CN113368833B - Inorganic-organic flocculant and preparation method thereof - Google Patents
Inorganic-organic flocculant and preparation method thereof Download PDFInfo
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- CN113368833B CN113368833B CN202110806194.4A CN202110806194A CN113368833B CN 113368833 B CN113368833 B CN 113368833B CN 202110806194 A CN202110806194 A CN 202110806194A CN 113368833 B CN113368833 B CN 113368833B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004005 microsphere Substances 0.000 claims abstract description 69
- 239000000230 xanthan gum Substances 0.000 claims abstract description 65
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 65
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 65
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 18
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 22
- 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
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 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
- 238000001035 drying Methods 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 238000005406 washing 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
- 238000000034 method Methods 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 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
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 13
- 229960003638 dopamine Drugs 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 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
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000007281 self degradation Effects 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 23
- 235000010410 calcium alginate Nutrition 0.000 description 7
- 239000000648 calcium alginate Substances 0.000 description 7
- 229960002681 calcium alginate Drugs 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
- 238000009413 insulation Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 5
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008394 flocculating agent Substances 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
- 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
- 150000001875 compounds Chemical class 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
- 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
- 238000004321 preservation Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method 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
- 238000005303 weighing Methods 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an inorganic-organic flocculant and a preparation method thereof, comprising the steps of preparing calcium alginate-xanthan gum microsphere and SiO 2 The invention promotes the formation of mesopores by introducing xanthan gum, obviously increases the specific surface area of the microsphere by 3 steps of crosslinking calcium alginate-xanthan gum microsphere and preparing inorganic-organic flocculant, and utilizes active groups adsorbed on organic polymers to generate net capturing effect by self bridging effect, thereby enhancing the adsorption capacity of the microsphere and the introduced SiO 2 The shell layer can protect the structural integrity of the microsphere, improve the mechanical strength of the whole microsphere system and prevent the microsphere system from being compounded with Fe 3+ The heavy metal adsorption capacity is reduced due to interference, dopamine (DA) with spontaneous polymerization capacity is adopted as a precursor, and Fe is used as a catalyst 3+ Under the action of (a) to coordinate and further oxidize and crosslink, DA-Fe is formed in situ in the system 3+ Nano aggregate beneficial to Fe 3+ And simultaneously has certain biological self-degradation capability.
Description
Technical Field
The invention relates to the technical field of flocculant preparation, in particular to an inorganic-organic flocculant and a preparation method thereof.
Background
For heavy metal ions in wastewater, a common treatment method is to add a chemical precipitation treatment before a flocculation treatment unit or add a treatment unit 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 precipitate which is easy to filter and remove in a short time.
The flocculant has various varieties from low molecular weight to high molecular weight, and the general trend is to develop in the directions of low cost, practicability, non-toxicity and high efficiency from single type to compound type, and the heavy metal trapping agent which is used at present mainly comprises xanthates and dithiocarbamate Derivatives (DTCs), the two agents cannot be biodegraded, residual monomers are toxic, and a large amount of use tends to cause secondary pollution to the environment.
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 heavy metal flocculation capability and cannot be degraded by biology.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing an inorganic-organic flocculant, comprising the steps of:
(1) Preparing calcium alginate-xanthan gum microsphere: adding sodium alginate and xanthan gum into deionized water, stirring, mixing, and adding CaCl dropwise 2 Carrying out a crosslinking reaction on the solution, and after the reaction is finished, filtering, washing and drying the reaction product to obtain the calcium alginate-xanthan gum microsphere;
(2) Preparation of SiO 2 Crosslinked calcium alginate-xanthan gum microspheres: stirring tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and HCl solution, mixing uniformly, adding calcium alginate-xanthan gum microsphere prepared in the step (1), transferring to a baking oven for reaction after mixing uniformly, washing and drying a reaction product after the reaction is finished, and obtaining SiO 2 Crosslinked calcium alginate-xanthan gum microspheres;
(3) Preparation of inorganic-organic flocculant: adding the SiO prepared in the step (2) into a mixed solvent of ethanol and water 2 Crosslinking calcium alginate-xanthan gum microsphere, reflux reacting, standing and cooling to room temperature after the reaction is finished, and addingAdding dopamine hydrochloride, stirring uniformly, and then adding FeCl 3 And (3) oscillating the solution, and obtaining the inorganic-organic flocculant after the oscillation is finished.
Preferably, in step (1), sodium alginate, xanthan gum, deionized water and CaCl 2 The mass ratio of (2) 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 10-15h.
Preferably, in the step (2), the mass ratio of tetraethyl orthosilicate, ethanol, deionized water, HCl and calcium alginate-xanthan gum microsphere 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 3-6h.
Preferably, in the step (3), the mass ratio of ethanol to water is 7:3, siO 2 The mass ratio of the crosslinked calcium alginate-xanthan gum microsphere 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 2-3h.
Preferably, in step (3), siO 2 Crosslinked calcium alginate-xanthan gum microsphere, dopamine hydrochloride and FeCl 3 The mass ratio of (2) is 10-15:1:0.06-0.1.
Preferably, in the step (3), the shaking time is 30-60min.
The invention also provides an 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 shell is formed on the surface of the soft gum adsorption matrix through a sol-gel process to ensure the stability of a spherical structure of the soft gum adsorption matrix, the soft gum adsorption matrix is grafted onto a Dopamine (DA) macromolecular chain through crosslinking, and meanwhile, dopamine residues and Fe are grafted on the Dopamine (DA) macromolecular chain 3+ Coordinated and further oxidized cross-linked to form DA-Fe 3+ Nano-aggregates.
(2) The present invention provides an inorganic materialThe organic flocculant and the preparation method thereof, hydroxyl in xanthan gum molecules and carboxyl in sodium alginate molecules are subjected to intermolecular condensation, are connected with each other in a hydrogen bond mode, and the introduced xanthan gum promotes the formation of mesopores, so that the specific surface area of the microsphere is obviously increased, the active groups adsorbed on organic polymers are utilized to generate a net capturing effect through the self bridging effect, the adsorption capacity of the microsphere is enhanced, and in addition, the introduced SiO is improved 2 The shell layer can protect the structural integrity of the microsphere, improve the mechanical strength of the whole microsphere system and prevent the microsphere system from being compounded with Fe 3+ Interference results in a decrease 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 capability is adopted as a precursor, and Fe is used as a catalyst 3+ Under the action of (a) to coordinate and further oxidize and crosslink, DA-Fe is formed in situ in the system 3+ Nano aggregate beneficial to Fe 3+ At the same time, has a certain biological self-degradation capability, fe 3+ Can adsorb impurities and suspended particles, so that the adsorbed particles are gradually increased, fe 3+ The flocculant has good flocculation performance, plays a role in synergism of cations, plays a role in bridging, and improves the capability of the flocculant for adsorbing heavy metals.
Detailed Description
The present invention will be described in further detail with reference to the following preferred examples, but the present invention is not limited to the following examples.
Unless otherwise specified, the chemical reagents involved in the present invention are all commercially available.
Example 1
A method for preparing an inorganic-organic flocculant, comprising the steps of:
(1) Preparing calcium alginate-xanthan gum microsphere: to 1000g deionized water, 20g sodium alginate and 10g xanthan gum were added, followed by stirring in an electric stirrer at 450rpm for 2 hours, and then 20mL, 20g/L CaCl was added dropwise thereto 2 The solution is crosslinked for 12 hours, and after the reaction is finished, the reaction product is filtered, washed and dried to obtain the seaCalcium alginate-xanthan gum microspheres;
(2) Preparation of SiO 2 Crosslinked calcium alginate-xanthan gum microspheres: stirring and mixing 10g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of 1g/L of HCl solution uniformly, adding 30g of calcium alginate-xanthan gum microsphere prepared in the step (1) into the mixture, uniformly mixing, transferring the mixture to a 65 ℃ oven for thermal insulation reaction for 3 hours, washing and drying a reaction product after the reaction is finished, and obtaining SiO 2 Crosslinked calcium alginate-xanthan gum microspheres;
(3) Preparation of inorganic-organic flocculant: adding 30g of SiO prepared in the step (2) to a mixed solvent of 700g of ethanol and 300g of water 2 The crosslinked calcium alginate-xanthan gum microsphere is refluxed and stirred for 2 hours at 80 ℃, and after the reaction is finished, the mixture is stood and cooled to room temperature, 3g of dopamine hydrochloride is added into the mixture and stirred evenly, and then 15mL of FeCl with the concentration of 10g/L is added into the mixture 3 And (3) oscillating the solution for 30min, and obtaining the inorganic-organic flocculant after the oscillation is finished.
Example 2
A method for preparing an inorganic-organic flocculant, comprising the steps of:
(1) Preparing calcium alginate-xanthan gum microsphere: 15g sodium alginate and 10g xanthan gum were added to 1000g deionized water, followed by stirring in an electric stirrer at 450rpm for 2 hours, and then 20mL, 30g/L CaCl was added dropwise thereto 2 The solution is subjected to a crosslinking reaction for 10 hours, and after the reaction is finished, the reaction product is filtered, washed and dried to obtain the calcium alginate-xanthan gum microsphere;
(2) Preparation of SiO 2 Crosslinked calcium alginate-xanthan gum microspheres: stirring and mixing 12g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of 1g/L of HCl solution uniformly, adding 30g of calcium alginate-xanthan gum microsphere prepared in the step (1) into the mixture, uniformly mixing, transferring the mixture to a 65 ℃ oven for thermal insulation reaction for 3 hours, washing and drying a reaction product after the reaction is finished, and obtaining SiO 2 Crosslinked calcium alginate-xanthan gum microspheres;
(3) Preparation of inorganic-organic flocculant: adding 20g of SiO prepared in the step (2) into a mixed solvent of 700g of ethanol and 300g of water 2 The crosslinked calcium alginate-xanthan gum microsphere is refluxed and stirred for 2 hours at 85 ℃, and after the reaction is finished, the mixture is stood and cooled to room temperature, 2g of dopamine hydrochloride is added into the mixture and stirred evenly, and then 15mL of FeCl with the concentration of 10g/L is added into the mixture 3 And (5) oscillating the solution for 45min, and obtaining the inorganic-organic flocculant after the oscillation is finished.
Example 3
A method for preparing an inorganic-organic flocculant, comprising the steps of:
(1) Preparing calcium alginate-xanthan gum microsphere: to 1000g deionized water, 18g sodium alginate and 10g xanthan gum were added, followed by stirring in an electric stirrer at 480rpm for 2 hours, and then 20mL, 25g/L CaCl was added dropwise thereto 2 The solution is subjected to a crosslinking reaction for 12 hours, and after the reaction is finished, the reaction product is filtered, washed and dried to obtain the calcium alginate-xanthan gum microsphere;
(2) Preparation of SiO 2 Crosslinked calcium alginate-xanthan gum microspheres: stirring and mixing 10g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of 1g/L of HCl solution uniformly, adding 35g of calcium alginate-xanthan gum microsphere prepared in the step (1) into the mixture, uniformly mixing, transferring the mixture to a 65 ℃ oven for thermal insulation reaction for 3 hours, washing and drying a reaction product after the reaction is finished, and obtaining SiO 2 Crosslinked calcium alginate-xanthan gum microspheres;
(3) Preparation of inorganic-organic flocculant: 15g of SiO prepared in step (2) was added to a mixed solvent of 700g of ethanol and 300g of water 2 The crosslinked calcium alginate-xanthan gum microsphere is refluxed and stirred for 2 hours at 85 ℃, and is kept stand and cooled to room temperature after the reaction is finished, 1g of dopamine hydrochloride is added into the microsphere and stirred evenly, and then 10mL and 10g/L FeCl are added into the microsphere 3 And (5) oscillating the solution for 45min, and obtaining the inorganic-organic flocculant after the oscillation is finished.
Example 4
A method for preparing an inorganic-organic flocculant, comprising the steps of:
(1) Preparing calcium alginate-xanthan gum microsphere: to 1000g of deionized water, 20g of sodium alginate and 10g of xanthan gum were added, followed by stirring in an electric stirrer at 550rpm for 3 hours, and then 20m was added dropwise theretoL、30g/L CaCl 2 The solution is subjected to a crosslinking reaction for 10 hours, and after the reaction is finished, the reaction product is filtered, washed and dried to obtain the calcium alginate-xanthan gum microsphere;
(2) Preparation of SiO 2 Crosslinked calcium alginate-xanthan gum microspheres: stirring and mixing 12g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of 1g/L of HCl solution uniformly, adding 40g of calcium alginate-xanthan gum microsphere prepared in the step (1) into the mixture, uniformly mixing, transferring the mixture to a 65 ℃ oven for thermal insulation reaction for 3 hours, washing and drying a reaction product after the reaction is finished, and obtaining SiO 2 Crosslinked calcium alginate-xanthan gum microspheres;
(3) Preparation of inorganic-organic flocculant: adding 30g of SiO prepared in the step (2) to a mixed solvent of 700g of ethanol and 300g of water 2 The crosslinked calcium alginate-xanthan gum microsphere is refluxed and stirred for 2 hours at 85 ℃, and after the reaction is finished, the mixture is stood and cooled to room temperature, 2g of dopamine hydrochloride is added into the mixture and stirred evenly, and then 20mL of FeCl with the concentration of 10g/L is added into the mixture 3 And (5) oscillating the solution for 45min, and obtaining the inorganic-organic flocculant after the oscillation is finished.
Comparative example 1
A method for preparing a flocculant, comprising the steps of:
(1) Preparing calcium alginate microspheres: 20g sodium alginate was added to 1000g deionized water, followed by stirring in an electric stirrer at 550rpm for 3 hours, and then 20mL, 30g/L CaCl was added dropwise thereto 2 The solution is subjected to a crosslinking reaction for 10 hours, and after the reaction is finished, the reaction product is filtered, washed and dried to obtain calcium alginate microspheres;
(2) Preparation of SiO 2 Crosslinked calcium alginate microspheres: stirring and mixing 12g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of 1g/L of HCl solution uniformly, adding 40g of calcium alginate microspheres prepared in the step (1), transferring to a 65 ℃ oven for thermal insulation reaction for 3 hours after uniform mixing, and washing and drying a reaction product after the reaction is finished to obtain SiO 2 Crosslinked calcium alginate microspheres;
(3) Preparing a flocculating agent: adding into a mixed solvent of 700g of ethanol and 300g of water30g of SiO prepared in step (2) are introduced 2 The crosslinked calcium alginate microsphere is refluxed and stirred for 2 hours at 85 ℃, and after the reaction is finished, the mixture is stood and cooled to room temperature, 2g of dopamine hydrochloride is added into the mixture and stirred evenly, and then 20mL of FeCl with the concentration of 10g/L is added into the mixture 3 And (5) oscillating the solution for 45min, and obtaining the flocculant after the oscillation is finished.
Comparative example 2
A method for preparing a flocculant, comprising the steps of:
(1) Preparing calcium alginate-xanthan gum microsphere: to 1000g deionized water, 18g sodium alginate and 10g xanthan gum were added, followed by stirring in an electric stirrer at 480rpm for 2 hours, and then 20mL, 25g/L CaCl was added dropwise thereto 2 The solution is subjected to a crosslinking reaction for 12 hours, and after the reaction is finished, the reaction product is filtered, washed and dried to obtain the calcium alginate-xanthan gum microsphere;
(2) Preparation of SiO 2 Crosslinked calcium alginate-xanthan gum microspheres: stirring and mixing 10g of tetraethyl orthosilicate, 10g of absolute ethyl alcohol, 20g of deionized water, 0.5mL of 1g/L of HCl solution uniformly, adding 35g of calcium alginate-xanthan gum microsphere prepared in the step (1) into the mixture, uniformly mixing, transferring the mixture to a 65 ℃ oven for thermal insulation reaction for 3 hours, washing and drying a reaction product after the reaction is finished, and obtaining SiO 2 Crosslinked 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 water 2 The crosslinked calcium alginate-xanthan gum microsphere is refluxed and stirred for 2 hours at 85 ℃, and is kept stand and cooled to room temperature after the reaction is finished, and then 10mL and 10g/L FeCl are added into the mixture 3 And (5) oscillating the solution for 45min, and obtaining the flocculant after the oscillation is finished.
The flocculant prepared in examples 1-4 and comparative examples 1-2 was subjected to a heavy metal adsorption experiment, and the specific experimental procedure was as follows:
1) Selecting a 200ml polyethylene collecting bottle, then repeatedly eluting with ultrapure water to remove metal ions possibly existing, drying, and sealing for preservation to prevent dust pollution;
2) Collecting a sewage sample by using a polyethylene bottle, filtering the sewage sample by using a 0.45 mu m 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 so as to prevent the wall of the bottle from influencing the adsorption of heavy metal ions;
3) Weighing 0.01g of the flocculant prepared in the examples 1-4 and the flocculant prepared in the comparative examples 1-2 respectively, adding 100mL of the treated sewage sample in the step (2), placing the sewage sample in a polyethylene centrifuge tube, shaking the sewage sample on a shaking table at 200rpm for 150min, transferring the supernatant to a clean centrifuge tube, measuring the lead content in the supernatant by ICP-MS, and calculating the removal rate, wherein the experimental results are shown in the following table:
as can be seen from the table, the flocculant prepared in the embodiment has good adsorption effect on heavy metals, the removal rate can reach more than 98%, xanthan gum is not added in the comparative example 1, the adsorption capacity on the heavy metals is obviously reduced, the introduction of the xanthan gum can promote the formation of mesopores, the specific surface area of the microsphere is increased, the heavy metal ions are adsorbed, dopamine is not added in the comparative example 2, the adsorption capacity on the heavy metals is reduced, the introduction of a dopamine precursor is demonstrated, and Fe 3+ Can coordinate with the catalyst and further oxidize and crosslink with the catalyst to form DA-Fe in situ in the system 3+ Nano aggregate beneficial to Fe 3+ And enhances the adsorption capacity thereof.
Finally, it should be noted that: the above examples are not intended to limit the present invention in any way. Modifications and improvements will readily occur to those skilled in the art upon the basis of the present invention. Accordingly, any modification or improvement made without departing from the spirit of the invention is within the scope of the invention as claimed.
Claims (2)
1. A method for preparing an inorganic-organic flocculant, which is characterized by comprising the following steps:
(1) Preparing calcium alginate-xanthan gum microsphere: adding sodium alginate and xanthan gum into deionized water, stirring, mixing, and adding CaCl dropwise 2 Carrying out a crosslinking reaction on the solution, and after the reaction is finished, filtering, washing and drying the reaction product to obtain the calcium alginate-xanthan gum microsphere;
(2) Preparation of SiO 2 Crosslinked calcium alginate-xanthan gum microspheres: stirring tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and HCl solution, mixing uniformly, adding calcium alginate-xanthan gum microsphere prepared in the step (1), transferring to a baking oven for reaction after mixing uniformly, washing and drying a reaction product after the reaction is finished, and obtaining SiO 2 Crosslinked calcium alginate-xanthan gum microspheres;
(3) Preparation of inorganic-organic flocculant: adding the SiO prepared in the step (2) into a mixed solvent of ethanol and water 2 Crosslinking calcium alginate-xanthan gum microsphere, reflux reacting, standing and cooling to room temperature after the reaction, adding dopamine hydrochloride, stirring uniformly, and adding FeCl 3 Oscillating the solution to obtain an inorganic-organic flocculant after the oscillation is finished;
in the step (1), sodium alginate, xanthan gum, deionized water and CaCl 2 The mass ratio of (2) is 1.5-3:1-1.5:100:4-8;
in the step (1), the stirring speed is 450-550rpm, the stirring time is 2-3h, and the crosslinking reaction time is 10-15h;
in the step (2), the mass ratio of tetraethyl orthosilicate, ethanol, deionized water, HCl and calcium alginate-xanthan gum microspheres is 1-1.5:1:2:0.002-0.01:3-4;
in the step (2), the reaction temperature is 60-70 ℃ and the reaction time is 3-6h;
in the step (3), the mass ratio of ethanol to water is 7:3, siO 2 The mass ratio of the crosslinked calcium alginate-xanthan gum microsphere to the mixed solvent is 2-3:100;
in the step (3), the reflux reaction temperature is 75-85 ℃ and the reflux time is 2-3h;
in step (3), siO 2 Crosslinked calcium alginate-xanthan gum microsphere, dopamine hydrochloride and FeCl 3 The mass ratio of (2) is 10-15:1:0.06-0.1;
in the step (3), the oscillation time is 30-60min.
2. An inorganic-organic flocculant obtained by the production process according to claim 1.
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