CN114669270B - Composite material for efficiently passivating sediment phosphorus and preparation method thereof - Google Patents
Composite material for efficiently passivating sediment phosphorus and preparation method thereof Download PDFInfo
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- CN114669270B CN114669270B CN202210412604.1A CN202210412604A CN114669270B CN 114669270 B CN114669270 B CN 114669270B CN 202210412604 A CN202210412604 A CN 202210412604A CN 114669270 B CN114669270 B CN 114669270B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000011574 phosphorus Substances 0.000 title claims abstract description 105
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 105
- 239000013049 sediment Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 14
- 238000002161 passivation Methods 0.000 abstract description 7
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 238000005067 remediation Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000003643 water by type Substances 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 115
- 229910052791 calcium Inorganic materials 0.000 description 28
- 238000001179 sorption measurement Methods 0.000 description 27
- 238000002474 experimental method Methods 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- -1 aluminum-phosphorus compound Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229960000892 attapulgite Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000415 inactivating effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052625 palygorskite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000005422 algal bloom Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical class [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/004—Sludge detoxification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the technical field of water sediment remediation, and particularly relates to a composite material for efficiently passivating sediment phosphorus and a preparation method thereof. The preparation method of the composite material comprises the following steps: laCl is added 3 ·7H 2 O、CaCl 2 And AlCl 3 ·6H 2 Mixing O, adding the mixture into water, heating in a water bath under alkaline condition for coprecipitation and crystallization, collecting precipitate, and drying to obtain the precipitate phosphorus passivation material Ca/Al or La/Ca/Al composite material. The Ca/Al and La/Ca/Al composite material prepared by the method can adapt to a larger pH value range in eutrophic lakes, and can keep high sediment phosphorus passivation effect in acidic, neutral and alkaline lake waters. In addition, the phosphorus passivation of Ca/Al and La/Ca/Al is effective in both anaerobic and aerobic environments and can cope with a variety of redox environments that frequently vary in lakes.
Description
Technical Field
The invention belongs to the technical field of water sediment remediation, and particularly relates to a composite material for efficiently passivating sediment phosphorus and a preparation method thereof.
Background
Phosphorus (P) has proven to be a major limiting factor in most lakes and rivers, and its excessive input is likely to cause eutrophication of water bodies. In lakes with heavy endogenous loads, the sediment releases enough phosphorus to sustain a sustained burst of detrimental algal bloom even if the exogenous phosphorus input is completely cut off. Thus, inhibition of phosphorus release in sediments is one of the keys to long-term control of lake eutrophication after sustained reduction of exogenous phosphorus load.
Metal salts and phosphorus adsorbents for metal-based solid phase products are considered to be an effective method of deposit remediation. To date, many materials based on iron, calcium, aluminum and lanthanum groups have been widely used for lake recovery. Iron-based phosphorus adsorbents are more advantageous for use in aerobic conditions, since the reduction of iron-phosphorus complexes under anoxic conditions will result in a significant release of phosphate in the sediment to the overlying water. The performance of aluminum-based phosphorus inactivating agents such as aluminum sulfate, polyaluminum chloride and the like is not affected by oxidation-reduction conditions. However, under alkaline conditions, phosphate is desorbed from the aluminum-phosphorus compound due to competition between hydroxide and phosphate, and thus an increase in the pH of the overlying water will result in a decrease in its efficiency for inactivating phosphorus in the deposit of aluminum-based material. When the pH of the overlying water is greater than 8, the phosphorus inactivating agent of the aluminum-based material may be significantly degraded. Although lanthanum has high reactivity and selectivity to phosphate, its stability is affected by pH like aluminum-based materials, such as the commercial deposit phosphorus passivating agent lanthanum modified bentonite, whose adsorption capacity is also significantly reduced under alkaline conditions. Calcium-based materials such as calcium salt, calcium modified biochar and the like have higher inactivation performance on phosphorus in sediment under the condition of high pH value, but the pH value of overlying water is often further increased. It was reported that after adding 5% and 20% calcium silicate material to the sediment, the pH of the overlying water increased from 8.56 to 11.79 and 12.68, respectively. With Ca (OH) 2 The modified biochar dephosphorization process will result in an increase in the pH of the water to 11-12.CaO (CaO) 2 After correction of the sediment, the pH of the overlying water was increased from 7.1 to 11.38. Some natural mineral materials are rich in calciumElements such as magnesium and the like have phosphorus adsorption capacity, but the adsorption amount is often low. The adsorption capacity can be improved by modifying the aluminum, such as aluminum modified calcium-rich attapulgite, clay, calcite and zeolite. It was reported that aluminum modified heat-treated porous calcium-rich attapulgite (Al@TCAP) increased the maximum phosphorus adsorption capacity to 8.79mg/g, which is 2 times the adsorption capacity of the heat-treated porous calcium-rich attapulgite (TCAP) without aluminum modification. However, the modified natural mineral material still has a low phosphorus adsorption capacity, and a high heat treatment or a high acid-base treatment is often required, so that the material preparation cost increases.
The stability and safety of the phosphorus passivating agent are critical for the repair of eutrophic deposits. In eutrophic lakes, it is common to have a high pH due to the anaerobic environment of sediment-water interfaces driven by the microbial degradation of accumulated algae and the proliferation of algae. Therefore, the development of an environmentally friendly phosphorus passivating agent which can cope with frequent redox state transitions and a wide range of pH values in lakes is very important for the remediation of eutrophic lake sediments. In addition, the phosphorus passivating agent should be inexpensive, easy to prepare and use.
Disclosure of Invention
Aiming at the problems in the sediment phosphorus passivating agent in the prior art, the invention aims to provide a composite material for efficiently passivating sediment phosphorus and a preparation method thereof. The preparation method is low in cost and simple to operate, and the composite material prepared by the method has the following advantages: can be widely applied to the oxidation-reduction state and pH value change of lakes to efficiently control the release of sediment phosphorus, does not influence the pH value of water body, and can correct the pH value under acidic and alkaline conditions.
The conception of the invention is as follows: caCl is added with 2 And AlCl 3 ·6H 2 After mixing O or CaCl containing lanthanum 2 And AlCl 3 ·6H 2 Mixing O, adding the mixture into water, heating in a water bath under alkaline condition for coprecipitation and crystallization, collecting precipitate, and drying to obtain the precipitate phosphorus passivation material Ca/Al or La/Ca/Al composite material.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of a composite material for efficiently passivating sediment phosphorus comprises the following steps:
(1) Lanthanum chloride LaCl 3 ·7H 2 O, calcium chloride CaCl 2 And aluminum chloride AlCl 3 ·6H 2 O mixing; wherein the ratio of the mass of (lanthanum chloride+calcium chloride) to the mass of aluminum chloride is (0.8-1.2): 1, lanthanum chloride accounts for 0-5% of the total mass of (lanthanum chloride and calcium chloride);
preferably, the ratio of the mass of (lanthanum chloride+calcium chloride) to the mass of aluminum chloride is 1:1, a step of; preferably, lanthanum chloride comprises 5% of the sum of the (lanthanum chloride + calcium chloride) masses;
(2) Adding the mixture obtained in the step (1) into water for dissolution; wherein the ratio of the mixture to water is 1g: (5-10) mL;
(3) Adjusting the ph=9-10 of the solution obtained in step (2) with an inorganic alkaline solution; wherein the inorganic alkali solution can be NaOH solution, KOH solution and the like, preferably NaOH solution, and the concentration of the NaOH solution is 1 mol/L-5 mol/L; preferably, the method comprises the steps of firstly adjusting by using a NaOH solution with higher concentration, and then adjusting by using a NaOH solution with lower concentration;
(4) The solution with the pH value regulated is placed in a water bath condition of 50 ℃ to 60 ℃ for coprecipitation and crystallization for 12 to 24 hours; preferably, the mixture is subjected to coprecipitation and crystallization for 24 hours under the water bath condition of 60 ℃;
(5) Centrifuging to collect precipitate, drying, and grinding to obtain composite material (Ca/Al or La/Ca/Al); preferably, the precipitation drying temperature is 60-80 ℃.
The application of the composite material prepared by the method in passivating sediment phosphorus comprises the following specific steps: the Ca/Al or La/Ca/Al composite material is added to or coated on the deposit in a proportion of not less than 2% by dry weight of the deposit or not less than 0.75% by fresh weight of the deposit.
Compared with the prior art, the invention has the advantages and beneficial effects that:
the preparation method has the advantages of low cost of raw materials, simple preparation method and process, easy operation and good application prospect. The Ca/Al and La/Ca/Al composite material avoids the problem of pH rise caused by calcium-based materials, overcomes the defects of reduced adsorption capacity and obviously reduced phosphorus inactivation effect of aluminum-based (lanthanum-based) materials under the slightly alkaline condition, can effectively control the release of phosphorus in bottom mud, further reduces the concentration of phosphorus in overlying water, and has good control effect on the release of sediment phosphorus in eutrophic water under natural conditions. The Ca/Al and La/Ca/Al composite material prepared by the method has large adsorption capacity, can effectively and continuously control the release of phosphorus in eutrophic lake sediment, and effectively solves the problem that when the water quality is improved, the phosphorus in the sediment can be released upwards to cause secondary pollution caused by the water. The Ca/Al and La/Ca/Al composite material prepared by the method can adapt to a larger pH value range in eutrophic lakes, and can keep high sediment phosphorus passivation effect in acidic, neutral and alkaline lake waters. In addition, the phosphorus passivation of Ca/Al and La/Ca/Al is effective in both anaerobic and aerobic environments and can cope with a variety of redox environments that frequently vary in lakes. The preparation method of the Ca/Al and La/Ca/Al composite material is simple and feasible, has low cost, can be applied under wider physical and chemical conditions, can maintain the excellent phosphorus passivation capability, and is beneficial to practical popularization and application.
Drawings
FIG. 1 is a graph of the adsorption of Ca/Al and La/Ca/Al composites to phosphate in aqueous solutions at different pH conditions.
FIG. 2 is a graph showing the effect of Ca/Al and La/Ca/Al composites on pH of aqueous solutions;
in the figure, the ordinate is the final pH minus the initial pH divided by the initial pH.
FIG. 3 is a phosphorus adsorption isotherm of the original east lake sediment, 4% Ca/Al modified east lake sediment and 4% La/Ca/Al modified east lake sediment.
FIG. 4 is a graph of total phosphorus in water solubility of an original east lake sediment, a 2% Ca/Al modified east lake sediment, a 2% La/Ca/Al modified east lake sediment, a 4% Ca/Al modified east lake sediment, and a 4% La/Ca/Al modified east lake sediment over different pH conditions.
FIG. 5 is a graph of total phosphorus change in the water solubility of the original east lake sediment, 4% Ca/Al modified east lake sediment, and 4% La/Ca/Al modified east lake sediment under anaerobic and aerobic conditions, wherein: the graph A is under aerobic condition, and the graph B is under anaerobic condition.
FIG. 6 is a graph of pH change of an original east lake sediment, 4% Ca/Al modified east lake sediment, and 4% La/Ca/Al modified east lake sediment overlaid with water under anaerobic and aerobic conditions, wherein: the graph A is under aerobic condition, and the graph B is under anaerobic condition.
FIG. 7 is a graph showing the change in total phosphorus concentration of Ca/Al modified small southern lake sediment overlaid with water solubility under aerobic and anaerobic conditions.
FIG. 8 is a STEM-EDS diagram of Ca/Al and La/Ca/Al composites, where (A, B) is the STEM and EDS diagram of Ca/Al composites, respectively, and (C, D) is the STEM and EDS diagram of La/Ca/Al composites.
Detailed Description
The applicant makes further detailed description of the technical scheme of the present invention with reference to specific embodiments and drawings.
The raw material CaCl used in the examples 2 、AlCl 3 ·6H 2 O、LaCl 3 ·7H 2 O and the like are conventional commercial products.
It should be noted that: the simultaneous occurrence of M and Arabic numerals refers to the concentration unit of the solution, and the concentration unit is mol/L.
Example 1: caCl is added with 2 (5g) And AlCl 3 ·6H 2 O (5 g) was dissolved in 100mL of 60 ℃ deionized water in sequence, and then NaOH solution (5M and 1M) was slowly added to the above solution in sequence to adjust the pH of the solution to a stable pH of 9.0. The solution was then placed on a thermostatic water bath, co-precipitated and crystallized at 60 ℃ for 24 hours. Centrifuging to collect precipitate, drying in a blast drying oven at about 60deg.C to constant weight, and grinding to obtain Ca/Al composite material. Several 25mL of potassium dihydrogen phosphate aqueous solution with a phosphorus concentration (calculated as phosphorus element, the same applies below) of 70mg/L are taken, and the pH values are adjusted to be 4, 5, 6, 7, 8, 9, 10 and 11 respectively by using hydrochloric acid (1M) and NaOH (1M) solutions. After 0.01g of each Ca/Al composite material is respectively added into the potassium dihydrogen phosphate aqueous solutions with different pH values, the mixture is oscillated for 24 hours at a constant temperature of 25 ℃ at 150rpm, a proper amount of water sample is taken, filtered by a 0.45 mu m filter membrane, and the total dissolved phosphorus concentration (GB/T11893-1989) is measured by an ammonium molybdate spectrophotometry, and the final pH value of the solution is measured. Calculation of CaAdsorption amount of phosphorus by Al composite materialWherein C is a And C b Respectively the initial phosphorus concentration and the final phosphorus concentration) and the influence of the Ca/Al composite adsorption process on the pH value. The calculation result shows (figure 1) that the phosphorus adsorption capacity of the Ca/Al composite material is 23.86mg/g on average at the pH of 4-7 and reaches 75.45mg/g at the pH of 8-11. The Ca/Al composite material has high adsorption capacity under both acidic and alkaline water environment conditions, especially under alkaline conditions. From the final pH of the solution measured (FIG. 2), the Ca/Al composite had some effect on pH, the pH increased under acidic conditions, the pH decreased under alkaline conditions, and little effect under neutral conditions. The overall effect is shown as a correction of the deviation of the pH value of the water body from the neutral range.
Example 2: laCl is added 3 ·7H 2 O(0.25g)、CaCl 2 (4.75 g) and AlCl 3 ·6H 2 O (5 g) was dissolved in 100mL of 60 ℃ deionized water in sequence, and then NaOH (5M and 1M) solution was slowly added to the above solutions in sequence to achieve a stable pH of 9.0. The pH-adjusted solution was placed on a constant temperature water tank, co-precipitated and crystallized at 60℃for 24 hours. Centrifuging to collect precipitate, drying in a blast drying oven at 60deg.C to constant weight, and grinding to obtain La/Ca/Al composite material. Several 25mL of aqueous potassium dihydrogen phosphate solution with a phosphorus concentration of 70mg/L are taken, and the pH values are adjusted to be 4, 5, 6, 7, 8, 9, 10 and 11 respectively by using hydrochloric acid (1M) and NaOH (1M) solutions. 0.01g of La/Ca/Al composite material is respectively added into the potassium dihydrogen phosphate aqueous solution with different pH values, and then the mixture is vibrated for 24 hours at a constant temperature of 25 ℃ at 150 rpm. Filtering a proper amount of water sample with a 0.45 μm filter membrane, measuring the total concentration of soluble phosphorus (GB/T11893-1989) by adopting an ammonium molybdate spectrophotometry, measuring the final pH value of the solution, and calculating the adsorption amount of La/Ca/Al composite material on phosphorusWherein C is a And C b Respectively the initial phosphorus concentration and the final phosphorus concentration) and the effect of the adsorption process of the La/Ca/Al composite material on the pH valueAnd (5) sounding. The calculation result shows that (figure 1) the phosphorus adsorption capacity of the La/Ca/Al composite material is 29.02mg/g on average at the pH of 4-7 and 74.45mg/g at the pH of 8-11. The La/Ca/Al composite material has high adsorption capacity under both acidic and alkaline water environment conditions, especially under alkaline conditions. The adsorption capacity of the La/Ca/Al composite material is improved to a certain extent compared with that of the Ca/Al composite material under the acidic condition, and the adsorption capacity is equivalent under the alkaline condition. From the final pH value of the measured solution (figure 2), the La/Ca/Al composite material also plays a certain role in correcting the deviation of the pH value of the water body from the neutral range.
Example 3: collecting the deposition of the Donghu lake temple, naturally air-drying, grinding and sieving to obtain the original deposition of the Donghu lake for later use. 4g of the Ca/Al composite material in the example 1 and 4g of the La/Ca/Al composite material in the example 2 were added to 96g of dried sediment of the Dongfu Miao lake in a mass ratio (dry weight ratio) respectively, and the mixture was thoroughly mixed, ground and sieved (100 meshes) to obtain 4% of Ca/Al composite material modified Dongfu sediment and 4% of La/Ca/Al composite material modified Dongfu sediment. 0.20 g each of the original east lake sediment, 4% Ca/Al composite modified east lake sediment and 4% La/Ca/Al composite modified east lake sediment was added to a 50ml polyethylene tube, followed by 20ml of a series of high concentration phosphate solutions (phosphorus concentrations 1,2,4,10,20,50,80mg/L, respectively) having an initial pH of 7.0. Then, the polyethylene centrifuge tube was placed on a thermostatic shaker and shaken on a thermostatic shaker at 150rpm and 25℃for 24 hours to reach adsorption equilibrium. The phosphorus concentration in the balanced solution (i.e., the phosphorus equilibrium concentration) was measured according to the method described in example 1, and the phosphorus adsorption amount was calculatedWherein C is a And C b Respectively, initial phosphorus concentration and phosphorus equilibrium concentration), and the adsorption isotherms of the original east lake sediment, the east lake sediment modified by the 4% Ca/Al composite material and the east lake sediment modified by the 4% La/Ca/Al composite material are obtained by fitting with a Langmuir model (figure 3). Fitting results showed that the maximum phosphorus adsorption capacity of the original Donghu sediment was 1.09mg/g,4%The maximum phosphorus adsorption capacity of the Ca/Al composite modified east lake sediment was 1.99mg/g, and the maximum phosphorus adsorption capacity of the 4% La/Ca/Al composite modified east lake sediment was 2.21mg/g. The results show that the affinity of the east lake sediment corrected by the Ca/Al composite material and the La/Ca/Al composite material to phosphorus is obviously enhanced, and the maximum adsorption capacity is obviously increased.
Example 4: 2g of the Ca/Al composite material in the example 1 and 2g of the La/Ca/Al composite material in the example 2 are respectively added into the Dongfu Miao lake sediment with the dry weight of 98g, and the mixture is sufficiently mixed, ground and sieved (100 meshes) to respectively obtain the Dongfu sediment corrected by the 2 percent Ca/Al composite material and the Dongfu sediment corrected by the 2 percent La/Ca/Al composite material. Taking 5 grams of original east lake sediment, 2% Ca/Al composite modified east lake sediment and 2% La/Ca/Al composite modified east lake sediment, and placing into a 250ml conical flask containing 100ml deionized water. The pH of the sediment-water mixture was adjusted to stable 5.5, 7.5 and 9.5 with 1M HCl and 1M NaOH. The flask was then placed on a shaker (150 rpm,25 ℃) and shaken. The pH was adjusted to the set pH over 1,2,4, 8, 12, 24, 36, 48 and 72 hours and samples were taken to determine the total dissolved phosphorus concentration (DTP, mg/L) in the water and the effect of the addition of 2% Ca/Al and 2% La/Ca/Al composites on controlling the release of phosphorus from the east lake sediment was evaluated. The measurement showed that at ph=5.5 (fig. 4A), the total dissolved phosphorus concentration of the water coating on the original sediment group of the eastern lake increased continuously (from 0.064 to 0.207 mg/L) over the first 36 hours, then decreased and stabilized at 0.158mg/L, with an average value of 0.126mg/L over the whole period. The average total overburden water solubility phosphorus concentrations for the east lake sediment groups repaired with 2% Ca/Al composite and 2% La/Ca/Al composite were 0.072 and 0.054mg/L, respectively. Under acidic conditions, the addition of Ca/Al composite and La/Ca/Al composite significantly inhibited the release of phosphorus from the sediment, and the total phosphorus solubility of the overburden water of the repaired Dong lake sediment group was significantly lower than that of the original Dong lake sediment group. At ph=7.5 (fig. 4B), the total water-soluble phosphorus concentration of the top water of the eastern lake original sediment group increased from 0.153mg/L to 0.374mg/L, with an average value of 0.220mg/L throughout the experiment. The total phosphorus of the water solubility of the 2% Ca/Al composite and 2% La/Ca/Al composite repaired east lake sediment groups remained very low throughout the experiment with average values of 0.042 and 0.035mg/L, respectively. When the pH was adjusted to 9.5 (FIG. 4C), the phosphorus release in the original east lake sediment increased dramatically, and the total phosphorus concentration of the overlying water solubility reached a maximum concentration of 2.227mg/L at 1 h. Slowly decreasing to a minimum concentration of 0.931mg/L over time and then steadily increasing to 1.489mg/L, with an average value of 1.570mg/L throughout the experiment. Whereas the total phosphorus concentration of the overburden water solubility of the east lake sediment group modified with 2% Ca/Al composite and 2% La/Ca/Al composite was significantly lower than the original east lake sediment group, with average values of 0.159 and 0.123mg/L, respectively. These results demonstrate that the addition of 2% Ca/Al and 2% la/Ca/Al composites will facilitate the fixation of phosphorus in the sediment and significantly reduce the phosphorus concentration in the overlying water at different pH conditions.
Example 5: the dried original sediment of the temple lake of the Donghu, the 4% Ca/Al composite modified Donghu sediment and the 4% La/Ca/Al composite modified Donghu sediment in example 3 above were taken in 5g portions each and placed in 250ml conical flasks with 100ml deionized water. The pH of the sediment-water mixture was adjusted to stable 5.5, 7.5 and 9.5 with 1M HCl and 1M NaOH. The flask was then placed on a shaker (150 rpm,25 ℃) and shaken. The pH was adjusted to the set pH over 1,2,4, 8, 12, 24, 36, 48 and 72 hours and samples were taken to determine the total dissolved phosphorus concentration in the water and the effect of the addition of the 4% Ca/Al and 4% La/Ca/Al composites on the control of the release of phosphorus from the east lake sediment was evaluated. The measurement results showed that at ph=5.5 (fig. 4A), the average total water-soluble phosphorus concentration of the 4% Ca/Al composite and 4% la/Ca/Al composite repaired eastern lake sediment groups was 0.050 and 0.032mg/L, respectively, significantly lower than the original eastern lake sediment (average 0.126 mg/L). At ph=7.5 (fig. 4B), the total water-soluble phosphorus concentration of the 4% Ca/Al composite and 4% la/Ca/Al composite-repaired eastern lake sediment groups remained very low throughout the experiment, with average values of 0.030 and 0.019mg/L, respectively, significantly lower than the original eastern lake sediment (average value of 0.220 mg/L). At ph=9.5 (fig. 4C), the average values of the total water solubility phosphorus concentration of the 4% Ca/Al composite and 4% la/Ca/Al composite modified eastern lake sediment groups were 0.094 and 0.059mg/L, respectively, significantly lower than the original eastern lake sediment group (average 1.570 mg/L). These results demonstrate that the addition of 4% Ca/Al and 4% La/Ca/Al composites significantly reduced the phosphorus concentration in the overlying water at different pH conditions.
Example 6: taking 10 grams of dried original east lake sediment, 4% Ca/Al composite modified east lake sediment and 4% La/Ca/Al composite modified east lake sediment in the above example 3, adding into a beaker with an inner diameter of 6.0 cm and a height of 20cm, slowly injecting water to reach a water column height of 10 cm, and closing a beaker mouth. The experiment was performed at room temperature, and an aerobic group and an anaerobic group were set. During the first 15 days of the experiment, air (for aerobic treatment) and pure N were continuously injected by 2 hours per day, respectively 2 (for anaerobic treatment), the upper layer was controlled to be in an aerobic state (DO)>6 mg/L) and anaerobic (DO)<0.5 mg/L). And then standing still to maintain the sealing state for 50 days. Water samples were taken every 2 days for the first 17 days, every 4 days for the last 33 days, the total phosphorus concentration of the water-over-coating solubility was determined (see fig. 5 for results), and the pH change of the water-over-coating during the experiment was determined (see fig. 6 for results). The measurement results of the aerobic treatment group showed that in the case where the Dongfu raw sediment group was exposed to sufficient air every day for the first fifteen days to maintain the DO of not less than 6mg/L (FIG. 5A), the total phosphorus concentration of the overlying water solubility fluctuated in the range of 0.111-0.168mg/L from day 3 to day 15, and then was continuously raised and stabilized at 0.516mg/L after the air exposure was stopped. The total phosphorus concentration of the water-soluble coating of the east lake sediment group modified by the 4% Ca/Al composite material and the east lake sediment group modified by the 4% La/Ca/Al composite material are maintained at lower concentrations under the aerobic state, and the average values are 0.040mg/L and 0.025mg/L respectively. The results of the anaerobic treatment group showed that the total phosphorus concentration of the upper water solubility was continuously increased to 2.244mg/L in the case where the original Dongfu sediment group was exposed to enough pure nitrogen gas every day for the first fifteen days to maintain DO not greater than or equal to 0.5mg/L (FIG. 5B), and then the total phosphorus concentration of the upper water solubility was decreased after stopping the exposure to nitrogen gas, and stabilized around 0.853mg/L in the final stage of the cultivation. Donghu sediment group modified by 4% Ca/Al composite material and 4% La/Ca/Al composite materialThe total phosphorus concentration of the material-modified Donghu sediment group in the water-solubility was kept low, and the average values were 0.064mg/L and 0.035mg/L, respectively. This result demonstrates that 4% added Ca/Al composite material and 4% added La/Ca/Al composite material can well control the release of phosphorus from the sediment, and the control effect is not affected by the dissolved oxygen and oxidation-reduction potential of the water body. The results of the pH measurements of the whole experimental group showed that neither the Ca/Al composite nor the La/Ca/Al composite had a significant effect on the pH of the overlying water, either in the aerobic or anaerobic state (fig. 6, where fig. 6A is an aerobic treatment and fig. 6B is an anaerobic treatment).
Example 7: about 250g (fresh weight, water content about 67%) of fresh sediment on the surface layer of the Wuhan Xiaonan lake is taken and added into a container with the inner diameter of 8cm and the height of 30cm, so that the sediment is 5cm in height and the overlying water height is 20cm. After standing and stabilizing, the Ca/Al composite material (2.8 g) in the above example 1 was added at a weight ratio of 1.12% of the material to fresh sediment, and the sediment was covered uniformly in an experimental vessel, and a continuous aerobic-anaerobic experiment was performed. The experimental period was 67 days, with the first 30 days being the aerobic phase (slow aeration, maintenance of DO > 6 mg/L) and the second 37 days being the anaerobic phase (slow aeration, maintenance of DO <1 mg/L). The total phosphorus concentration of the overburden water solubility was determined with the deposit of the uncovered Ca/Al composite as a control (FIG. 7). The concentration of water-coated phosphorus in the aerobic section of the original sediment of the small south lake and the small south lake sediment group covered with the Ca/Al composite material is continuously reduced. The concentration of water-soluble total phosphorus on the southern lake sediment group covered with the Ca/Al composite material drops faster and lower. After the Ca/Al composite material is covered by the south lake sediment under the aerobic condition, the total phosphorus concentration of the overlying water is obviously reduced, and the lower total phosphorus concentration of the overlying water is maintained from the 8 th day to the 30 th day (the average value is 0.004 mg/L). The phosphorus release strength of the original small southern lake sediment in the anaerobic section is obviously enhanced, and the total phosphorus concentration of the overlying water solubility is sharply increased. On anaerobic day 8 (i.e., day 38 of the experiment), the water-soluble total phosphorus on the initial sediment group of the small south lake suddenly increased to 0.451mg/L, and reached a peak of 1.374mg/L on anaerobic day 32 (i.e., day 62 of the experiment). The Ca/Al composite material covered has remarkable control effect on phosphorus release of the small southern lake sediment in the whole anaerobic stage, and the average value of the total phosphorus concentration of the water-solubility covered is 0.049mg/L.
Claims (8)
1. The application of the composite material in passivating sediment phosphorus of eutrophic water body is characterized in that the preparation method of the composite material comprises the following steps:
(1) Mixing lanthanum chloride, calcium chloride and aluminum chloride; wherein the ratio of the mass of lanthanum chloride and calcium chloride to the mass of aluminum chloride is (0.8-1.2): 1, lanthanum chloride accounts for 0-5% of the total mass of lanthanum chloride and calcium chloride;
(2) Adding the mixture obtained in the step (1) into water for dissolution;
(3) Adjusting the ph=9-10 of the solution obtained in step (2) with an inorganic alkaline solution; the inorganic alkali solution is NaOH solution or KOH solution;
(4) The solution with the pH value regulated is placed in a water bath condition of 50 ℃ to 60 ℃ for coprecipitation and crystallization for 12 to 24 hours;
(5) Centrifuging, collecting precipitate, drying, and grinding to obtain composite material;
the composite material can be widely suitable for lake oxidation-reduction state and pH value change to efficiently control sediment phosphorus release, does not influence the pH value of water body, and can correct the pH value under acidic and alkaline conditions.
2. Use according to claim 1, characterized in that lanthanum chloride constitutes 5% of the sum of the masses lanthanum chloride + calcium chloride.
3. The use according to claim 1 or 2, characterized in that the ratio of the mass of lanthanum chloride+calcium chloride to the mass of aluminum chloride is 1:1.
4. the use according to claim 1 or 2, wherein the ratio of the mixture to water in step (2) is 1g: (5-10) mL.
5. The use according to claim 1, wherein the concentration of the inorganic alkaline solution in the step (3) is 1mol/L to 5mol/L; the method comprises the steps of firstly adjusting by using a higher-concentration inorganic alkali solution, and then adjusting by using a lower-concentration inorganic alkali solution.
6. The use according to claim 1 or 2, wherein in step (4) the pH-adjusted solution is subjected to co-precipitation and crystallization for 24 hours in a water bath at 60 ℃.
7. The use according to claim 1 or 2, wherein the precipitation drying temperature in step (5) is 60 ℃ to 80 ℃.
8. The use according to claim 1 or 2, characterized by the specific steps of: the composite material is added to or overlaid on the sediment in a proportion of not less than 2% by dry weight of the sediment or not less than 0.75% by fresh weight of the sediment.
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