CN108314170B - Preparation method and use method of high-efficiency dispersed fluidized micron iron powder applied to wastewater treatment - Google Patents
Preparation method and use method of high-efficiency dispersed fluidized micron iron powder applied to wastewater treatment Download PDFInfo
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- CN108314170B CN108314170B CN201810047471.6A CN201810047471A CN108314170B CN 108314170 B CN108314170 B CN 108314170B CN 201810047471 A CN201810047471 A CN 201810047471A CN 108314170 B CN108314170 B CN 108314170B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 150000002505 iron Chemical class 0.000 claims description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 230000008878 coupling Effects 0.000 claims description 16
- 238000010168 coupling process Methods 0.000 claims description 16
- 238000005859 coupling reaction Methods 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000002351 wastewater Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- -1 hydroxyl compound Chemical class 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 229910052603 melanterite Inorganic materials 0.000 claims description 2
- 238000005243 fluidization Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 229960001701 chloroform Drugs 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical class [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 230000000593 degrading 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
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a preparation method and a use method of high-efficiency dispersed fluidized micron iron powder applied to wastewater treatment. The stable complex system can realize mixing and fluidization in a reactor easily, improve the utilization rate and the fluidization rate of micron iron powder, and avoid the deposition and hardening of iron powder particles in the reactor, a pipeline and the like. The preparation method has the advantages of simple operation, low cost, high safety and large-scale application.
Description
Technical Field
The invention relates to a preparation method of high-efficiency dispersed fluidized micron iron powder, belongs to the technical field of wastewater treatment, and particularly relates to a preparation and use method of high-efficiency dispersed fluidized micron iron powder applied to wastewater treatment.
Background
In recent years, due to the rapid development of industries such as mining industry, metallurgy, chemical industry, medicine, papermaking, printing and dyeing, leather and the like, a large amount of heavy metal and toxic degradation-resistant wastewater are discharged into a water body, and the wastewater has the characteristics of high toxicity, slow metabolism, easiness in accumulation, poor biodegradability, irreversibility and the like, seriously pollutes surface water and underground water, and causes frequent industrial pollution events.
Iron metal is used as an environment-friendly reducing agent, and is applied to water environment pollution treatment to obtain more attention and application. The reaction is usually carried out at normal temperature and normal pressure, and the method has the characteristics of low energy consumption, high pollutant degradation efficiency, capability of degrading various pollutants and the like. The prior results show that the zero-valent iron technology has excellent performance in solving a series of environmental problems such as heavy metal pollution, organic matter pollution, groundwater pollution remediation and the like, particularly shows good application prospect in the aspect of treating industrial wastewater with high toxicity and difficult biochemical treatment, and is an environmental management technology with great application prospect.
At present, the zero-valent iron material in practical engineering application mainly comprises iron shavings, various iron-carbon sintered bodies, iron-carbon composites, scrap iron, micron iron powder, nano iron powder and the like, and the particle diameter and the size of the zero-valent iron material range from centimeter to nanometer.
The zero-valent iron material is difficult to fluidize due to high density, and the iron material is stacked or structured by a carrier to form an iron fixed bed, which is a reactor and a reaction mode popular in the current practical engineering. For example, Chinese patent CN1183316A describes a reactor for quickly catalyzing and dechlorinating polychlorinated organic compounds in water by using zero-valent iron and palladium catalysts, in the method, a metal palladium and zero-valent iron composite system is loaded on activated carbon, ceramic or zeolite, and 1 (1-10) is mixed into a filler to form an immobilized filter bed, and the porosity of the filler layer is about 0.6. Patents mainly based on the fixed iron bed include patents CN104591426A, CN105502817A, CN204981432U, CN103951140A, CN101624250A, CN101591064A, CN101928066A, CN102120675A, CN102120674A and CN 102381760A. There are several problems with such fixed beds during use: (1) because the surface of the zero-valent iron material is easy to oxidize, insoluble iron oxide is formed and deposited on the surface of the zero-valent iron, the effective contact area of the filler and the wastewater is reduced, and the reaction efficiency is reduced; (2) the formed insoluble iron oxide is easy to deposit in the filter bed, which causes the blockage and short flow of the fixed bed reactor and reduces the mass transfer efficiency in the reactor. The two problems seriously affect the treatment effect and the utilization rate of the zero-valent iron, so that the obvious efficiency reduction occurs after a fixed bed in practical engineering runs for a period of time, and the application of the technology is limited.
Recently, the application of nano zero-valent iron in wastewater treatment is concerned. The nano zero-valent iron is ultrafine iron particles with a small particle size (1-100 nm), and is easily fluidized by direct mechanical or hydraulic stirring. For example, patent CN103112918A describes an integrated process for treating heavy metal wastewater by using nano zero-valent iron, which utilizes the characteristic of easy fluidization of nano zero-valent iron to achieve sufficient mixing of nano zero-valent iron and heavy metal wastewater by mechanical mixing and stirring, so as to remove target pollutants in water. The patent using nano zero-valent iron as the main invention point also comprises CN102897889A, CN103253757A, CN101857295A, CN102583689A, CN102500613A, CN102380505A, CN102276045A, CN102951749A, CN102887614A, CN103949469A and the like. However, the nano zero-valent iron also has many problems in practical engineering application, such as the cost of the nano zero-valent iron is too high; the high reactivity of the catalyst causes the catalyst to be easy to age and lose in the preparation, transportation and application processes; part of the complex wastewater has certain acidity, which causes unnecessary consumption of the nano zero-valent iron.
In order to solve the problems of the application of the fixed bed of the iron material and the application of the nano zero-valent iron, patent CN102795690A introduces a method for treating wastewater by using ultrasonic reinforced micron-sized iron-copper bimetallic particles, wherein the method mainly uses the ultrasonic to enable the iron-copper bimetallic particles to be in a fluidized state, improves the mass transfer efficiency of a reactor, and solves the problems that the fixed bed is easy to harden and the cost of the nano zero-valent iron is too high. However, the following disadvantages also exist:
(1) although the method realizes the fluidization of micron iron powder, iron and copper particles are easy to lose in the fluidization state, so that the consumption of iron is greatly increased, the treatment cost is increased, and the water quality after treatment is difficult to ensure;
(2) the ultrasonic probe is easy to generate serious cavitation corrosion under an acidic condition, so that the service life and the treatment effect of the ultrasonic probe are influenced;
(3) ultrasound technology has many limitations in scale-up applications and is difficult to engineer.
In summary, from the practical engineering application point of view, the existing method (patent) for treating wastewater by adopting zero-valent iron material has the following defects:
(1) the iron shaving fixed bed has small specific surface area and low mass transfer efficiency, and is easy to generate the phenomena of deposition, short flow and blockage after long-term operation, the treatment effect is very limited, the service life of the reactor is short, and the obvious efficiency reduction is generated within a plurality of months;
(2) the nano zero-valent iron is used for treating complex wastewater, so that the cost is high;
(3) the pH value of some complex wastewater is low, iron powder is corroded after water is fed, unnecessary consumption is caused, and the engineering cost is greatly increased;
(4) the method for improving the fluidization rate or the reaction activity of the zero-valent iron material is not suitable for large-scale application at present;
therefore, a zero-valent iron material which is cheap, has high treatment efficiency and can avoid blockage or deposition is required to be searched for in practical engineering application.
Disclosure of Invention
In view of the defects of the zero-valent iron material in the practical engineering application in the environmental field, the invention aims to provide a preparation and use method of high-efficiency dispersed fluidized micron iron powder for wastewater treatment. The method adopts iron/aluminum salt solution and micron iron powder to prepare, mix and disperse, then the mixture reacts with alkaline reagent solution, and a stable composite system of inorganic hydroxyl compound and micron iron powder coupling is prepared by controlling a certain proportion and synthesis conditions (formula 1 and formula 2). The complex system can realize mixing and fluidization in a reactor easily, improve the utilization rate and the fluidization rate of micron iron powder, and avoid the deposition and hardening of iron powder particles in the reactor, a pipeline and the like. The preparation method has the advantages of simple operation, low cost, high safety and large-scale application.
The invention provides a preparation method of high-efficiency dispersed fluidized micron iron powder for wastewater treatment, which comprises the steps of preparing, mixing and dispersing an iron/aluminum salt solution and micron iron powder, reacting with an alkaline reagent solution, and preparing a concentrated coupling stable system coupling an inorganic hydroxyl compound and the micron iron powder by controlling the preparation ratio and synthesis conditions; the method comprises the following specific steps:
(1) weighing iron salt and aluminum salt, dissolving into water to obtain an inorganic hydroxyl compound, controlling the concentration of the prepared iron/aluminum salt solution to be 10.0-50.0 g/L, and simultaneously adjusting the pH value of the iron/aluminum salt solution to be 6.0-7.0;
(2) weighing micron iron powder, and controlling the molar ratio of iron/aluminum salt to micron iron powder to be (0.1-2.0): 1;
(3) will step withThe micron iron powder obtained in the step (2) and the iron/aluminum solution prepared in the step (1) are mixed and mechanically stirred, and the G value of the stirring speed gradient is controlled to be 400--1Controlling the stirring time to be 0.5-2.0 min;
(4) weighing an alkaline reagent, dissolving the alkaline reagent in water, and controlling the concentration of the prepared alkaline reagent to be 1.0-10.0 g/L;
(5) pumping the alkaline reagent obtained in the step (4) into the mixed solution of the micron iron powder and the iron/aluminum salt obtained in the step (3), controlling the molar ratio of the iron/aluminum salt to the alkaline reagent to be 1 (2.5-3.5), and controlling the stirring speed gradient G value to be less than 500 s in the process-1Controlling the pH value of the whole system to be 7.0-10.0 by increasing or decreasing the dropping speed of the alkaline reagent, and controlling the reaction time not to exceed 10.0 min to form a concentrated coupling stable system;
(6) after the step (5) is finished, stopping stirring, settling the concentration coupling stable system, controlling the concentration of iron powder in the concentration coupling stable system to be 100.0-150.0 g/L, and controlling the concentration of micron iron powder in the concentration coupling stable system added into the wastewater reactor to be 5.0-40.0 g/L; and according to the consumption, the corresponding inorganic hydroxyl compound or micron iron powder is supplemented.
In the invention, the iron salt is FeSO4·7H2O, the aluminum salt is Al2(SO4)3·18H2O）。
In the invention, dilute sulfuric acid or dilute sodium hydroxide is adopted for adjusting the pH value of the iron/aluminum salt solution in the step (1).
In the invention, the alkaline reagent in the step (4) adopts sodium hydroxide or potassium hydroxide.
In the invention, the size of the micron iron powder in the step (2) is 0.1-80 μm.
The invention has the beneficial effects that:
(1) the coupled stable type micron iron powder prepared by the invention is easy to fluidize and not easy to lose through mechanical or hydraulic stirring, improves the fluidization rate and the utilization rate of the micron iron powder, and avoids the hardening phenomenon;
(2) the medicament used in the invention is industrial ferrous sulfate salt or aluminum sulfate salt, and the cost is low;
(3) the inorganic hydroxyl compound prepared by the method can improve the adsorption capacity of the coupling stable type micron iron powder to organic matters/inorganic matters, increase the hydraulic retention time of pollutants and improve the removal efficiency of the pollutants;
(4) the inorganic hydroxyl compound prepared by the invention can avoid the reaction of micron iron powder and H + in wastewater under an acidic condition, reduces unnecessary consumption cost, and is suitable for large-scale application.
Drawings
FIG. 1 shows the sedimentation test of 1 micron iron powder in example under different stirring speeds.
Fig. 2 is a sedimentation experiment of micron iron powder in the coupled stable micron iron powder system in example 2 under different stirring rotating speeds.
FIG. 3 is a graph comparing the removal of chloroform by various systems of example 2.
FIG. 4 is a graph comparing the removal of chloroform by various systems of example 2.
Detailed Description
The following examples further illustrate the present invention and its practical effects.
Example 1:
enhanced suspension of micron iron powder
(1) Weighing 25.0 g of 3000-mesh micron iron powder, and putting the powder into a 5.0L container for stirring, wherein the stirring speed is 150.0 rpm;
(2) an additional 124.0 g of FeS0 were weighed out4·7H2Placing O and 25.0 g of 3000-micron iron powder into another 5.0L container for stirring, wherein the stirring speed is 400.0 rpm, and the stirring time is 5.0 min;
(3) weighing 35.7 g of NaOH, dissolving in 1.0L of tap water, slowly pouring into a container, monitoring the pH value of the solution, controlling the pH value of the whole system to be 7.0-10.0, keeping the whole process for about 3min, and then adjusting the stirring speed to be 150 rpm;
(4) after stirring for 60 min, sampling and digesting at sampling points with different heights to measure solid content;
(5) converting the stirring speed into 100.0 rpm and 50.0 rpm, stirring for 60 min, sampling and digesting at different sampling points, and measuring the solid content;
from fig. 1, it can be seen that the concentration of the micron iron powder at the five sampling points is about 5.0 g/L, which indicates that the pure micron iron powder is fully fluidized in water at 150 rpm and uniformly distributed; when the stirring speed is 100 rpm, the concentration of pure micron iron powder at the position of five sampling points is about 2.0 g/L, which indicates that part of micron iron powder is deposited at the bottom of the reactor; when the stirring speed is 50 rpm, the concentration of pure micron iron powder at five sampling points is basically 0 g/L, which indicates that most of micron iron powder can not be fluidized by mechanical stirring and is completely deposited at the bottom of the reactor. It can be seen from fig. 2 that the coupled stable iron powder can be fully fluidized no matter at the stirring speed of 150, 100 and 50 rpm, the concentration range of the coupled stable micron iron powder at three rotating speeds is between 4.7 and 5.0 g/L, and the whole system is uniformly and stably distributed.
Example 2:
stable coupling type micro-iron powder trichloromethane removal method
(1) Weighing 5.0 g of 3000-mesh micron iron powder, adding the micron iron powder into 3L of 15.0 g/L FeSO4·7H2In the O solution, the stirring speed is adjusted to 400 rpm, and the stirring time is 5 min;
(2) adjusting the pH value of the mixed solution to 6.5 by using 0.10 mol/L NaOH;
(3) preparing 2L of NaOH solution with the concentration of 6.5 g/L;
(4) pumping NaOH solution into the solution obtained in the step (1), controlling the pH value of the whole system to be 7.0-10.0, and keeping the duration time in the whole process to be not more than 3 min;
(5) preparing 20 mg/L trichloromethane solution, pumping into a coupling stable type micron iron powder system, and sampling and measuring samples at different reaction time points;
meanwhile, 1.0 g/L of nano zero-valent iron suspension and an iron shaving fixed bed are prepared, and a comparison experiment is carried out on the three, wherein the experiment period is 1 h. The chloroform concentration of the water was measured and the experimental results are shown in fig. 3 and 4.
FIG. 3 is a comparison graph of chloroform removal in three reactors, from which it can be seen that the chloroform concentration in the effluent of the nano zero-valent iron reactor decreased from 20 mg/L to 12 mg/L after 1 h of reaction time, and the chloroform concentration in the effluent of the coupled stabilized type micron iron powder reactor decreased from 20 mg/L to 13.5 mg/L, which shows that the chloroform removal capacity of the coupled stabilized type micron iron powder is not much different from that of the nano zero-valent iron, while the chloroform concentration in the effluent of the iron-coated fixed bed is 16 mg/L; it can be seen from fig. 4 that the three reactors have certain difference in the effect of removing the trichloromethane, the nano zero-valent iron has the best effect of removing the trichloromethane, the coupling stable type micron iron powder has the second order, and the iron shaving fixed bed has the worst effect. After 1 h of reaction time, the removal rate of the nano zero-valent iron to the trichloromethane is about 40%, the removal rate of the coupling stable type micron iron powder to the trichloromethane is about 33%, and the removal rate of the iron-coated flower fixed bed is only about 20%, which is basically consistent with the results reported in the previous literature.
Claims (4)
1. A preparation method of high-efficiency dispersed fluidized micron iron powder applied to wastewater treatment is characterized in that iron/aluminum salt solution and micron iron powder are prepared, mixed, dispersed, reacted with alkaline reagent solution, and a concentrated coupled stable system of inorganic hydroxyl compound and micron iron powder is prepared by controlling the proportion and synthesis conditions; the method comprises the following specific steps:
(1) weighing iron salt or aluminum salt, dissolving into water to obtain inorganic hydroxyl compound, controlling the concentration of the prepared iron/aluminum salt solution to be 10.0-50.0 g/L, and simultaneously adjusting the pH value of the iron/aluminum salt solution to be 6.0-7.0;
(2) weighing micron iron powder, and controlling the molar ratio of iron/aluminum salt to micron iron powder to be (0.1-2.0): 1;
(3) mixing and mechanically stirring the micron iron powder obtained in the step (2) and the iron/aluminum solution prepared in the step (1), and controlling the gradient G value of the stirring speed to be 400--1Controlling the stirring time to be 0.5-2.0 min;
(4) weighing an alkaline reagent, dissolving the alkaline reagent in water, and controlling the concentration of the prepared alkaline reagent to be 1.0-10.0 g/L;
(5) pumping the alkaline reagent obtained in the step (4) into the mixed solution of the micron iron powder and the iron/aluminum salt obtained in the step (3), controlling the molar ratio of the iron/aluminum salt to the alkaline reagent to be 1 (2.5-3.5), and controlling the stirring speed gradient G value to be less than 500 s in the process-1Controlling the pH value of the whole system to be 7.0-10.0 by increasing or decreasing the dropping speed of the alkaline reagent, and controlling the reaction time not to exceed 10.0 min to form a concentrated coupling stable system;
(6) after the step (5) is finished, stopping stirring, settling the concentration coupling stable system, controlling the concentration of iron powder in the concentration coupling stable system to be 100.0-150.0 g/L, and controlling the concentration of micron iron powder in the concentration coupling stable system added into the wastewater reactor to be 5.0-40.0 g/L; according to the consumption, the corresponding inorganic hydroxyl compound or micron iron powder is supplemented;
the iron salt is FeSO4·7H2O, the aluminum salt is Al2(SO4)3·18H2O。
2. The method for preparing micron iron powder in high-efficiency dispersed fluidized state for wastewater treatment as claimed in claim 1, wherein the pH value of the iron/aluminum salt solution is adjusted in step (1) by using dilute sulfuric acid or dilute sodium hydroxide.
3. The method for preparing high-efficiency dispersed fluidized micron iron powder for wastewater treatment as claimed in claim 1, wherein the alkaline reagent in step (4) is sodium hydroxide or potassium hydroxide.
4. The method for preparing high-efficiency dispersed fluidized micron iron powder for wastewater treatment as claimed in claim 1, wherein the size of the micron iron powder in step (2) is 0.1-80 μm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS591117B2 (en) * | 1978-08-31 | 1984-01-10 | 環境エンジニアリング株式会社 | How to treat organic wastewater |
| CN101386075A (en) * | 2008-10-23 | 2009-03-18 | 安徽工业大学 | Preparation method of nano ferrous powder |
| CN106007169A (en) * | 2016-05-17 | 2016-10-12 | 中国科学院生态环境研究中心 | Method for effectively retarding ultrafiltration membrane pollution by using in-situ Fe(OH)3 floccules and nano-iron |
| CN107052328A (en) * | 2017-05-10 | 2017-08-18 | 同济大学 | A kind of preparation method of simple stable highly active Fe sill |
| CN107252673A (en) * | 2017-07-12 | 2017-10-17 | 北京科技大学 | A kind of preparation method and applications of Nano/micron iron oxide sorbing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS591117B2 (en) * | 1978-08-31 | 1984-01-10 | 環境エンジニアリング株式会社 | How to treat organic wastewater |
| CN101386075A (en) * | 2008-10-23 | 2009-03-18 | 安徽工业大学 | Preparation method of nano ferrous powder |
| CN106007169A (en) * | 2016-05-17 | 2016-10-12 | 中国科学院生态环境研究中心 | Method for effectively retarding ultrafiltration membrane pollution by using in-situ Fe(OH)3 floccules and nano-iron |
| CN107052328A (en) * | 2017-05-10 | 2017-08-18 | 同济大学 | A kind of preparation method of simple stable highly active Fe sill |
| CN107252673A (en) * | 2017-07-12 | 2017-10-17 | 北京科技大学 | A kind of preparation method and applications of Nano/micron iron oxide sorbing material |
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