CN113368833A - Inorganic-organic flocculant and preparation method thereof - Google Patents
Inorganic-organic flocculant and preparation method thereof Download PDFInfo
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- CN113368833A CN113368833A CN202110806194.4A CN202110806194A CN113368833A CN 113368833 A CN113368833 A CN 113368833A CN 202110806194 A CN202110806194 A CN 202110806194A CN 113368833 A CN113368833 A CN 113368833A
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- xanthan gum
- microspheres
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- calcium alginate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 66
- 239000000230 xanthan gum Substances 0.000 claims abstract description 65
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 65
- 239000004005 microsphere Substances 0.000 claims abstract description 64
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 49
- 239000011575 calcium Substances 0.000 claims abstract description 49
- 238000004132 cross linking Methods 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 20
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 20
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 20
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 20
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 12
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 11
- 235000010413 sodium alginate Nutrition 0.000 claims description 11
- 239000000661 sodium alginate Substances 0.000 claims description 11
- 229940005550 sodium alginate Drugs 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 9
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 22
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 229960003638 dopamine Drugs 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000007281 self degradation Effects 0.000 abstract 1
- 235000010410 calcium alginate Nutrition 0.000 description 7
- 239000000648 calcium alginate Substances 0.000 description 7
- 229960002681 calcium alginate Drugs 0.000 description 7
- 239000008394 flocculating agent Substances 0.000 description 7
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- -1 polysaccharide calcium alginate Chemical class 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000000706 filtrate Substances 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
- 239000012535 impurity Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000012991 xanthate 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
-
- 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
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses an inorganic-organic flocculant and a preparation method thereof, which comprises the steps of preparing calcium alginate-xanthan gum microspheres and preparing SiO2The invention promotes the formation of mesopores by introducing xanthan gum, obviously increases the specific surface area of the microspheres, utilizes active groups adsorbed on organic macromolecules to generate a net catching effect through the bridging effect of the xanthan gum, enhances the adsorption capacity of the microspheres, and introduces SiO2The shell layer can protect the integrity of the structure of the microsphere and promote the whole microsphere systemMechanical strength of, Fe prevented from being compounded3+The interference causes the reduction of the heavy metal adsorption capacity, and Dopamine (DA) with the spontaneous polymerization capacity is adopted as a precursor, and in Fe3+Under the action of the catalyst, coordination and further oxidation crosslinking are carried out, and DA-Fe is formed in situ in the system3+Nano-aggregate of Fe3+The dispersion of (2) and a certain biological self-degradation capability.
Description
Technical Field
The invention relates to the technical field of flocculant preparation, and particularly relates to an inorganic-organic flocculant and a preparation method thereof.
Background
For heavy metal ions in wastewater, a common treatment method is to add chemical precipitation treatment before a flocculation treatment unit, or add treatment units such as ion exchange, adsorption, reverse osmosis, electrodialysis and the like after the flocculation unit. The metal trapping agent is a chemical agent which can coordinate or chelate with heavy metal ions and generate insoluble flocculent precipitates which are easy to filter and remove in a short time.
The flocculating agent has various varieties, from low molecules to high molecules, from single type to composite type, the general trend is to develop towards low price, practicability, non-toxicity and high efficiency, the prior heavy metal trapping agent mainly uses xanthates and dithiocarbamate Derivatives (DTC), the two agents cannot be biodegraded, residual monomers are toxic, and secondary pollution to the environment is inevitably caused by using a large amount of the flocculating agent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an inorganic-organic flocculant and a preparation method thereof, which solve the technical problems that the traditional flocculant has poor flocculation capability on heavy metals and can not be degraded by organisms.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an inorganic-organic flocculant comprises the following steps:
(1) preparing calcium alginate-xanthan gum microspheres: adding sodium alginate and xanthan gum into deionized water, stirring and mixing uniformly, and then dripping CaCl into the mixture2Carrying out crosslinking reaction on the solution, and after the reaction is finished, filtering, washing and drying a reaction product to obtain calcium alginate-xanthan gum microspheres;
(2) preparation of SiO2Cross-linked calcium alginate-xanthan gumMicrosphere preparation: stirring and mixing tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and HCl solution uniformly, then adding the calcium alginate-xanthan gum microspheres prepared in the step (1), mixing uniformly, transferring the mixture into an oven for reaction, and after the reaction is finished, washing and drying the reaction product to obtain SiO2Crosslinking calcium alginate-xanthan gum microspheres;
(3) preparing an inorganic-organic flocculant: adding the SiO prepared in the step (2) into a mixed solvent of ethanol and water2Crosslinking calcium alginate-xanthan gum microspheres, carrying out reflux reaction, standing and cooling to room temperature after the reaction is finished, adding dopamine hydrochloride, stirring uniformly, and then adding FeCl3And (5) oscillating the solution to obtain the inorganic-organic flocculant after oscillation is finished.
Preferably, in the step (1), sodium alginate, xanthan gum, deionized water and CaCl2The mass ratio of (A) to (B) is 1.5-3:1-1.5:100: 4-8.
Preferably, in the step (1), the stirring speed is 450-550rpm, the stirring time is 2-3h, and the crosslinking reaction time is 10-15 h.
Preferably, in the step (2), the mass ratio of tetraethyl orthosilicate to ethanol to deionized water to HCl to calcium alginate-xanthan gum microspheres is 1-1.5:1:2:0.002-0.01: 3-4.
Preferably, in the step (2), the reaction temperature is 60-70 ℃ and the reaction time is 3-6 h.
Preferably, in the step (3), the mass ratio of the ethanol to the water is 7:3 and SiO is2The mass ratio of the cross-linked calcium alginate-xanthan gum microspheres to the mixed solvent is 2-3: 100.
Preferably, in the step (3), the reflux reaction temperature is 75-85 ℃ and the reflux time is 2-3 h.
Preferably, in step (3), SiO2Crosslinked calcium alginate-xanthan gum microspheres, dopamine hydrochloride and FeCl3The mass ratio of (A) to (B) is 10-15:1: 0.06-0.1.
Preferably, in the step (3), the shaking time is 30-60 min.
The invention also provides the inorganic-organic flocculant obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides an inorganic-organic flocculant and a preparation method thereof, wherein natural polysaccharide calcium alginate and xanthan gum are crosslinked into a soft gum adsorption matrix, a layer of silica shells is formed on the surface of the matrix through a sol-gel process to ensure the stability of a spherical structure of the matrix, the matrix is grafted to a Dopamine (DA) macromolecular chain through crosslinking, and meanwhile, dopamine residues and Fe are grafted on the Dopamine (DA) macromolecular chain3+Coordination occurs and further oxidation crosslinking is carried out to form DA-Fe3+A nano-aggregate.
(2) The invention provides an inorganic-organic flocculant and a preparation method thereof, wherein hydroxyl in xanthan gum molecules and carboxyl in sodium alginate molecules are subjected to intermolecular condensation and are mutually connected in a hydrogen bond form, the introduction of xanthan gum promotes the formation of mesopores, the specific surface area of microspheres is remarkably increased, active groups adsorbed on organic macromolecules are utilized to generate a net catching effect through the bridging effect of the xanthan gum, the adsorption capacity of the microspheres is enhanced, and in addition, the introduced SiO generates a net catching effect2The shell layer can protect the integrity of the structure of the microsphere, improve the mechanical strength of the whole microsphere system and prevent the microsphere system from being compounded with Fe3+The interference results in a reduction in the ability to adsorb heavy metals.
(3) The invention provides an inorganic-organic flocculant and a preparation method thereof, wherein Dopamine (DA) with spontaneous polymerization capacity is adopted as a precursor in the presence of Fe3+Under the action of the catalyst, coordination and further oxidation crosslinking are carried out, and DA-Fe is formed in situ in the system3+Nano-aggregate of Fe3+Has a certain biodegradation capacity, Fe3+Can adsorb impurities and suspended particles, and gradually increase the adsorbed particles, Fe3+The flocculant has better flocculation performance, plays a role in synergy of cations, plays a role in bridging, and improves the capacity of adsorbing heavy metals of the flocculant.
Detailed Description
The present invention will be described in more detail with reference to specific preferred embodiments, but the present invention is not limited to the following embodiments.
It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention are commercially available.
Example 1
A preparation method of an inorganic-organic flocculant comprises the following steps:
(1) preparing calcium alginate-xanthan gum microspheres: adding 20g of sodium alginate and 10g of xanthan gum into 1000g of deionized water, then placing the mixture into an electric stirrer with 450rpm for stirring for 2 hours, and then dropwise adding 20mL of CaCl with the concentration of 20g/L2Carrying out crosslinking reaction on the solution for 12h, and after the reaction is finished, filtering, washing and drying a reaction product to obtain calcium alginate-xanthan gum microspheres;
(2) preparation of SiO2Crosslinking calcium alginate-xanthan gum microspheres: stirring and mixing 10g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of HCl solution and 1g/L of HCl solution uniformly, then adding 30g of calcium alginate-xanthan gum microspheres prepared in the step (1), mixing uniformly, transferring the mixture to a 65 ℃ oven for heat preservation reaction for 3 hours, and after the reaction is finished, washing and drying a reaction product to obtain SiO2Crosslinking calcium alginate-xanthan gum microspheres;
(3) preparing an inorganic-organic flocculant: to a mixed solvent of 700g of ethanol and 300g of water was added 30g of SiO prepared in step (2)2Cross-linked calcium alginate-xanthan gum microspheres are stirred under reflux at 80 ℃ for 2 hours, after the reaction is finished, the mixture is kept stand and cooled to room temperature, 3g of dopamine hydrochloride is added into the mixture, the mixture is stirred uniformly, and then 15mL of FeCl with the concentration of 10g/L is added into the mixture3And (5) oscillating the solution for 30min to obtain the inorganic-organic flocculant after oscillation is finished.
Example 2
A preparation method of an inorganic-organic flocculant comprises the following steps:
(1) preparing calcium alginate-xanthan gum microspheres: adding 15g of sodium alginate and 10g of xanthan gum into 1000g of deionized water, then placing the mixture into an electric stirrer with 450rpm for stirring for 2 hours, and then dropwise adding 20mL of 30g/L CaCl into the mixture2Carrying out crosslinking reaction on the solution for 10h, and after the reaction is finished, filtering, washing and drying a reaction product to obtain calcium alginate-xanthan gum microspheres;
(2) preparation of SiO2Crosslinking calcium alginate-xanthan gum microspheres: stirring and mixing 12g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of HCl solution and 1g/L of HCl solution uniformly, then adding 30g of calcium alginate-xanthan gum microspheres prepared in the step (1), mixing uniformly, transferring the mixture to a 65 ℃ oven for heat preservation reaction for 3 hours, and after the reaction is finished, washing and drying a reaction product to obtain SiO2Crosslinking calcium alginate-xanthan gum microspheres;
(3) preparing an inorganic-organic flocculant: to a mixed solvent of 700g of ethanol and 300g of water was added 20g of SiO prepared in step (2)2Cross-linked calcium alginate-xanthan gum microspheres are refluxed and stirred for 2 hours at 85 ℃, after the reaction is finished, the mixture is kept stand and cooled to room temperature, 2g of dopamine hydrochloride is added into the mixture, the mixture is stirred evenly, and then 15mL of FeCl with the concentration of 10g/L is added into the mixture3And oscillating the solution for 45min to obtain the inorganic-organic flocculant after oscillation is finished.
Example 3
A preparation method of an inorganic-organic flocculant comprises the following steps:
(1) preparing calcium alginate-xanthan gum microspheres: adding 18g of sodium alginate and 10g of xanthan gum into 1000g of deionized water, then placing the mixture into a 480rpm electric stirrer to stir for 2 hours, and then dropwise adding 20mL of 25g/L CaCl into the mixture2Carrying out crosslinking reaction on the solution for 12h, and after the reaction is finished, filtering, washing and drying a reaction product to obtain calcium alginate-xanthan gum microspheres;
(2) preparation of SiO2Crosslinking calcium alginate-xanthan gum microspheres: stirring and mixing 10g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of HCl solution and 1g/L of HCl solution uniformly, then adding 35g of calcium alginate-xanthan gum microspheres prepared in the step (1), mixing uniformly, transferring the mixture to a 65 ℃ oven for heat preservation reaction for 3 hours, and after the reaction is finished, washing and drying a reaction product to obtain SiO2Crosslinking calcium alginate-xanthan gum microspheres;
(3) preparing an inorganic-organic flocculant: 15g of SiO prepared in step (2) was added to a mixed solvent of 700g of ethanol and 300g of water2Cross-linked calcium alginate-xanthan gum microspheres, and refluxing and stirring at 85 deg.CStirring for 2h, standing and cooling to room temperature after the reaction is finished, adding 1g dopamine hydrochloride, stirring uniformly, and then adding 10mL of 10g/L FeCl3And oscillating the solution for 45min to obtain the inorganic-organic flocculant after oscillation is finished.
Example 4
A preparation method of an inorganic-organic flocculant comprises the following steps:
(1) preparing calcium alginate-xanthan gum microspheres: adding 20g of sodium alginate and 10g of xanthan gum into 1000g of deionized water, then placing the mixture into a 550rpm electric stirrer to stir for 3 hours, and then dropwise adding 20mL of 30g/L CaCl into the mixture2Carrying out crosslinking reaction on the solution for 10h, and after the reaction is finished, filtering, washing and drying a reaction product to obtain calcium alginate-xanthan gum microspheres;
(2) preparation of SiO2Crosslinking calcium alginate-xanthan gum microspheres: stirring and mixing 12g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of HCl solution and 1g/L of HCl solution uniformly, then adding 40g of calcium alginate-xanthan gum microspheres prepared in the step (1), mixing uniformly, transferring the mixture to a 65 ℃ oven for heat preservation reaction for 3 hours, and after the reaction is finished, washing and drying a reaction product to obtain SiO2Crosslinking calcium alginate-xanthan gum microspheres;
(3) preparing an inorganic-organic flocculant: to a mixed solvent of 700g of ethanol and 300g of water was added 30g of SiO prepared in step (2)2Cross-linked calcium alginate-xanthan gum microspheres are refluxed and stirred for 2 hours at 85 ℃, after the reaction is finished, the mixture is kept stand and cooled to room temperature, 2g of dopamine hydrochloride is added into the mixture, the mixture is stirred evenly, and 20mL of FeCl with the concentration of 10g/L is added into the mixture3And oscillating the solution for 45min to obtain the inorganic-organic flocculant after oscillation is finished.
Comparative example 1
A preparation method of a flocculating agent comprises the following steps:
(1) preparing calcium alginate microspheres: adding 20g of sodium alginate into 1000g of deionized water, then placing the mixture in an electric stirrer at 550rpm for stirring for 3h, and then dropwise adding 20mL of 30g/L CaCl2Solution and crosslinking reaction for 10h, and after the reaction is finished, carrying out reaction on the reaction productFiltering, washing and drying to obtain calcium alginate microspheres;
(2) preparation of SiO2Crosslinking calcium alginate microspheres: stirring and mixing 12g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of HCl solution and 1g/L of HCl solution uniformly, then adding 40g of calcium alginate microspheres prepared in the step (1), transferring the mixture to a 65 ℃ oven for heat preservation reaction for 3h after uniform mixing, and after the reaction is finished, washing and drying the reaction product to obtain SiO2Crosslinking calcium alginate microspheres;
(3) preparing a flocculating agent: to a mixed solvent of 700g of ethanol and 300g of water was added 30g of SiO prepared in step (2)2Crosslinking calcium alginate microspheres, refluxing and stirring at 85 ℃ for 2h, standing and cooling to room temperature after the reaction is finished, adding 2g dopamine hydrochloride, stirring uniformly, and then adding 20mL of 10g/L FeCl3And oscillating the solution for 45min to obtain the flocculant after oscillation is finished.
Comparative example 2
A preparation method of a flocculating agent comprises the following steps:
(1) preparing calcium alginate-xanthan gum microspheres: adding 18g of sodium alginate and 10g of xanthan gum into 1000g of deionized water, then placing the mixture into a 480rpm electric stirrer to stir for 2 hours, and then dropwise adding 20mL of 25g/L CaCl into the mixture2Carrying out crosslinking reaction on the solution for 12h, and after the reaction is finished, filtering, washing and drying a reaction product to obtain calcium alginate-xanthan gum microspheres;
(2) preparation of SiO2Crosslinking calcium alginate-xanthan gum microspheres: stirring and mixing 10g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of HCl solution and 1g/L of HCl solution uniformly, then adding 35g of calcium alginate-xanthan gum microspheres prepared in the step (1), mixing uniformly, transferring the mixture to a 65 ℃ oven for heat preservation reaction for 3 hours, and after the reaction is finished, washing and drying a reaction product to obtain SiO2Crosslinking calcium alginate-xanthan gum microspheres;
(3) preparing a flocculating agent: 15g of SiO prepared in step (2) was added to a mixed solvent of 700g of ethanol and 300g of water2Cross-linked calcium alginate-xanthan gum microspheres are stirred under reflux at 85 ℃ for 2 hours,after the reaction is finished, the mixture is kept stand and cooled to room temperature, and then 10mL of FeCl with the concentration of 10g/L is added into the mixture3And oscillating the solution for 45min to obtain the flocculant after oscillation is finished.
The flocculants prepared in examples 1-4 and comparative examples 1-2 were subjected to heavy metal adsorption experiments, and the specific experimental procedures were as follows:
1) selecting a 200ml polyethylene collecting bottle, then repeatedly leaching with ultrapure water to remove metal ions possibly existing, drying, and sealing for storage to prevent dust pollution;
2) collecting a sewage sample by using a polyethylene bottle, filtering the sewage sample by using a 0.45-micron mixed cellulose ester microporous filter membrane to remove insoluble particles in the sample, transferring the corresponding filtrate into the sample bottle, and adjusting the pH value to be below 2.0 by using dilute nitric acid to prevent the bottle wall from generating influence on the adsorption of heavy metal ions;
3) 0.01g of the flocculant prepared in the examples 1 to 4 and the comparative examples 1 to 2 is weighed respectively, 100mL of the treated sewage sample in the step (2) is added, the mixture is placed in a polyethylene centrifuge tube, a shaking table at 200rpm is used for oscillating reaction for 150min, then the supernatant is transferred to a clean centrifuge tube, the content of lead in the supernatant is measured by ICP-MS, the removal rate is calculated, and the experimental results are shown in the following table:
as can be seen from the table, the flocculant prepared in the embodiment has a good adsorption effect on heavy metals, the removal rate can reach more than 98%, xanthan gum is not added in comparative example 1, the adsorption capacity of the flocculant on heavy metals is obviously reduced, the introduction of xanthan gum is illustrated, the formation of mesopores can be promoted, the specific surface area of microspheres is increased, the adsorption of heavy metal ions is facilitated, dopamine is not added in comparative example 2, the adsorption capacity on heavy metals is reduced, the introduction of dopamine precursor is illustrated, and Fe is added3+Can be combined with itCoordination and further oxidation crosslinking occur, and DA-Fe is formed in situ in the system3+Nano-aggregate of Fe3+The adsorption capacity of the material is enhanced.
Finally, it is to be noted that: the above examples do not limit the invention in any way. It will be apparent to those skilled in the art that various modifications and improvements can be made to the present invention. Accordingly, any modification or improvement made without departing from the spirit of the present invention is within the scope of the claimed invention.
Claims (10)
1. The preparation method of the inorganic-organic flocculant is characterized by comprising the following steps:
(1) preparing calcium alginate-xanthan gum microspheres: adding sodium alginate and xanthan gum into deionized water, stirring and mixing uniformly, and then dripping CaCl into the mixture2Carrying out crosslinking reaction on the solution, and after the reaction is finished, filtering, washing and drying a reaction product to obtain calcium alginate-xanthan gum microspheres;
(2) preparation of SiO2Crosslinking calcium alginate-xanthan gum microspheres: stirring and mixing tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and HCl solution uniformly, then adding the calcium alginate-xanthan gum microspheres prepared in the step (1), mixing uniformly, transferring the mixture into an oven for reaction, and after the reaction is finished, washing and drying the reaction product to obtain SiO2Crosslinking calcium alginate-xanthan gum microspheres;
(3) preparing an inorganic-organic flocculant: adding the SiO prepared in the step (2) into a mixed solvent of ethanol and water2Crosslinking calcium alginate-xanthan gum microspheres, carrying out reflux reaction, standing and cooling to room temperature after the reaction is finished, adding dopamine hydrochloride, stirring uniformly, and then adding FeCl3And (5) oscillating the solution to obtain the inorganic-organic flocculant after oscillation is finished.
2. The method for preparing an inorganic-organic flocculant according to claim 1, wherein in the step (1), sodium alginate, xanthan gum, deionized water and CaCl2The mass ratio of (A) to (B) is 1.5-3:1-1.5:100: 4-8.
3. The method for preparing an inorganic-organic flocculant according to claim 1, wherein in the step (1), the stirring speed is 450-550rpm, the stirring time is 2-3h, and the crosslinking reaction time is 10-15 h.
4. The preparation method of the inorganic-organic flocculant according to claim 1, wherein in the step (2), the mass ratio of tetraethyl orthosilicate to ethanol to deionized water to HCl to calcium alginate-xanthan gum microspheres is 1-1.5:1:2:0.002-0.01: 3-4.
5. The method for preparing an inorganic-organic flocculant according to claim 1, wherein the reaction temperature in the step (2) is 60 to 70 ℃ and the reaction time is 3 to 6 hours.
6. The method for preparing an inorganic-organic flocculant according to claim 1, wherein in the step (3), the mass ratio of ethanol to water is 7:3, SiO2The mass ratio of the cross-linked calcium alginate-xanthan gum microspheres to the mixed solvent is 2-3: 100.
7. The method for preparing an inorganic-organic flocculant according to claim 1, wherein in the step (3), the reflux reaction temperature is 75 to 85 ℃ and the reflux time is 2 to 3 hours.
8. The method for preparing an inorganic-organic flocculant according to claim 1, wherein in the step (3), SiO is used2Crosslinked calcium alginate-xanthan gum microspheres, dopamine hydrochloride and FeCl3The mass ratio of (A) to (B) is 10-15:1: 0.06-0.1.
9. The method for preparing an inorganic-organic flocculant according to claim 1, wherein in the step (3), the shaking time is 30 to 60 min.
10. An inorganic-organic flocculant obtained by the production process according to claims 1 to 9.
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