1.
Filtering the mixed solution after oscillation, naturally air-drying the precipitate or drying the precipitate at 60 ℃, grinding the precipitate, and sieving the precipitate with a 60-mesh sieve to obtain uniform precipitate powder; the mass ratio of the dried precipitated waste powder to the sodium silicate is respectively 0.5:1, 1:1, 4:1, 6:1, 10:1 and 20:1, and the mixing conditions are set as follows: mixing the dry powders, adding water, ethanol, and Tween 80. Placing the materials in a crucible uniformly, setting the muffle furnace temperature to be 200, 300, 400, 500 and 700 ℃, calcining for 2.0h, and naturally cooling. Adsorbents under different conditions were prepared.
As can be seen from fig. 1 to 3, the si@al adsorbents prepared under different conditions have a certain adsorption performance, but the adsorption performance of the adsorbents prepared under different conditions is different, and as a whole, when the precipitate powder: the mass ratio of the sodium silicate is 4:1, the temperature is 200 ℃, and the adsorption performance of the adsorbent prepared by mixing the powder is best. The microscopic morphology of the si@al adsorbent was characterized by Scanning Electron Microscopy (SEM), the results are shown in fig. 5. The figure shows that the adsorbent has uniform flower shape, uniform particle size, distinct layers and loose and porous performance after calcination at 200 ℃, which indicates that the obvious porous medium adsorbent appearance is formed. FIG. 4 is an XRD pattern showing that neither the electroflocculation desilication precipitation waste nor the Si@Al adsorbent formed after calcination has distinct characteristic diffraction peaks, which indicates that the material exhibits an amorphous structure inside.
Example 2: preparation of Si@Al adsorbent, and adsorption effect and recycling of Si@Al adsorbent on methylene blue
The Si@Al adsorbent was prepared as in example 1, wherein the mass ratio of precipitate to sodium silicate was 4: and 1, uniformly mixing the materials in an air medium in a powder-powder mixing mode, calcining for 2.0h at the muffle temperature of 200 ℃, and naturally cooling. The adsorbents with different mass concentrations (2, 4, 6, 8g/L and 10 g/L) were added to 10mL of a solution containing methylene blue, and the concentration of the methylene blue was measured by spectrophotometry in a shaking box at 25℃and at 100rpm for 30 min.
As can be seen from FIGS. 6 and 7, when the amount of the adsorbent is 4g/L, the removal rate of methylene blue is as high as 90.77% at 30min, and the removal rate can be increased by 94.27% by continuing to increase the amount of the adsorbent, and if the adsorption time is increased to 60min, the removal rate can be increased to 99.2%. As shown in fig. 8, the removal rate of the adsorbent at different pH values can be seen to have a good removal effect in the pH value range of 4 to 10, and the change of the pH value hardly affects the removal rate (the change is not significant p > 0.05). As shown in fig. 9, the removal rate was reduced by about 6% after 5 times of use, and the recycling rate was high, in view of the influence of the recycling times.
Example 3: preparation of Si@Al adsorbent, adsorption effect of Si@Al adsorbent on tetracycline and heavy metal and recycling
The Si@Al adsorbent was prepared as in example 1, wherein the mass ratio of precipitate to sodium silicate was 4: and 1, uniformly mixing the materials in an air medium in a powder-powder mixing mode, calcining for 2.0h at the muffle temperature of 200 ℃, and naturally cooling. Adding adsorbent with different mass concentrations to 10mL containing tetracycline and Cd 2+ In a shaking box at 25 ℃, shaking for 30min at 100rpm, and determining the concentration of the tetracycline by utilizing a high performance liquid chromatography-mass spectrometry/mass spectrometry combined technology.
As can be seen from FIGS. 10 and 11, when the amount of the adsorbent was increased from 0mg/5mL to 0.01mg/5mL, the removal rate of tetracycline increased to 80.93%, and when the reaction time was 10min, the removal rate of tetracycline reached 97.85%, which indicates that Si@Al adsorbed tetracycline very rapidly and adsorption equilibrium was reached in 10 min. The effect of different temperatures on tetracycline removal was not apparent. As is clear from fig. 12 and 13, the removal rate after 5 times of use is reduced by about 8% and the recycling rate is high, from the influence of the recycling times. When the amount of the adsorbent is increased from 0mg/10mL to 0.04mg/10mL, the Cd removal rate is increased to 96.44%; the influence of different pH values on the tetracycline removal rate is not obvious; from the influence of the recycling times, the removal rate is reduced by about 3% after the recycling is performed for 5 times, and the recycling rate is high.
Example 4: comparison of sodium silicate and calcium hydroxide added in preparation of Si@Al adsorbent
The preparation method of the Si@Al adsorbent is as in example 1, wherein the precipitate and sodium silicate or calcium hydroxide are mixed in an air medium in a powder-powder mixing mode, and the mixing mass ratio is 4:1, calcining for 2.0h at the muffle temperature of 200 ℃ and naturally cooling. The adsorbent with the mass concentration of 6.0g/L is added into 10mL of solution containing different methylene blue concentrations (100, 300 and 500 mg/L), and the mixture is vibrated for 30min at 100rpm in a vibrating box at 25 ℃ to determine the concentration of the methylene blue by utilizing a spectrophotometry.
As can be seen from Table 1, the adsorption performance of the adsorbent prepared by doping sodium silicate is significantly better than that of the adsorbent prepared by doping calcium hydroxide, and particularly, at a higher initial concentration, the adsorption capacity of the adsorbent prepared in the invention is higher, for example, when the initial methylene blue concentration is 500mg/L, the adsorption capacity of the adsorbent prepared by mixing with sodium silicate and calcining after 30min of adsorption is 81.93mg/g, and the adsorption capacity of the adsorbent prepared by doping with calcium hydroxide and calcining is only 54.64mg/g. From the viewpoint of the equilibrium time of adsorption, the time for the adsorbent prepared by doping sodium silicate to reach equilibrium is shorter, the adsorbent prepared by mixing with sodium silicate only needs 5-15 min to reach the equilibrium of adsorption, and the time for the adsorbent prepared by mixing with calcium hydroxide to reach the equilibrium of adsorption is about 15-30 min. In conclusion, the adsorbent prepared by mixing with sodium silicate has more excellent performance.
TABLE 1 adsorption Capacity of sodium silicate and calcium hydroxide doped adsorbents for methylene blue (mg/g)
Meanwhile, as can be seen from comparative examples 1 and 4, the steps of mixing sodium silicate with precipitate powder and sodium silicate in a powder-powder mixing manner in the preparation method of the invention have a synergistic effect, and the relative performance of the prepared composite porous Si@Al adsorbent can be synergistically improved.
Example 5: si@Al adsorbents of the present invention are compared to adsorbents of other technologies
The preparation method of the Si@Al adsorbent is as in example 1, wherein the precipitate is mixed with sodium silicate or calcium hydroxide in an air medium, and the mixing mass ratio is 4:1, calcining for 2.0h at the muffle temperature of 200 ℃ and naturally cooling. The performance of the prepared adsorbent is compared with the adsorbent effect in the prior art in many ways.
Table 2 detailed comparisonThe removal effect of the adsorbent type, the preparation condition, the experimental condition and the target object in different researches is achieved. From the source of raw materials, the invention uses industrial solid waste, which not only has zero cost, but also can lighten the solid waste treatment pressure of enterprises and generate environmental effect. From the viewpoint of the preparation method, most of the existing adsorbents have long preparation flow, and various other compounds can be used, so that the cost of the medicament is greatly increased; the calcination temperature is usually high (450-800 ℃), even nitrogen environment or a large amount of water is used for flushing, so that resources are wasted and time cost is increased. In addition, the amount of the adsorbent used in the present study was 1 g.L -1 ～3g·L -1 Substantially identical to or lower than the amount of adsorbent used in other studies (0.5 g.L -1 ～5g·L -1 ). From the aspect of reaction time, the adsorbent realizes the adsorption process of antibiotics and heavy metal ions within 30min, and partial researches can be completed in a few hours, so that the adsorbent has the advantage of time and cost. From the aspect of the removal efficiency, the Si@Al adsorbent provided by the invention also has a good effect, and is obviously higher than the adsorption efficiency in part of researches. In summary, the adsorbent in the invention has remarkable advantages in various aspects and can be widely used for adsorbing and removing pollutants with different properties.
Table 2si@al adsorbents vs. adsorbents in other literature
Although embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments.
Claims (8)
1. A method for preparing a composite porous Si@Al adsorbent by utilizing electric flocculation precipitation waste is characterized by comprising the following steps of: the method comprises the following steps:
(1) The raw materials adopt the precipitation waste generated in the electric flocculation water treatment process;
(2) Adding chlorella concentrate into the precipitate waste, wherein the adding mass concentration of the chlorella concentrate is 0.5%, and placing the mixture in an illumination incubator at 26 ℃ under 3500lx illumination 2h; simultaneously, vibrating the mixed solution at 120 rpm;
wherein the chlorella concentrate is a solid substance formed by filtering chlorella liquid, and polyethylene glycol is added for soaking for 10min, and the solid substance is: the mass of the polyethylene glycol is 1:1;
(3) Filtering the mixed solution after shaking in the step (2), naturally air-drying the precipitate or drying the precipitate at 60 ℃, grinding the precipitate, and sieving the precipitate with a 60-mesh sieve to obtain uniform precipitate powder;
(4) Mixing the precipitate powder obtained in the step (3) with sodium silicate in a powder-powder mixing manner to obtain a mixture;
(5) Calcining the mixture in the step (4) at 200 ℃ for 2h to obtain a composite porous Si@Al adsorbent;
the precipitated waste in the step (1) is generated by industrial hydropower flocculation to remove silicon, and the initial concentration of the silicon is 10-60mg/L; the anode plate is an aluminum electrode and the cathode plate is a stainless steel electrode when the silicon is removed by electric flocculation;
the electric flocculation uses a direct current power supply, and the current density is 3.2mA/cm 2 The distance between the polar plates is 0.5 and cm, the water inflow rate is 0.25 and L/min, and the hydraulic retention time is 10 and s.
2. The method according to claim 1, characterized in that: the precipitate powder in step (4) is mixed with sodium silicate in air.
3. The method according to claim 1, characterized in that: precipitate powder in step (4): the mass ratio of the sodium silicate is 1:1 to 6:1.
4. a composite porous si@al adsorbent prepared by the method of any one of claims 1 to 3.
5. The method for using the composite porous Si@Al adsorbent according to claim 4, which is characterized by comprising the following steps: the method comprises the following steps:
and (3) weighing the composite porous Si@Al adsorbent, and directly putting the composite porous Si@Al adsorbent into a water body for adsorption operation.
6. The method for regenerating a composite porous si@al adsorbent according to claim 5, wherein: the method comprises the following steps:
the regeneration method of the composite porous Si@Al adsorbent after use is solvent regeneration or calcination regeneration.
7. Use of a composite porous si@al adsorbent according to claim 4 for the simultaneous adsorption of a plurality of contaminants.
8. The use according to claim 7, characterized in that: the plurality of contaminants includes organics or heavy metals.
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| JP2002059001A (en) * | 2000-08-11 | 2002-02-26 | Okutama Kogyo Co Ltd | Anion adsorbent |
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| CN106946434A (en) * | 2017-03-24 | 2017-07-14 | 合肥供水集团有限公司 | A kind of resource utilization method of water treatment plant's contained manganess aluminium iron sludge |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02164406A (en) * | 1988-12-19 | 1990-06-25 | Merusu Giken:Kk | Pretreatment of granular filter medium |
| JP2002059001A (en) * | 2000-08-11 | 2002-02-26 | Okutama Kogyo Co Ltd | Anion adsorbent |
| CN102294227A (en) * | 2011-06-30 | 2011-12-28 | 国家海洋局天津海水淡化与综合利用研究所 | Preparation method and application method of chlorella seawater purifying biological adsorbent |
| CN106946434A (en) * | 2017-03-24 | 2017-07-14 | 合肥供水集团有限公司 | A kind of resource utilization method of water treatment plant's contained manganess aluminium iron sludge |
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