CN111186971A - Recoverable bottom mud covering device and application - Google Patents

Recoverable bottom mud covering device and application Download PDF

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Publication number
CN111186971A
CN111186971A CN202010017600.4A CN202010017600A CN111186971A CN 111186971 A CN111186971 A CN 111186971A CN 202010017600 A CN202010017600 A CN 202010017600A CN 111186971 A CN111186971 A CN 111186971A
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gas
iron
covering device
recoverable
based material
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林建伟
詹艳慧
王艳
雷佳佳
吴丹红
白先尚
韩梦凡
刘妞妞
刘驰
常明玥
辛慧敏
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Shanghai Ocean University
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Shanghai Ocean University
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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
    • C02F11/00—Treatment of sludge; Devices therefor
    • 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
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/16—Alumino-silicates
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    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/28002—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 physical properties
    • B01J20/28009—Magnetic properties

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Abstract

The invention provides a recoverable sediment covering device and application thereof, wherein an outer layer structure of the covering device is coated with an inner layer structure; the inner layer structure consists of a magnet active material, is added above a sediment-water interface, and is removed from a water body under the action of an external magnetic field after the adsorption of pollutants reaches saturation; the magnet active material in the mononuclear type sediment covering device is selected from a magnetic iron-based material, a magnetic zirconium-based material, a magnetic magnesium iron-based material and a magnetic lanthanum-based material, the inner layer structure in the double-core type sediment covering device comprises an inner core and an outer core, the inner core is made of ferroferric oxide, and the outer core is made of an iron-based material, a zirconium-based material, a magnesium iron-based material and a lanthanum-based material; the outer layer structure is a porous fabric material; the covering device of the invention can not only prevent the covering magnetic material from being washed away by water flow and lost, but also prevent the sediment from being mixed with the covering magnetic material, thereby greatly saving the repair cost of the sediment and maximally realizing the recovery of pollutants in the sediment.

Description

Recoverable bottom mud covering device and application
Technical Field
The invention belongs to the technical field of endogenous pollution treatment and restoration in a water area, and particularly relates to a recoverable sediment covering device and application.
Background
The sources of pollutants in the water body are external sources (such as sewage point source discharge, surface runoff, atmospheric sedimentation and the like) and internal sources (the pollutants in the sediment are released to the overlying water body). After the exogenous pollutants are effectively controlled, the release of the endogenous pollutants in the bottom sediment becomes an important source of the pollutants in the water body. Therefore, the research and development of the efficient and economic water body endogenous pollution control technology has important significance.
At present, the release control technology of endogenous pollutants in sediment mainly comprises sediment dredging, aeration oxygen supply, in-situ covering technology and the like. The sediment dredging technology has the defects of thoroughly destroying the benthic ecosystem, high cost, needing an additional sediment dredging treatment and disposal site and the like. The aeration and oxygen supply are only temporary measures, and once the aeration is stopped, the pollutants in the bottom sludge can be released again. The in-situ covering technology not only has high efficiency of controlling the release of the pollutants in the bottom sediment, but also has the advantages of convenient implementation, low repair cost and the like, and becomes a very promising technology for controlling the release of the pollutants in the bottom sediment.
The method selects proper covering materials to construct a sediment in-situ covering system, and is the key for controlling the release of endogenous pollutants in a water body by applying an in-situ covering technology. In recent years, a number of cover materials have been investigated for the control of the release of endogenous pollutants in water bodies, such as activated carbon, zeolites, lanthanum modified bentonite, attapulgite, and waterworks sludge, among others. However, these conventional non-magnetic cover materials are difficult to recover after application, which increases the cost of sediment remediation. To this end, researchers have proposed that powdered magnetic adsorbent materials can be used as a means of blanketing for controlling the release of endogenous pollutants in a body of water. However, this technique has significant drawbacks: after the powdery magnetic material is added above the sediment-water interface, the powdery magnetic material is inevitably mixed with the sediment under the action of hydrodynamic force and biological disturbance. On one hand, the effect of the materials for repairing the bottom mud can be reduced, on the other hand, the difficulty of material recovery can be increased, and therefore the cost of bottom mud repair is increased. Therefore, it is highly desirable to overcome the shortcomings of the prior art magnetic material coating techniques and to control the release of water body sediment contaminants.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a simple, convenient and efficient recyclable sediment covering device, provides a construction method of the device, and applies the device to the release control of sediment pollutants in a water body.
In order to achieve the above purpose, the solution of the invention is as follows:
a recoverable sediment covering device comprises an inner layer structure and an outer layer structure, wherein the inner layer structure is coated by the outer layer structure; the inner layer structure is composed of a magnet active material; the outer layer structure is made of porous material; the pore diameter of the porous material is smaller than the particle diameter of the magnet active material in the inner layer structure; the widest part of the recoverable bottom mud covering device is 1-50cm in size, the recoverable bottom mud covering device is thrown above a bottom mud-water interface, and after the adsorption of pollutants in the bottom mud is saturated, the recoverable bottom mud covering device is removed from the water body by using the action of an external magnetic field. Since the whole sediment covering device exhibits magnetism and can be attracted by the magnet, when the sediment covering device is placed in water, the sediment covering device can be fished out under the action of an external magnetic field (namely, the attraction force of the magnet).
Further, the recyclable substrate sludge covering apparatus includes a recyclable single-core substrate sludge covering apparatus and a recyclable double-core substrate sludge covering apparatus.
Further, the recyclable mononuclear type substrate covering device comprises an inner layer structure and an outer layer structure, wherein the magnet active material of the inner layer structure is selected from a magnetic iron-based material, a magnetic zirconium-based material, a magnetic magnesium iron-based material and a magnetic lanthanum-based material, and the porous material of the outer layer structure is a fabric.
Further, the shape of the recoverable mononuclear type bottom mud covering device comprises a circular cake-shaped body, a cuboid, a spindle body, a sphere, an ellipsoid, a cone, a table body and a cylinder.
Further, the diameter of the recoverable mononuclear type bottom mud covering device of the circular cake-shaped body is 1-50cm, and the thickness is 1-5 cm.
Further, the length of the rectangular recoverable mononuclear type bottom mud covering device is 1-50cm, the width is 1-20cm, and the height is 1-10 cm.
Further, the height of the recoverable mononuclear type sediment covering device of the spindle body is 2-20cm, and the diameter of the widest part is 1-10 cm.
Further, the diameter of the recoverable mononuclear type sediment covering device of the sphere is 1-20 cm.
Further, the long diameter of the recoverable mononuclear type sediment covering device of the ellipsoid is 2-20cm, and the short diameter is 1-10 cm.
Further, the linear distance of the widest position of the bottom surface of the recoverable mononuclear type bottom mud covering device of the vertebral body is 1-20cm, and the height is 1-20 cm.
Furthermore, the linear distance of the widest part of the bottom surface of the recoverable mononuclear type bottom mud covering device of the platform body is 2-20cm, the linear distance of the widest part of the top surface is 1-10cm, and the height is 1-10 cm.
Further, the linear distance of the widest part of the cross section of the recyclable mononuclear type substrate mud covering device of the cylinder is 1-20cm, and the height of the recyclable mononuclear type substrate mud covering device is 1-20 cm.
Further, the preparation process of the magnetic iron-based material comprises the following steps: mixing a carrier material and a soluble ferric iron/ferrous iron mixed solution, reacting for 0.5-2h at 70-80 ℃, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 10-11, cleaning and drying.
Wherein the carrier material is selected from more than one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and active carbon.
The molar ratio of ferric iron to ferrous iron in the soluble ferric iron/ferrous iron mixed solution is (2-4):1, preferably 2: 1.
Ferric ions in the soluble ferric iron/ferrous iron mixed solution are prepared by ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and ferrous ions are prepared by ferrous chloride tetrahydrate, ferrous sulfate heptahydrate or ferrous nitrate.
Further, the preparation process of the magnetic zirconium-based material comprises the following steps: mixing the magnetic iron-based material and zirconium oxychloride octahydrate, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, cleaning and drying.
Further, the preparation process of the magnetic magnesium-iron-based material comprises the following steps: mixing the magnetic iron-based material and a magnesium-iron solution, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 11-13, cleaning and drying.
Wherein, magnesium ions in the magnesium-iron solution are prepared by magnesium chloride hexahydrate, iron ions are prepared by ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and the molar ratio of the magnesium ions to the iron ions is (2-4): 1.
Further, the magnetic lanthanum-based material is selected from a magnetic lanthanum hydroxide-based material or a magnetic lanthanum carbonate-based material.
The preparation process of the magnetic lanthanum hydroxide-based material comprises the following steps: mixing the magnetic iron-based material and a lanthanum salt solution, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 8-11, cleaning and drying. Wherein the lanthanum salt is selected from lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate.
Further, the preparation process of the magnetic lanthanum carbonate-based material comprises the following steps: mixing the magnetic iron-based material and a lanthanum salt solution, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium carbonate solution, adjusting the pH value of the mixed solution to 8-11, cleaning and drying. Wherein the lanthanum salt is selected from lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate.
Further, the recoverable double-core type bottom mud covering device comprises an inner layer structure and an outer layer structure, wherein the inner layer structure comprises an inner core and an outer core, the magnet active material of the inner core is commercial or self-made ferroferric oxide, the active material of the outer core is selected from an iron-based material, a zirconium-based material, a magnesium-iron-based material and a lanthanum-based material, the inner core and the outer core are separated by a fabric, and the volume ratio of the inner core to the outer core is 1 (1-10); the porous material of the outer layer structure is a fabric.
Further, the commercial ferroferric oxide is selected from ferroferric oxide prepared by domestic or foreign manufacturers, and the purity of the ferroferric oxide is 95 +/-1%.
Further, the preparation process of the self-made ferroferric oxide comprises the following steps: putting 0.1-2mol/L soluble ferric iron/ferrous iron mixed solution into a container, placing the container at 70-80 ℃ for reaction, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 10-11, cleaning and drying.
Wherein the molar ratio of ferric iron to ferrous iron in the soluble ferric iron/ferrous iron mixed solution is (2-4):1, ferric iron in the soluble ferric iron/ferrous iron mixed solution is prepared from ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and ferrous iron is prepared from ferrous chloride tetrahydrate, ferrous sulfate heptahydrate or ferrous nitrate.
Further, the preparation process of the iron-based material comprises the following steps: mixing iron salt, carrier material and water, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, cleaning and drying.
Wherein the ferric salt is selected from more than one of ferric chloride hexahydrate, ferric sulfate and ferric nitrate.
The carrier material is selected from more than one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and active carbon.
Further, the preparation process of the zirconium-based material comprises the following steps: mixing zirconium oxychloride octahydrate, a carrier material and water, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, cleaning and drying.
Wherein the carrier material is selected from more than one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and active carbon.
Further, the preparation process of the magnesium-iron-based material comprises the following steps: mixing the carrier material and the magnesium-iron solution, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 11-13, cleaning and drying.
Wherein the carrier material is selected from more than one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and active carbon.
Magnesium ions in the magnesium-iron solution are prepared from magnesium chloride hexahydrate, iron ions are prepared from ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and the molar ratio of the magnesium ions to the iron ions is (2-4): 1.
Further, the lanthanum-based material is selected from a lanthanum hydroxide-based material or a lanthanum carbonate-based material.
Further, the preparation process of the lanthanum hydroxide-based material comprises the following steps: mixing lanthanum salt, carrier material and water, then dripping 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 8-11, cleaning and drying. Wherein the lanthanum salt is selected from lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate.
The carrier material is selected from more than one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and active carbon.
Further, the preparation process of the lanthanum carbonate-based material comprises the following steps: mixing lanthanum salt, carrier material and water, then dropwise adding 0.2-2mol/L sodium carbonate solution, adjusting the pH value of the mixed solution to 8-11, cleaning and drying. Wherein the lanthanum salt is selected from lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate.
The carrier material is selected from more than one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and active carbon.
Further, the shape of the recoverable double-core sediment covering device comprises a circular cake-shaped body, a cuboid, a spindle body, a sphere, an ellipsoid, a cone, a table body and a cylinder.
Further, the diameter of the recoverable double-core type bottom mud covering device of the circular cake-shaped body is 1-50cm, and the thickness is 1-5 cm.
Further, the length of the rectangular recoverable double-core type bottom mud covering device is 1-50cm, the width is 1-20cm, and the height is 1-10 cm.
Further, the height of the recoverable double-core sediment covering device of the spindle body is 2-20cm, and the diameter of the widest part is 1-10 cm.
Further, the diameter of the spherical recyclable double-core sediment covering device is 1-20 cm.
Further, the long diameter of the recoverable double-core sediment covering device of the ellipsoid is 2-20cm, and the short diameter is 1-10 cm.
Further, the linear distance of the widest position of the bottom surface of the recoverable double-core sediment covering device of the vertebral body is 1-20cm, and the height is 1-20 cm.
Further, the linear distance of the widest position of the bottom surface of the recoverable double-core sediment covering device of the platform body is 2-20cm, the linear distance of the widest position of the top surface is 1-10cm, and the height is 1-10 cm.
Further, the straight line distance of the widest part of the cross section of the recoverable double-core type bottom mud covering device of the cylinder is 1-20cm, and the height of the recoverable double-core type bottom mud covering device is 1-20 cm.
The application of the recoverable bottom sediment covering device in the release control of endogenous pollutants in the bottom sediment of the water body.
Due to the adoption of the scheme, the invention has the beneficial effects that:
first, compared with the simple powder magnetic material, the recyclable sediment covering device can prevent the covering magnetic material from being washed away by water flow and lost, and can prevent the sediment from being mixed with the covering magnetic material, so that the covering magnetic material is prevented from being mixed with the sediment or the covering magnetic material is prevented from being lost, the covering efficiency is reduced due to the mixing of the covering magnetic material with the sediment or the loss of the covering magnetic material, the difficulty in recycling the covering magnetic material is avoided, the repairing cost of the sediment is greatly saved, the recycling of pollutants in the sediment can be realized to the greatest extent, the sustainable development concept is better met, and the recyclable sediment covering device has a wider application prospect.
Secondly, the recoverable double-core type sediment covering device can be assembled and constructed by fully utilizing the existing materials, so that the defect that the preparation difficulty of a magnetic iron-based material, a magnetic zirconium-based material, a magnetic magnesium iron-based material or a magnetic lanthanum-based material is high is overcome.
Thirdly, the invention comprehensively considers the efficiency of the recyclable bottom sediment covering device for controlling the release of the bottom sediment pollutants, the influence on the original ecological system of the water body benthos and the convenience of the device recovery, develops the recyclable bottom sediment covering device with the widest dimension not more than 50cm, can effectively control the release of the pollutants in the bottom sediment and recover the beneficial resources in the bottom sediment, and can conveniently recover the bottom sediment covering device by the action of an external magnetic field, thereby realizing great technical progress.
Drawings
FIG. 1 is a schematic structural view of a recyclable substrate sludge blanket apparatus according to the present invention.
FIG. 2 is a partial structural view of the recoverable double-core sediment covering device of the invention.
FIG. 3 is a schematic view of the recycling process of the recyclable substrate sludge blanket apparatus of the present invention.
FIG. 4 is a schematic structural view of three recyclable mononuclear type sediment coverage devices according to embodiment 1 of the present invention.
Detailed Description
The invention provides a recoverable bottom mud covering device and application.
< recycled bottom mud covering apparatus >
The recoverable sediment covering device comprises an inner layer structure and an outer layer structure, wherein the inner layer structure is coated by the outer layer structure, the inner layer structure is composed of a magnet active material, and the outer layer structure is made of a porous material; the pore diameter of the porous material is smaller than the particle diameter of the magnet active material in the inner layer structure; the widest part of the recoverable bottom mud covering device is 1-50cm in size, the recoverable bottom mud covering device is thrown above a bottom mud-water interface, and after the adsorption of pollutants in the bottom mud is saturated, the recoverable bottom mud covering device is removed from the water body by using the action of an external magnetic field.
Wherein the recoverable sediment covering device comprises a recoverable mononuclear sediment covering device and a recoverable binuclear sediment covering device.
< recyclable mononuclear type bed mud covering apparatus >
Specifically, as shown in fig. 1, the recyclable mononuclear-type substrate covering device of the present invention includes an inner layer structure and an outer layer structure, the magnet active material of the inner layer structure is selected from a magnetic iron-based material, a magnetic zirconium-based material, a magnetic magnesium iron-based material and a magnetic lanthanum-based material, and the material of the outer layer structure is an acid-resistant and corrosion-resistant porous fabric material. In fact, the inner layer structure material is firstly prepared, and then the inner layer structure is wrapped by the porous fabric material with water permeability, so that the whole body presents a certain three-dimensional structure, and the closed parts are bonded, namely the recyclable mononuclear type substrate mud covering device is formed.
(magnetic iron-based Material)
The preparation process of the powdery magnetic iron-based material comprises the following steps: mixing carrier material (at least one selected from bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and activated carbon), Fe3+/Fe2+Solution (Fe)3+Prepared by ferric chloride hexahydrate, ferric sulfate or ferric nitrate, Fe2+Prepared by ferrous chloride tetrahydrate, ferrous sulfate heptahydrate or ferrous nitrate, Fe3 +/Fe2+In a molar ratio of (2-4):1, preferably 2:1, Fe3+/Fe2+The total concentration of iron in the solution is 0.2-3mol/L), wherein the mass of the support material and Fe3+/Fe2+The ratio of the volumes of the solutions was (500-10) g: 1L, reacting at 70-80 ℃ for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 10-11, washing with water for 3-5 times, collecting, and drying to obtain a solid material.
(magnetic zirconium-based Material)
The preparation process of the powdery magnetic zirconium-based material comprises the following steps: mixing the powdery magnetic iron-based material with a zirconium oxychloride octahydrate solution, wherein the mass ratio of the magnetic iron-based material to the zirconium oxychloride octahydrate solution is (10-1): 1, the ratio of the mass of the magnetic iron-based material to the volume of the zirconium oxychloride octahydrate solution is (500-10) g: 1L, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, washing with water for 3-5 times, collecting, and drying to obtain a solid material.
(magnetic magnesium iron-based Material)
The preparation process of the powdery magnetic magnesium-iron-based material comprises the following steps: mixing the powdery magnetic iron-based material and a magnesium-iron solution (magnesium ions are prepared by magnesium chloride hexahydrate, iron ions are prepared by ferric chloride hexahydrate, ferric sulfate or ferric nitrate, the molar ratio of the magnesium ions to the iron ions is (2-4):1), wherein the mass ratio of the magnetic iron-based material to ferric salt (ferric chloride hexahydrate, ferric sulfate or ferric nitrate) is (10-1): 1, the ratio of the mass of the magnetic iron-based material to the volume of the magnesium-iron solution is (500-10) g: 1L, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 11-13, cleaning, and drying to obtain the magnetic magnesium-iron-based material.
(magnetic lanthanum-based Material)
The magnetic lanthanum-based material is selected from a magnetic lanthanum hydroxide-based material or a magnetic lanthanum carbonate-based material.
The preparation process of the powdery magnetic lanthanum hydroxide-based material comprises the following steps: mixing the powdery magnetic iron-based material with a lanthanum chloride hexahydrate or a lanthanum nitrate hexahydrate solution, wherein the mass ratio of the magnetic iron-based material to the lanthanum chloride hexahydrate or the lanthanum nitrate hexahydrate is (10-1): 1, the ratio of the mass of the magnetic iron-based material to the volume of the lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate solution is (500-10) g: 1L, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 8-11, washing for 3-5 times with water, collecting, and drying to obtain a solid material.
The preparation process of the powdery magnetic lanthanum carbonate-based material comprises the following steps: mixing the powdery magnetic iron-based material with a lanthanum chloride hexahydrate solution, wherein the mass ratio of the magnetic iron-based material to the lanthanum chloride hexahydrate or the lanthanum nitrate hexahydrate is (10-1): 1, the ratio of the mass of the magnetic iron-based material to the volume of the lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate solution is (500-10) g: 1L, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium carbonate solution, adjusting the pH value of the mixed solution to 8-11, washing with water for 3-5 times, collecting, and drying to obtain a solid material.
Specifically, the shape of the recoverable mononuclear type sediment covering device comprises a circular cake-shaped body, a cuboid, a spindle body, a sphere, an ellipsoid, a cone, a table body and a cylinder.
Wherein, the diameter of the recyclable mononuclear type bottom mud covering device of the circular cake-shaped body can be 1-50cm, and the thickness can be 1-5 cm.
The length of the rectangular recoverable mononuclear type bottom mud covering device can be 1-50cm, the width can be 1-20cm, and the height can be 1-10 cm.
The height of the recoverable mononuclear type sediment covering device of the spindle body can be 2-20cm, and the diameter of the widest part can be 1-10 cm.
The diameter of the recoverable mononuclear type sediment covering device of the sphere can be 1-20 cm.
The long diameter of the recoverable mononuclear type sediment covering device of the ellipsoid can be 2-20cm, and the short diameter can be 1-10 cm.
The linear distance of the widest position of the bottom surface of the recoverable mononuclear type bottom mud covering device of the vertebral body can be 1-20cm, and the height can be 1-20 cm.
The linear distance of the widest position of the bottom surface of the recyclable mononuclear type bottom mud covering device of the platform body can be 2-20cm, the linear distance of the widest position of the top surface can be 1-10cm, and the height can be 1-10 cm.
The straight line distance of the widest part of the cross section of the recyclable mononuclear type substrate mud covering device of the cylinder can be 1-20cm, and the height can be 1-20 cm.
(recoverable double-core type bed mud covering device)
Specifically, as shown in fig. 1, the recyclable dual-core type sediment covering device comprises an inner layer structure and an outer layer structure, wherein the inner layer structure comprises an inner core and an outer core, the magnet active material of the inner core can be commercial or self-made ferroferric oxide, the active material of the outer core is selected from an iron-based material, a zirconium-based material, a magnesium-iron-based material and a lanthanum-based material, and the material of the outer layer structure is an acid-resistant and corrosion-resistant porous fabric material. In practice, firstly, the ferroferric oxide is wrapped into a certain shape by adopting a water-permeable porous fabric material to obtain a device I, then, magnet active materials (an iron-based material, a zirconium-based material, a magnesium-iron-based material and a lanthanum-based material) are prepared, and then, the device I and the magnet active materials are wrapped by adopting the water-permeable fabric to be in a certain shape, so that the recyclable double-core sediment covering device is obtained.
(ferroferric oxide)
The commercial ferroferric oxide can be selected from ferroferric oxides prepared by domestic or foreign manufacturers as long as the purity of the ferroferric oxide meets the requirement of 95 +/-1 percent.
The preparation process of the self-made ferroferric oxide comprises the following steps: preparation of Fe3+/Fe2+Solution (Fe)3+Prepared by ferric chloride hexahydrate, ferric sulfate or ferric nitrate, Fe2+Prepared by ferrous chloride tetrahydrate, ferrous sulfate heptahydrate or ferrous nitrate) to lead Fe3+/Fe2+In a molar ratio of (2-4) to 1, Fe3+/Fe2+The total iron concentration in the solution is 0.1-2 mol/L. And then placing the solution in an oscillation system at 70-80 ℃ for reaction, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the solution to 10-11, collecting solid materials, washing for 3-5 times by using water, and drying.
(iron-based Material)
The preparation process of the iron-based material comprises the following steps: mixing ferric salt (selected from ferric chloride hexahydrate, ferric sulfate or ferric nitrate), a carrier material (selected from at least one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and activated carbon) and deionized water, wherein the mass ratio of the ferric salt to the carrier material is 1: (1-100), wherein the ratio of the mass of the carrier material to the volume of the aqueous solution is 1 g: (1-100) mL, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, collecting the solid material, washing with water for 3-5 times, and drying.
(zirconium-based Material)
The preparation process of the zirconium-based material comprises the following steps: mixing zirconium oxychloride octahydrate, a carrier material (at least one selected from bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and activated carbon) and deionized water, wherein the mass ratio of the zirconium oxychloride octahydrate to the carrier material is 1: (1-100), wherein the ratio of the mass of the carrier material to the volume of the aqueous solution is 1 g: (1-100) mL, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, collecting the solid material, washing with water for 3-5 times, and drying.
(magnesium iron base material)
The preparation process of the magnesium-iron-based material comprises the following steps: mixing a carrier material (at least one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and activated carbon) and a magnesium-iron solution (magnesium ions are prepared by magnesium chloride hexahydrate, iron ions are prepared by ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and the molar ratio of the magnesium ions to the iron ions is (2-4):1), wherein the mass ratio of the ferric salt (ferric chloride hexahydrate, ferric sulfate or ferric nitrate) to the carrier material is 1: (1-100), wherein the ratio of the mass of the carrier material to the volume of the aqueous solution is 1 g: (1-100) mL, then reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 11-13, cleaning and drying.
(lanthanum-based Material)
The lanthanum-based material is a lanthanum hydroxide-based material or a lanthanum carbonate-based material.
The preparation process of the lanthanum hydroxide-based material comprises the following steps: mixing lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate, a carrier material (at least one selected from bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and activated carbon) and deionized water, wherein the mass ratio of the lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate to the carrier material is 1: (1-100), wherein the ratio of the mass of the carrier material to the volume of the aqueous solution is 1 g: (1-100) mL, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 8-11, collecting the solid material, washing with water for 3-5 times, and drying.
The preparation process of the lanthanum carbonate-based material comprises the following steps: mixing lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate, a carrier material (at least one selected from bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and activated carbon) and deionized water, wherein the mass ratio of the lanthanum chloride hexahydrate or lanthanum nitrate hexahydrate to the carrier material is 1: (1-100), wherein the ratio of the mass of the carrier material to the volume of the aqueous solution is 1 g: (1-100) mL, then dropwise adding 0.2-2mol/L sodium carbonate solution, adjusting the pH value of the mixed solution to 8-11, collecting the solid material, washing with water for 3-5 times, and drying.
In practice, the outer core shape of the recoverable dual-core sediment covering device may include a circular cake, a cuboid, a spindle, a sphere, an ellipsoid, a cone, a table and a cylinder, and the inner core shape may also include a circular cake, a cuboid, a spindle, a sphere, an ellipsoid, a cone, a table and a cylinder. As shown in fig. 2, the shape of the outer core and the shape of the inner core of the apparatus can be freely combined, and the recyclable dual-core type sediment covering apparatus of the present invention includes, but is not limited to, the structure of fig. 2.
Wherein, the diameter of the recoverable double-core type bottom mud covering device of the circular cake-shaped body can be 1-50cm, and the thickness can be 1-5 cm.
The length of the rectangular recoverable double-core type bottom mud covering device can be 1-50cm, the width can be 1-20cm, and the height can be 1-10 cm.
The height of the recoverable double-core bed mud covering device of the spindle body can be 2-20cm, and the diameter of the widest part can be 1-10 cm.
The diameter of the recoverable double-core sediment covering device of the sphere can be 1-20 cm.
The long diameter of the recoverable double-core sediment covering device of the ellipsoid can be 2-20cm, and the short diameter can be 1-10 cm.
The straight line distance of the widest position of the bottom surface of the recoverable double-core sediment covering device of the vertebral body can be 1-20cm, and the height can be 1-20 m.
The linear distance of the widest position of the bottom surface of the recoverable double-core sediment covering device of the platform body can be 2-20cm, the linear distance of the widest position of the top surface can be 1-10cm, and the height can be 1-10 cm.
The straight line distance of the widest part of the cross section of the recoverable double-core sediment covering device of the cylinder can be 1-20cm, and the height can be 1-20 cm.
< application of recoverable sediment covering apparatus >
The recoverable bottom mud covering device can be applied to release control of endogenous pollutants in the bottom mud of the water body.
The mechanism that the magnet active material of the inner layer structure in the recoverable sediment covering device controls the release of sediment phosphorus is as follows: phosphorus released from the sediment enters the interstitial water and migrates upwards, and when the phosphorus reaches the active material of the magnet, the phosphorus in the interstitial water is adsorbed by the active material of the magnet, so that the migration of the phosphorus in the interstitial water to the overlying water body is intercepted, and the release of the phosphorus in the sediment to the overlying water body is further prevented. The mechanism of adsorption of the magnet active material to phosphorus in the interstitial water is then related to its species. Specifically, for the magnetic iron-based material, the mechanism for adsorbing phosphorus in water is that phosphate in water firstly performs ligand exchange with hydroxyl on the surface of iron oxide and then forms an inner complex with iron. For magnetic zirconium-based materials, the mechanism for adsorbing phosphorus in water is firstly ligand exchange between phosphate and iron oxide/zirconium oxide surface hydroxyl groups in water, and then inner layer complexation between iron/zirconium and phosphate. For the magnetic lanthanum-based material, the mechanism for adsorbing phosphorus in water is as follows: firstly, ligand exchange occurs between hydroxyl on the surface of iron/lanthanum oxide and phosphate in water, and then an inner layer complex is formed between the iron/lanthanum and the phosphate. For the magnetic magnesium-iron-based material, the mechanism for adsorbing phosphorus in water is as follows: (1) ligand exchange occurs between hydroxyl on the surface of the magnetic magnesium-iron-based material and phosphate in water, and then an inner layer complex is formed; (2) anion exchange and electrostatic attraction between chloride ions in the magnetic magnesium-iron-based material and phosphate in water.
Specifically, the recoverable bottom mud covering device is thrown onto the water surface of a water body, the covering device automatically settles above a bottom mud-water interface under the action of gravity to form a layer of covering system, pollutants released from bottom mud to upward overlying water are intercepted by utilizing the adsorption effect of the covering system on the pollutants in the water in the bottom mud gaps, and the purpose of controlling the release of endogenous pollutants in the water body is achieved. The concentration of the pollutants in the water body is tested regularly, and when the concentration of the pollutants in the water body exceeds a specified value required to be reached, the pollutants in the bottom mud adsorbed by the covering system can be judged to reach a saturated state. After the cover system is saturated with adsorbed pollutants, as shown in fig. 3, the cover system is recovered from the water body by using a recovery device formed by magnets. The adding amount of the recoverable bottom mud covering device is 0.1-200kg/m2. Equivalent to 0.1-200kg of recoverable bottom mud cover device per square meter of bottom mud-water interface.
The present invention will be further described with reference to the following examples.
Example 1:
the preparation process of the magnetic zirconium-based material comprises the following steps: mixing 10g of bentonite with 200mL of Fe3+/Fe2+Mixing solutions (the concentration of ferric chloride hexahydrate is 0.215mol/L and the concentration of ferrous sulfate heptahydrate is 0.1075mol/L), reacting at 70 ℃ for 30min, adding 1mol/L NaOH solution into the solutions until the pH value of the mixed solution reaches 10, continuing to react for 1h, adding 100mL of zirconium oxychloride octahydrate solution (the initial concentration is 50g/L), then dropwise adding 1mol/L NaOH solution into the mixed solution until the pH value of the solution reaches 10, and then performing centrifugal separation to obtain a solid material, namely the magnetic zirconium-based material.
Constructing a recyclable mononuclear type bottom mud covering device: the magnetic zirconium-based material is wrapped by water permeable fabric, and three covering devices, namely a covering device 1, a covering device 2 and a covering device 3 are respectively constructed. As shown in FIG. 4, the covering device 1 was a covering device of a circular cake-like body having a diameter d of 8cm and containing 10g of a magnetic zirconium-based material. The covering device 2 was a rectangular parallelepiped covering device having a length d1 of 3cm, a width d2 of 1.5cm and a height of 1cm, and contained 1g of the magnetic zirconium-based material. The covering device 3 is a spindle-shaped covering device containing 1g of a magnetic zirconium-based material, and has a widest diameter d4 of 2cm and a height d3 of 3.5 cm.
Constructing a bottom sediment culture system: four cylindrical reactors were taken with an internal diameter of 8cm and a height of 40 cm. And adding bottom sludge into each reactor until the thickness of the bottom sludge is 6 cm. The first reactor did not undergo any treatment. The second reactor covered 1 covering device 1. The third reactor covers 10 covering units 2. The fourth reactor covers 10 covering units 3. After 120 days of bottom mud culture, the concentration of the active phosphorus in the overlying water in the control group reactor is 0.582mg/L, and the concentrations of the active phosphorus in the overlying water under the action of the covering device 1, the covering device 2 and the covering device 3 are 0.0402mg/L, 0.0256mg/L and 0.0301mg/L respectively. It can be seen that the removal rates of the covering device 1, the covering device 2 and the covering device 3 for the active phosphorus in the overlying water in the dissolved state are 93.1%, 95.6% and 94.8%, respectively. Therefore, the recyclable mononuclear type substrate covering device of the embodiment can effectively control the release of phosphorus in the substrate.
Example 2:
the preparation process of the magnetic lanthanum-based material comprises the following steps: mixing 10g of bentonite with 200mL of Fe3+/Fe2+Mixing solutions (the concentration of ferric chloride hexahydrate is 0.215mol/L and the concentration of ferrous sulfate heptahydrate is 0.1075mol/L), placing the mixed solutions at 70 ℃ for reaction for 30min, adding 1mol/L NaOH solution into the solutions until the pH value of the mixed solution reaches 10, continuing to react for 1h, adding 100mL of lanthanum chloride hexahydrate solution (the initial concentration is 50g/L), then adding 1mol/L NaOH solution into the mixed solution until the pH value of the solution reaches 10, and then performing centrifugal separation to obtain a solid material, namely the magnetic lanthanum-based material.
Constructing a recyclable mononuclear type bottom mud covering device: the magnetic lanthanum-based material is wrapped by water permeable fabric, and three covering devices, namely a covering device 1, a covering device 2 and a covering device 3 are respectively constructed. The covering device 1 is a covering device of a circular cake-shaped body, has the diameter of 8cm and contains 20g of magnetic lanthanum-based material. The covering device 2 is a cuboid covering device with the length of 3cm, the width of 1.5cm and the height of 2cm and contains 3g of magnetic lanthanum-based material. The covering device 3 is a spindle covering device and contains 1g of magnetic lanthanum-based material, the widest part of the spindle covering device is 2cm in diameter, and the height of the spindle covering device is 3.5 cm.
Constructing a bottom sediment culture system: four cylindrical reactors were taken with an internal diameter of 8cm and a height of 40 cm. And adding bottom sludge into each reactor until the thickness of the bottom sludge is 6 cm. The first reactor did not undergo any treatment. The second reactor covered 1 covering device 1. The third reactor covers 10 covering units 2. The fourth reactor covers 20 covering units 3. After the sediment culture for 38d, the concentration of the dissolved active phosphorus in the overlying water of the reactor of the control group is 1.28mg/L, and the concentrations of the dissolved active phosphorus in the overlying water under the action of the covering device 1, the covering device 2 and the covering device 3 are 0.0281mg/L, 0.0218mg/L and 0.0106mg/L respectively. It can be seen that the removal rates of the covering device 1, the covering device 2 and the covering device 3 for the soluble active phosphorus in the overlying water were 97.8%, 97.8% and 99.2%, respectively. Therefore, the recyclable mononuclear type substrate covering device of the embodiment can effectively control the release of phosphorus in the substrate.
Example 3:
the preparation process of the magnetic iron-based material comprises the following steps: 100g of activated carbon was mixed with 250mL of Fe3+/Fe2+Mixing the solutions (the concentration of ferric chloride hexahydrate is 1720mmol/L and the concentration of ferrous sulfate heptahydrate is 860mmol/L), reacting at 70 ℃ for 30min, adding 1mol/L NaOH solution into the solution until the pH value of the mixed solution reaches 10, and then centrifuging to obtain a solid material, namely the magnetic iron-based material.
Constructing a recyclable mononuclear type bottom mud covering device: the magnetic iron-based material is wrapped by water permeable fabric, and three covering devices, namely a covering device 1, a covering device 2 and a covering device 3 are respectively constructed. The coating device 1 was a circular cake-shaped coating device having a diameter of 8cm and containing 20g of a magnetic iron-based material. The covering device 2 is a rectangular covering device with a length of 3cm, a width of 1.5cm and a height of 2cm, and contains 3g of magnetic iron-based material. The covering device 3 is a spindle covering device, and contains 1g of magnetic iron-based material, and the widest part has a diameter of 2cm and a height of 3.5 cm.
Constructing a bottom sediment culture system: four cylindrical reactors were taken with an internal diameter of 8cm and a height of 40 cm. And adding bottom sludge into each reactor until the thickness of the bottom sludge is 8 cm. The first reactor did not undergo any treatment. The second reactor covered 1 covering device 1. The third reactor covers 10 covering units 2. The fourth reactor covers 20 covering units 3. After the bottom mud is cultured for 35d, the concentration of the dissolved active phosphorus in the overlying water of the reactor of the control group is 1.65mg/L, and the concentrations of the dissolved active phosphorus in the overlying water under the action of the covering device 1, the covering device 2 and the covering device 3 are 0.054mg/L, 0.042mg/L and 0.037mg/L respectively. According to the calculation, the removal rate of the covering device 1, the covering device 2 and the covering device 3 to the water-soluble active phosphorus is 96.7%, 97.5% and 97.8%, respectively. Therefore, the recyclable mononuclear type sediment covering device of the embodiment can effectively control the release of phosphorus in the sediment.
Example 4:
preparation of zirconium-modified zeolite: respectively weighing 10g of ZrOCl2·8H2Placing O and 20g of zeolite into a 500mL conical flask, then adding 200mL of deionized water, and magnetically stirring to dissolve the zirconium oxychloride octahydrate and keep the zeolite in a suspended state; while stirring, 1.5mol/L sodium hydroxide solution was added dropwise to adjust the pH of the mixture to 10. And continuously stirring for 2 hours, performing solid-liquid separation, washing with deionized water until the pH of the supernatant is about 7.0, finally, drying the solid in an oven at 105 ℃, and crushing to obtain the zirconium modified zeolite.
Constructing a recyclable double-core sediment covering device: taking commercial ferroferric oxide and fabric, and wrapping the fabric with the commercial ferroferric oxide to form a circular cake-shaped body I, wherein the diameter of the device is 6cm, and the thickness of the device is 1 cm; then, a water permeable fabric was selected to wrap the zirconium modified zeolite and the device I to form a device II of a circular cake shape having a diameter of 8cm and a thickness of 2cm, and the device I was located at the center of the device II, that is, the device I was surrounded by the zirconium modified zeolite.
Constructing a bottom sediment culture system: two cylindrical reactors were taken, with an internal diameter of 8cm and a height of 40 cm. And adding bottom sludge into each reactor until the thickness of the bottom sludge is 6 cm. The first reactor did not undergo any treatment. The second reactor was covered with 1 covering unit II. After the sediment is cultured for 65 days, the concentration of the dissolved active phosphorus in the overlying water of the reactor of the control group is 1.12mg/L, and the concentration of the dissolved active phosphorus in the overlying water under the action of the covering device II is 0.024 mg/L. It can be seen that the concentration of active phosphorus in the overlying water in the covering device II is significantly lower than that of the control group. Therefore, the recoverable binuclear type sediment covering device of the present embodiment can effectively control the release of phosphorus from the sediment.
Example 5:
preparation of lanthanum modified zeolite: accurately weighing 200g of natural zeolite, putting the natural zeolite into 200mL of water to form a suspension, adding 20g of lanthanum chloride hexahydrate, dissolving the lanthanum chloride hexahydrate by magnetic stirring to enable the natural zeolite to be in a suspended state, adjusting the pH value of the mixed solution to 10 by using 2mol/L sodium hydroxide solution, and continuing stirring for a period of time. And after the reaction is finished, performing solid-liquid separation on the mixture, washing the solid by using deionized water until the pH value of a supernatant reaches about 7.5, and finally placing the solid in a drying oven at 105 ℃ for drying, crushing and sieving by using a 100-mesh sieve (the particle size is less than 0.15mm) to obtain the lanthanum modified zeolite.
Constructing a recyclable double-core sediment covering device: taking commercial ferroferric oxide and fabric, and wrapping the fabric with the commercial ferroferric oxide to form a circular cake-shaped body I, wherein the diameter of the device is 6cm, and the thickness of the device is 1 cm; then selecting water permeable fabric to wrap the zirconium modified zeolite and the device I to form a device II of a circular cake body, wherein the diameter of the device is 8cm, the thickness of the device is 2cm, and the device I is positioned in the center of the device II, namely the device I is surrounded by the lanthanum modified zeolite.
Constructing a bottom sediment culture system: two cylindrical reactors were taken, with an internal diameter of 8cm and a height of 40 cm. And adding bottom sludge into each reactor until the thickness of the bottom sludge is 6 cm. The first reactor did not undergo any treatment. The second reactor was covered with 1 covering unit II. After the sediment is cultured for 59 days, the concentration of the dissolved active phosphorus in the overlying water of the reactor of the control group is 0.817mg/L, and the concentration of the dissolved active phosphorus in the overlying water under the action of the covering device II is 0.012 mg/L. It can be seen that the removal rate of the covering device II to the active phosphorus dissolved in the overlying water is 98.5%. Therefore, the recoverable binuclear type sediment covering device of the present embodiment can effectively control the release of phosphorus from the sediment.
Example 6:
preparing iron modified activated carbon: mixing 100g of activated carbon, 20g of ferric chloride hexahydrate and 200mL of deionized water, carrying out oscillation reaction for 30min, then adjusting the pH value of the mixed solution to 9 by using 1mol/L NaOH solution, continuing to react for 2h, then collecting a solid material by using a centrifugal separation method, washing for 3 times by using water, and drying to obtain the iron modified activated carbon.
Construction of a recoverable double-core sediment covering device, ① firstly preparing ferroferric oxide, and specifically preparing 1000mL of Fe3+/Fe2+The method comprises the steps of heating a solution (the concentration of ferric chloride hexahydrate is 860mmol/L and the concentration of ferrous sulfate heptahydrate is 430mmol/L), adding 1mol/L NaOH solution into the solution until the pH value of a mixed solution reaches 10, dropwise adding the NaOH solution while maintaining an oscillation state, and then performing centrifugal separation to obtain a solid material, namely a ferroferric oxide material ②, wrapping the self-made ferroferric oxide into a device I with a square body by adopting a fabric, wherein the device I and iron modified activated carbon are wrapped by adopting a water-permeable fabric with the length of 6cm, the width of 5cm and the height of 2 cm. ③ to form a device II (a circular cake body with the diameter of 8cm and the thickness of 3cm), and the device I is located in the center of the device II, namely the device I is wrapped by the iron modified activated carbon.
Constructing a bottom sediment culture system: constructing a bottom sediment culture system: two cylindrical reactors were taken, with an internal diameter of 8cm and a height of 40 cm. And adding bottom sludge into each reactor until the thickness of the bottom sludge is 8 cm. The first reactor did not undergo any treatment. The second reactor was covered with 1 covering unit II. After the sediment is cultured for 110d, the concentration of the dissolved active phosphorus in the overlying water of the reactor of the control group is 1.92mg/L, and the concentration of the dissolved active phosphorus in the overlying water under the covering action is 0.0326 mg/L. The calculated reduction rate of the covering device II on the dissolved active phosphorus in the overlying water is 98.3%. Therefore, the recoverable dual-core type sediment covering device can effectively control the release of phosphorus in the sediment.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.

Claims (10)

1. A recoverable sediment covering device is characterized in that: the composite material comprises an inner layer structure and an outer layer structure, wherein the inner layer structure is coated by the outer layer structure;
the inner layer structure is composed of a magnet active material;
the outer layer structure is made of a porous material;
the pore diameter of the porous material is smaller than the particle size of the magnet active material in the inner layer structure;
the size of the widest part of the recoverable bottom mud covering device is 1-50cm, the recoverable bottom mud covering device is thrown above a bottom mud-water interface, and after the adsorption of pollutants in the bottom mud is saturated, the recoverable bottom mud covering device is removed from the water body by using the action of an external magnetic field.
2. The recoverable bottom mud cover device of claim 1, wherein: the recyclable substrate sludge covering device includes a recyclable single-core substrate sludge covering device and a recyclable double-core substrate sludge covering device.
3. The recoverable bottom mud cover device of claim 2, wherein: the recyclable mononuclear type substrate covering device comprises an inner layer structure and an outer layer structure, wherein the magnet active material of the inner layer structure is selected from a magnetic iron-based material, a magnetic zirconium-based material, a magnetic magnesium iron-based material and a magnetic lanthanum-based material, and the porous material of the outer layer structure is a fabric.
4. The recoverable substrate sludge cover apparatus of claim 3, wherein: the shape of the recyclable mononuclear type bottom mud covering device comprises a circular cake-shaped body, a cuboid, a spindle body, a sphere, an ellipsoid, a cone, a table body and a cylinder; and/or the presence of a gas in the gas,
the diameter of the recoverable mononuclear type bottom mud covering device of the round cake-shaped body is 1-50cm, and the thickness of the recoverable mononuclear type bottom mud covering device is 1-5 cm; and/or the presence of a gas in the gas,
the length of the rectangular recoverable mononuclear type bottom mud covering device is 1-50cm, the width is 1-20cm, and the height is 1-10 cm; and/or the presence of a gas in the gas,
the height of the recoverable mononuclear type bottom mud covering device of the spindle body is 2-20cm, and the diameter of the widest part is 1-10 cm; and/or the presence of a gas in the gas,
the diameter of the recoverable mononuclear type sediment covering device of the sphere is 1-20 cm; and/or the presence of a gas in the gas,
the long diameter of the recoverable mononuclear type bottom mud covering device of the ellipsoid is 2-20cm, and the short diameter is 1-10 cm; and/or the presence of a gas in the gas,
the linear distance of the widest position of the bottom surface of the recoverable mononuclear type bottom mud covering device of the vertebral body is 1-20cm, and the height is 1-20 cm; and/or the presence of a gas in the gas,
the linear distance of the widest part of the bottom surface of the recoverable mononuclear type bottom mud covering device of the platform body is 2-20cm, the linear distance of the widest part of the top surface is 1-10cm, and the height is 1-10 cm; and/or the presence of a gas in the gas,
the straight line distance of the widest part of the cross section of the recyclable mononuclear type bottom mud covering device of the cylinder is 1-20cm, and the height of the recyclable mononuclear type bottom mud covering device is 1-20 cm.
5. The recoverable substrate sludge cover apparatus of claim 3, wherein: the preparation process of the magnetic iron-based material comprises the following steps: mixing a carrier material and a soluble ferric iron/ferrous iron mixed solution, reacting for 0.5-2h at 70-80 ℃, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 10-11, cleaning and drying; and/or the presence of a gas in the gas,
the preparation process of the magnetic zirconium-based material comprises the following steps: mixing a magnetic iron-based material and zirconium oxychloride octahydrate, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, cleaning and drying; and/or the presence of a gas in the gas,
the preparation process of the magnetic magnesium-iron-based material comprises the following steps: mixing a magnetic iron-based material and a magnesium-iron solution, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 11-13, cleaning and drying; and/or the presence of a gas in the gas,
the preparation process of the magnetic lanthanum-based material comprises the following steps: mixing a magnetic iron-based material and a lanthanum salt solution, reacting for 0.5-2h, then dropwise adding 0.5-2mol/L alkaline solution, adjusting the pH value of the mixed solution to 8-11, cleaning and drying;
wherein the alkaline solution is selected from sodium hydroxide solution, potassium hydroxide solution or sodium carbonate solution.
6. The recoverable bottom mud cover device of claim 5, wherein: in the preparation process of the magnetic iron-based material, the carrier material is selected from more than one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and active carbon; the molar ratio of ferric iron to ferrous iron in the soluble ferric iron/ferrous iron mixed solution is (2-4):1, ferric iron in the soluble ferric iron/ferrous iron mixed solution is prepared by ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and ferrous iron is prepared by ferrous chloride tetrahydrate, ferrous sulfate heptahydrate or ferrous nitrate; and/or the presence of a gas in the gas,
in the preparation process of the magnetic magnesium-iron-based material, magnesium ions in a magnesium-iron solution are prepared from magnesium chloride hexahydrate, iron ions are prepared from ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and the molar ratio of the magnesium ions to the iron ions is (2-4): 1; and/or the presence of a gas in the gas,
in the preparation process of the magnetic lanthanum-based material, lanthanum salt is selected from more than one of lanthanum chloride hexahydrate and lanthanum nitrate hexahydrate.
7. The recoverable bottom mud cover device of claim 2, wherein: the recyclable dual-core sediment covering device comprises an inner layer structure and an outer layer structure, wherein the inner layer structure comprises an inner core and an outer core, the magnet active material of the inner core is commercial ferroferric oxide or self-made ferroferric oxide, the active material of the outer core is selected from iron-based materials, zirconium-based materials, magnesium-iron-based materials and lanthanum-based materials, and the volume ratio of the inner core to the outer core in the inner layer structure is 1 (1-10); the porous material of the outer layer structure is a fabric; and/or the presence of a gas in the gas,
the commercial ferroferric oxide is selected from ferroferric oxide prepared by domestic or foreign manufacturers, and the purity of the ferroferric oxide is 95 +/-1%; and/or the presence of a gas in the gas,
the preparation process of the self-made ferroferric oxide comprises the following steps: placing 0.1-2mol/L soluble ferric iron/ferrous iron mixed solution into a container, placing the container at 70-80 ℃ for reaction, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 10-11, cleaning and drying; and/or the presence of a gas in the gas,
the preparation process of the iron-based material comprises the following steps: mixing iron salt, a carrier material and water, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, cleaning and drying; and/or the presence of a gas in the gas,
the preparation process of the zirconium-based material comprises the following steps: mixing zirconium oxychloride octahydrate, a carrier material and water, then dropwise adding 0.2-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 7-10, cleaning and drying; and/or the presence of a gas in the gas,
the preparation process of the magnesium-iron-based material comprises the following steps: mixing a carrier material and a magnesium-iron solution, then dropwise adding 0.5-2mol/L sodium hydroxide or potassium hydroxide solution, adjusting the pH value of the mixed solution to 11-13, cleaning and drying; and/or the presence of a gas in the gas,
the preparation process of the lanthanum-based material comprises the following steps: mixing lanthanum salt, a carrier material and water, then dropwise adding 0.2-2mol/L alkaline solution, adjusting the pH value of the mixed solution to 8-11, cleaning and drying;
wherein the alkaline solution is selected from sodium hydroxide solution, potassium hydroxide solution or sodium carbonate solution.
8. The recoverable bottom mud covering device according to claim 7, wherein in the homemade ferroferric oxide preparation process, the molar ratio of ferric ions to ferrous ions in the soluble ferric/ferrous mixed solution is (2-4):1, the ferric ions are prepared from ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and the ferrous ions are prepared from ferrous chloride tetrahydrate, ferrous sulfate heptahydrate or ferrous nitrate; and/or the presence of a gas in the gas,
in the preparation process of the iron-based material, the zirconium-based material, the magnesium-iron-based material and the lanthanum-based material, the carrier material is selected from more than one of bentonite, kaolin, diatomite, zeolite, attapulgite, sepiolite, illite, siderite and activated carbon; and/or the presence of a gas in the gas,
in the preparation process of the iron-based material, the iron salt is selected from more than one of ferric chloride hexahydrate, ferric sulfate or ferric nitrate; and/or the presence of a gas in the gas,
in the preparation process of the magnesium-iron-based material, magnesium ions in a magnesium-iron solution are prepared from magnesium chloride hexahydrate, iron ions are prepared from ferric chloride hexahydrate, ferric sulfate or ferric nitrate, and the molar ratio of the magnesium ions to the iron ions is (2-4): 1; and/or the presence of a gas in the gas,
in the preparation process of the lanthanum-based material, the lanthanum salt is selected from more than one of lanthanum chloride hexahydrate and lanthanum nitrate hexahydrate.
9. The recoverable bottom mud cover device of claim 7, wherein: the shape of the recoverable double-core sediment covering device comprises a circular cake-shaped body, a cuboid, a spindle body, a sphere, an ellipsoid, a cone, a table body and a cylinder; and/or the presence of a gas in the gas,
the diameter of the recoverable double-core type bottom mud covering device of the circular cake-shaped body is 1-50cm, and the thickness of the recoverable double-core type bottom mud covering device is 1-5 cm; and/or the presence of a gas in the gas,
the length of the rectangular recoverable double-core type bottom mud covering device is 1-50cm, the width is 1-20cm, and the height is 1-10 cm; and/or the presence of a gas in the gas,
the height of the recoverable double-core type bottom mud covering device of the spindle body is 2-20cm, and the diameter of the widest part is 1-10 cm; and/or the presence of a gas in the gas,
the diameter of the recoverable double-core sediment covering device of the sphere is 1-20 cm; and/or the presence of a gas in the gas,
the recoverable double-core type bottom mud covering device of the ellipsoid has a long diameter of 2-20cm and a short diameter of 1-10 cm; and/or the presence of a gas in the gas,
the linear distance of the widest position of the bottom surface of the recoverable double-core sediment covering device of the vertebral body is 1-20cm, and the height is 1-20 cm; and/or the presence of a gas in the gas,
the linear distance of the widest part of the bottom surface of the recoverable double-core sediment covering device of the platform body is 2-20cm, the linear distance of the widest part of the top surface is 1-10cm, and the height is 1-10 cm; and/or the presence of a gas in the gas,
the linear distance of the widest part of the cross section of the recoverable double-core type bottom mud covering device of the column body is 1-20cm, and the height of the recoverable double-core type bottom mud covering device is 1-20 cm.
10. Use of the recoverable substrate cover apparatus of claim 1 for the release control of endogenous contaminants in the substrate sludge of a body of water.
CN202010017600.4A 2020-01-08 2020-01-08 Recoverable bottom mud covering device and application Pending CN111186971A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115518611A (en) * 2022-10-17 2022-12-27 北京中岩大地环境科技有限公司 Preparation method and application of magnetic ferrozirconium modified sepiolite artificial wetland matrix

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000308895A (en) * 1999-04-26 2000-11-07 Ebara Corp Treatment of organic sewage
CN104528868A (en) * 2014-12-31 2015-04-22 华南师范大学 Application of magnetic particles in in-situ treatment of eutrophic water and sedimentary phosphate
CN105668964A (en) * 2016-03-23 2016-06-15 上海海洋大学 In-situ combination method used for sediment nitrogen and phosphorus release control
CN105753276A (en) * 2016-03-23 2016-07-13 上海海洋大学 Contaminated bottom mud covering ball as well as preparation method and application thereof
CN108479689A (en) * 2018-04-23 2018-09-04 中国环境科学研究院 A kind of adsorbent of removal arsenic in waste water acid ion
CN110548490A (en) * 2018-05-31 2019-12-10 华中科技大学 Preparation method and application of recyclable lanthanum modified bentonite phosphorus removal material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000308895A (en) * 1999-04-26 2000-11-07 Ebara Corp Treatment of organic sewage
CN104528868A (en) * 2014-12-31 2015-04-22 华南师范大学 Application of magnetic particles in in-situ treatment of eutrophic water and sedimentary phosphate
CN105668964A (en) * 2016-03-23 2016-06-15 上海海洋大学 In-situ combination method used for sediment nitrogen and phosphorus release control
CN105753276A (en) * 2016-03-23 2016-07-13 上海海洋大学 Contaminated bottom mud covering ball as well as preparation method and application thereof
CN108479689A (en) * 2018-04-23 2018-09-04 中国环境科学研究院 A kind of adsorbent of removal arsenic in waste water acid ion
CN110548490A (en) * 2018-05-31 2019-12-10 华中科技大学 Preparation method and application of recyclable lanthanum modified bentonite phosphorus removal material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
吴俊麟: "镁铁层状双金属氢氧化物对磷酸盐的吸附作用及对内源磷释放的控制效果及机制", 《环境科学》 *
颜红侠: "《现代精细化工实验》", 31 January 2005 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115518611A (en) * 2022-10-17 2022-12-27 北京中岩大地环境科技有限公司 Preparation method and application of magnetic ferrozirconium modified sepiolite artificial wetland matrix

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Application publication date: 20200522