CN112604667A - Mud-water simultaneous treatment type bottom mud repairing material and preparation method and application thereof - Google Patents
Mud-water simultaneous treatment type bottom mud repairing material and preparation method and application thereof Download PDFInfo
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- CN112604667A CN112604667A CN202011336733.4A CN202011336733A CN112604667A CN 112604667 A CN112604667 A CN 112604667A CN 202011336733 A CN202011336733 A CN 202011336733A CN 112604667 A CN112604667 A CN 112604667A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
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- 230000035484 reaction time Effects 0.000 description 3
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
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- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a muddy water simultaneous treatment type bottom mud repairing agent material. Specifically, the sediment repair agent material takes natural aluminosilicate, calcium salt, magnesium salt, sodium salt, modified cellulose, acrylic acid polymer and polyhydroxy compound as raw materials, and the colloid-shaped sediment repair material with stable viscosity is obtained through the process flows of thermal crosslinking, drying, crushing, dissolving, high-speed shearing, emulsifying and the like. The bottom mud repairing agent disclosed by the invention is covered on the bottom mud of the river, so that the upward turning of the bottom mud and the escape of pollutants in the bottom mud can be effectively prevented, the secondary pollution of the bottom mud to a water body is avoided, the contents of total nitrogen, total phosphorus and the like in the water body can be reduced, the water quality is rapidly purified, and the purpose of treating the mud and the water at the same time is achieved. In addition, the invention also relates to a preparation method and a use method of the mud-water simultaneous treatment type bottom mud repairing agent material.
Description
Technical Field
The invention relates to the field of polluted water body remediation, in particular to a sediment remediation material for treating both mud and water, and a preparation method and application thereof.
Background
With the acceleration of industrialization and urbanization, the ecological environment is increasingly damaged in recent years, and the river pollution problem is particularly prominent. River pollution can be divided into endogenous pollution and exogenous pollution, wherein the endogenous pollution mainly comes from bottom mud pollution.
The river sediment is an important component of the river and can be continuously exchanged with flowing overlying water to generate biomass. When the pollutants enter the river, the microorganisms in the bottom mud can filter, adsorb and degrade the pollutants, and the self-cleaning of the river is facilitated. However, as more and more pollutants are deposited in the bottom sediment and are released into the overlying water after the load of the pollutants exceeds the load of the pollutants, secondary pollution is caused, the pollution degree of the pollutants even exceeds primary pollution, and the pollution of the bottom sediment becomes the primary endogenous pollution of the river channel.
At present, methods for treating river pollution are mainly divided into an ex-situ remediation method and an in-situ remediation method. The ex-situ remediation refers to that after sludge in the river is dug out, the bottom mud is treated to be qualified by adopting chemical, physical, biological and other methods outside the river and then is buried, and the in-situ remediation refers to that the pollution components in the bottom mud are degraded in situ in the river by adopting chemical, physical, biological and other methods. Although the ex-situ remediation takes effect quickly, a large amount of labor and cost investment is required, an additional site is required for landfill treatment of the removed bottom mud, and the pollution problem of the bottom mud to the landfill site needs to be considered. Therefore, the application of the ex-situ remediation technology in the modern sediment treatment is less and less, and the in-situ remediation technology has the advantages of small investment, easy operation, environmental protection, difficult generation of secondary pollution and the like because the in-situ remediation technology can directly fix and purify the sediment in any basin in any season, and becomes an important direction for solving the sediment pollution of the water body in future.
However, the existing in-situ sediment remediation method still has a plurality of problems. In-situ physical remediation, for example, the resuspension may have adverse effects on the water environment, and the aeration technology is difficult to meet the requirements on energy consumption and treatment effect; in-situ bioremediation, the repair period is longer, and the influence of uncontrollable environmental factors is greater; the selection of the repairing agent and the dosage is very important in the in-situ chemical repairing, otherwise, the secondary pollution is easily caused. For another example, CN 102775030a discloses a method of covering bottom mud, but when the bottom mud environment changes, the captured pollutants may be released into the water again. CN 102617089a discloses a covering material prepared from a cement cured material, but it is too alkaline and has a small specific surface area, and is easily deposited in the bottom mud, so that it cannot perform a covering function.
Therefore, the development of a new sediment in-situ remediation technology and a corresponding sediment remediation material have very important significance.
Disclosure of Invention
Aiming at the limitations of the prior art, the invention provides a sediment remediation material which aims at treating both mud and water and can carry out in-situ remediation on sediment and effectively purify water, and a preparation method and application thereof.
In a first aspect, the present invention provides a sludge-water compatible type bottom mud repairing material prepared by the process of: fully mixing the raw materials in the following proportion, stirring at a high speed for 2 hours at the temperature of 70-80 ℃ to fully react, cooling, filtering, drying and ball-milling to obtain powder of preferably 150-350 meshes, more preferably 200 meshes: 1000 parts by weight of natural aluminosilicate; 5 to 10 parts by weight of a calcium salt; 5 to 10 parts by weight of a magnesium salt; 5 to 10 parts by weight of a sodium salt; 10 to 15 parts by weight of a modified cellulose; 20 to 25 parts by weight of an acrylic polymer; 5 to 10 parts by weight of a polyhydroxy polymer.
Preferably, the sediment repair material has a gel colloid value of 1800-3000 mL/15g, an expansion multiple of 125-450 mL/g, and a viscosity of 1300-6000 mPas measured at 25 ℃, 4% concentration and 60r/min of rotation by a Brooks SNB-2 digital display viscometer.
In some embodiments, the natural aluminosilicate may be selected from one or more of bauxite and silica mixed powder, tourmaline powder, (fine) mica powder, montmorillonite powder, bentonite, and clay powder; preferably one or more selected from the group consisting of montmorillonite powder, clay powder and (fine) mica powder. By way of example only and not limitation, the (fine) mica powder can resist high temperature, acid, alkali and corrosion due to good insulation property and strong adhesive force, so that the stability of the gel can be effectively improved, and the service life of the bottom mud repairing agent can be prolonged; the clay powder has wide distribution, good settleability and great price advantage, can reduce the use of calcium salt and magnesium salt, and has good control effect on the cost input; the montmorillonite powder is fine and smooth in powder, has the colloid dispersion characteristic, can effectively adsorb impurities after water absorption and expansion, and is beneficial to improving the purification effect of the bottom mud repairing agent.
It should be understood that the calcium salt, magnesium salt and sodium salt used in the invention are non-toxic and harmless, and do not add new pollution burden to the watershed water body. In some embodiments, the calcium salt may be selected from calcium chloride, calcium oxide. In some embodiments, the magnesium salt may be selected from magnesium sulfate, magnesium oxide. In some embodiments, the sodium salt may be selected from, for example, sodium carbonate, sodium bicarbonate, and sodium percarbonate.
Preferably, the polyhydroxy polymer is selected from hydroxyl-containing drying alkyd resins and polyester resins, preferably having a weight average molecular weight of 1500 to 2500. Preferably, the dry alkyd resin is prepared from natural materials such as tung oil, soybean oil and catalpa oil, is not easy to dissolve in water at normal temperature, but has high stability and good viscosity after dissolution; preferably, the polyester resin is easily soluble in water although it has a low viscosity, and the cured gel layer has high hardness and is stable. Preferably, when the total mass of the polyhydroxy polymer and the acrylic acid polymer accounts for 3-4% of the mass of other raw materials, the bottom mud repairing agent has the best performance.
In the bottom mud repairing agent material, natural aluminosilicate, modified cellulose and acrylic acid polymer are polymerized at high temperature to form unique inorganic water-absorbing gel, so that the bottom mud repairing agent material has extremely strong water-absorbing swelling effect, obvious precipitation and aggregation effect after entering water, difficult dispersion and extremely strong covering and plugging effect, can plug pollutants in the bottom mud at the water bottom to prevent the pollutants from being released into natural water, and simultaneously has excellent phosphorus fixing effect, can solidify inorganic phosphorus in water into the gel, can also play a part of role in absorbing nutrients in water, and reduces water eutrophication.
In another aspect, the present invention provides a method for preparing the above-mentioned sediment remediation material, wherein the method comprises the following steps:
step 1), completely mixing 1000 parts by weight of natural aluminosilicate, 5 to 10 parts by weight of calcium salt, 5 to 10 parts by weight of magnesium salt, 5 to 10 parts by weight of sodium salt, 10 to 15 parts by weight of modified cellulose, 20 to 25 parts by weight of acrylic acid polymer and 5 to 10 parts by weight of polyhydroxy polymer, and then adding water, preferably deionized water, to prepare a 20% suspension;
step 2), stirring the suspension at a constant temperature of 70-80 ℃ for 2 hours at a high speed (such as more than 300r/min) to fully react the suspension;
step 3), cooling, filtering and drying the mixture obtained in the step 2);
and 4) ball-milling the mixture obtained in the step 3) into powder of preferably 150-350 meshes, more preferably 200 meshes.
In some embodiments, the method of the present invention further comprises preparing the modified cellulose prior to step 1). In some embodiments, the preparation of the modified cellulose is performed by: grinding natural cellulose into powder, adding the powder into an alkalizer, and then adding organic alcohol as a solvent; adding 30-35 wt% of alkaline solution at the temperature of 30-35 ℃ and at the stirring speed of 200-300 r/min; stirring is continued for at least 30 minutes to obtain the alkalized cellulose. In the adding process of the alkaline solution, the adding speed of the alkaline solution is not more than 1% per minute of the calculated amount (the adding alkali equivalent amount according to the detected amount of the carboxyl on the surface of the natural cellulose is 1: 2-1: 5), the whole adding process is controlled to be about 2 hours, and the adding time can be properly prolonged according to the reaction temperature of a system in the adding process.
In some embodiments, the method of preparing a modified cellulose may further comprise: and transferring the obtained alkalized cellulose to a (vertical) etherification machine, and adding an etherifying agent to obtain the etherified modified cellulose, wherein the pH value of a reaction system is controlled to be 6.8-7.0, the reaction temperature is controlled to be 70 ℃, and the reaction time is controlled to be 70 minutes. Preferably, the dosage of the alkalization agent and the etherifying agent can be adjusted, for example, the dosage of the alkalization agent is increased and the dosage of the etherifying agent is reduced simultaneously, so that the occurrence of side reactions is controlled and reduced, and the consumption of the etherifying agent is saved; and after the obtained etherified and modified cellulose is dissolved in water, no turbidity is generated. Wherein the etherifying agent used may be selected from cationic etherifying agents, preferably trimethyl (3-chloro-2-hydroxypropyl) ammonium chloride in combination with chloroacetic acid. Preferably, the equivalent ratio of the alkalizer to the natural cellulose carboxyl groups is 7: 1-5: 1, and the equivalent ratio of the etherifying agent to the natural cellulose is 1:12.5-1: 8.
Preferably, in the process of preparing the modified cellulose, the organic alcohol used may be an organic alcohol having a chain length of not more than 4 carbons, such as propanol, isopropanol, etc., preferably isopropanol. Preferably, the powdered cellulose is well dispersed in isopropanol and alkalized to give a homogeneous alkali-modified cellulose.
Preferably, hydroxyethyl cellulose, carboxymethyl cellulose and polyanionic cellulose can be obtained by changing the components of the organic solvent and natural cellulose, and the hydroxyethyl cellulose, the carboxymethyl cellulose and the polyanionic cellulose are all non-toxic and odorless white flocculent powder, are easy to dissolve in water and can improve the viscosity of the sediment repairing agent.
The production process of cellulose modification combines the advantages of a common kneading method and a slurry method, reduces the reaction time while reducing the use amount of an organic solvent, and the obtained alkaline cellulose has high stability and good uniformity and is beneficial to improving the quality of the bottom mud repairing agent. In some specific embodiments, the alkaline solution is selected from a solution of sodium hydroxide and/or potassium hydroxide.
In other aspects, the invention also provides a raw material composition for preparing the sediment remediation material.
In still another aspect, the invention provides a method for applying the sediment remediation material. Specifically, the bottom sediment repairing material and water are prepared into 10% suspension, high-speed shearing emulsification is carried out through a high-speed mechanical emulsifying machine at the rotating speed of 10000r/min to 13000r/min, solid is uniformly dispersed to obtain colloid, and then the colloid is cooled automatically in a natural environment to form the repairing material with stable viscosity.
The repairing material with stable viscosity is put into a water body environment to be treated in a liquid state, and forms off-white gel in a short time, the gel can be well covered on the bottom sediment, the pH value is stable at 6.0-9.0, and the repairing material is non-toxic and harmless. Thus, the method can be directly put into a river channel to treat bottom mud and watershed water.
In the invention, the bottom sludge is treated harmlessly by in-situ remediation and mud-water simultaneous treatment, so that pollution transfer is avoided. The bottom sediment repairing agent can comprehensively eliminate bottom sediment pollutants, eliminate organic pollutants and inorganic pollutants such as fluoride, sulfide, chloride and the like in the bottom sediment, eliminate non-degradable macromolecular organic pollutants such as PVA, heterocycles and phenols, and solve heavy metal pollution, particularly heavy metal mercury pollution, in the bottom sediment. In addition, the pH value of the bottom mud is kept within the range of 6.5-9 after the treatment, and the ORP (oxidation-reduction potential) reaches more than 300 mv.
In addition, practice proves that the total volume of the amount of the sediment mud after the treatment is reduced by 20-30%.
The bottom mud repairing material has the characteristics of cost saving, high treatment efficiency and environmental protection, and has good fixed viscosity and high adsorption capacity on water pollutants. The bottom mud repairing material has wide raw material materials and simple manufacturing process, can be used for treating various water environments, and can meet the treatment requirements of most water environments at the present stage.
Therefore, the bottom mud repairing material can be applied to treatment of various river waters. For example, the following water body environment treatments are applicable:
the bottom mud repairing agent can be used for river channels with exposed bottom mud caused by river water exhaustion, can be quickly solidified on the surface of the bottom mud, reduces the smell of the exposed bottom mud, prevents the loss of the exposed bottom mud, prevents the exposed bottom mud from polluting a watershed embankment and the surrounding environment, and also ensures good water inlet conditions in the later period of a treatment area;
the bottom sediment repairing agent can be used for a riverbed subjected to artificial dredging, the riverbed subjected to artificial dredging has low self immunity, and partial aquatic animal excrement and remains of aquatic plants;
the bottom mud repairing agent can be directly put into urban rivers and natural rivers, can be quickly settled, forms a sealing layer on the surface of the bottom mud, separates a water body from a riverbed, solves the problem of upward turning of the bottom mud in summer, and ensures that the total volume reduction of the bottom mud after treatment can reach 20-30%;
the bottom sediment repairing agent can be used for early-stage treatment of ecological wetland, and can be used for quickly fixing the bottom sediment and the remains of submerged plants in the bottom sediment at the early stage of wetland treatment of ecological system disorder, so that harmless treatment can be performed on the bottom sediment losing bioactivity, and further transfer of pollutants is avoided. In addition, the water environment system which is polluted secondarily is purified, pollutants are adsorbed, pollution indexes are reduced, and a good foundation is laid for later construction of the ecological wetland.
The bottom mud repairing agent can eliminate organic pollutants, inorganic pollutants such as fluoride, sulfide and chloride in the bottom mud, and non-degradable macromolecular organic pollutants (such as PVA, heterocycles and phenols), solve heavy metal pollution, particularly heavy metal mercury, in the bottom mud, and solve the problem of secondary pollution of upper river water. Specifically, the bottom sediment repairing agent disclosed by the invention is in close contact with a water body, and meanwhile, effective components in the bottom sediment repairing agent adsorb water body pollutants, so that the water body is purified, and indexes such as COD (chemical oxygen demand), ammonia nitrogen, total phosphorus and the like are effectively reduced. After the bottom sediment repairing agent is fixed and repaired, degradable organic pollutants and inorganic pollutants, non-degradable macromolecular organic pollutants and heavy metal pollutants in the bottom sediment are comprehensively controlled, and the water body is not polluted secondarily; meanwhile, the invention further purifies the water quality of the water body through close contact with water flow, thereby really realizing in-situ remediation and simultaneous treatment of muddy water.
Drawings
FIG. 1 is a photograph of the raw material of the present invention;
FIG. 2 is a photograph of the colloidal state formed by the sediment repair material of the present invention and water;
FIG. 3 is a photograph showing the effect of the sediment remediation agent of the present invention in fixing sediment.
Detailed Description
Generally, the invention provides a brand-new sediment in-situ remediation technology and a corresponding sediment remediation agent material. The bottom sediment repairing agent material is an inorganic water-absorbing gel, has extremely strong water-absorbing swelling effect, obvious water-entering precipitation and aggregation effect and better covering effect. Meanwhile, the inorganic phosphorus in the water body can be solidified into the gel by a good phosphorus solidification effect, so that the eutrophication of the water body is reduced. Therefore, the sediment in-situ remediation technology can effectively purify water while performing in-situ remediation on the sediment.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It is to be understood that the description herein is only illustrative of the present invention and is not intended to limit the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in the specification of the present invention are for the purpose of describing particular embodiments only and are not intended to limit the present invention. The reagents and instruments used herein are commercially available, and the values referred to in percentages are those conventionally used by those skilled in the art, and the characterization means referred to can be referred to the description in the prior art, and will not be described herein.
The invention provides an in-situ remediation and muddy water simultaneous treatment type bottom mud remediation agent material which is prepared from raw materials including natural aluminosilicate, calcium salt, magnesium salt, sodium salt, modified cellulose, acrylic acid polymer and polyhydroxy polymer.
Specifically, the bottom sediment repairing agent material is prepared by the following steps:
adding powdered natural cellulose into an alkalizer, taking an isopropanol solution as an organic solvent, wherein the weight ratio of the organic solvent to the natural cellulose is 2:1, adding a 30-35% sodium hydroxide solution while stirring, uniformly stirring at the temperature of 30-35 ℃, and carrying out alkalization reaction for 30 min; after alkalization, adding natural aluminosilicate, calcium magnesium salt, acrylic acid polymer and polyhydroxy polymer (1000 parts of natural aluminosilicate, 5-10 parts of calcium salt, 5-10 parts of magnesium salt, 5-10 parts of sodium salt, 10-15 parts of modified cellulose (dry component), 20-25 parts of polyacrylic acid and 5-10 parts of polyhydroxy polymer), and completely mixing to prepare the sediment repair material. The gel obtained by testing has a colloid value of 1800-3000 ml/15g, an expansion multiple of 125-450 ml/g, a rotation speed of 60r/min at a concentration of 4%, and a viscosity of 1300-6000 mPa & s.
The use method of the repair material comprises the following steps: preparing 10% turbid liquid from the prepared repairing material, stirring for 30min at a constant temperature of 70-80 ℃ to fully dissolve the turbid liquid to obtain the turbid liquid, and then stirring at a high speed by a high-speed mechanical emulsifying machine at a rotating speed of 10000 r/min-13000 r/min to uniformly disperse solid to obtain colloid, wherein the colloid is automatically cooled in a natural environment to form the bottom mud repairing agent material with stable viscosity. The obtained bottom mud repairing agent is in a beige gel state, the pH value is stable at 6.0-9.0, and the bottom mud repairing agent is non-toxic and harmless and can be directly thrown into a river channel to treat bottom mud and a watershed water body.
Next, the present invention will be further described with reference to specific embodiments.
Example 1
Adding powdered natural cellulose into an alkalizer, taking an isopropanol solution as an organic solvent, wherein the mass ratio of the organic solvent to the natural cellulose is 2:1, adding a 30 wt% sodium hydroxide solution while stirring, uniformly stirring at the temperature of 35 ℃, and carrying out alkalization reaction for 30 min.
After alkalization, 1000 parts by weight of natural aluminosilicate, 7.5 parts by weight of calcium chloride, 5 parts by weight of magnesium sulfate, 5 parts by weight of sodium carbonate, 20 parts by weight of polyacrylic acid (Mw: 3000 to 5000), and 5 parts by weight of a dry alkyd resin (average molecular weight about 2000) were added to 10 parts by weight of the obtained modified cellulose (dry component), and the above materials were uniformly mixed.
Subsequently, water was added under stirring to prepare a suspension having a solid content of 20%. The suspension was heated to 72 ℃ and stirred at high speed at 500r/min for 2 hours, after which the reaction was cooled to room temperature, filtered and dried.
The dried mixture was then added to a ball mill for ball milling to a 200 mesh powder.
The powder was reconstituted to a gel and the gel obtained was tested, wherein the gel value was 1900mL/15g, the swelling factor was 225mL/g, the number of revolutions at 4% concentration was 60r/min and the viscosity was 1400 mPas.
Example 2
Adding powdered natural cellulose into an alkalizer, taking an isopropanol solution as an organic solvent, wherein the mass ratio of the organic solvent to the natural cellulose is 2:1, adding a 35 wt% sodium hydroxide solution while stirring, uniformly stirring at the temperature of 35 ℃, and carrying out alkalization reaction for 30 min.
After alkalization, 1000 parts by weight of natural aluminosilicate, 5 parts by weight of calcium chloride, 5 parts by weight of magnesium sulfate, 5 parts by weight of sodium carbonate, 22.5 parts by weight of polyacrylic acid, and 7.5 parts by weight of drying alkyd resin were added to obtain modified cellulose (dry component) 12 parts by weight. A sediment remediation gel was then prepared in the same manner as in example 1.
The resulting gel was tested, wherein the gel value was 2800mL/15g, the swelling factor was 430mL/g, the number of revolutions at 4% concentration was 60r/min, and the viscosity was 5200 mPas.
Example 3
Adding powdered natural cellulose into an alkalizer, taking an isopropanol solution as an organic solvent, wherein the mass ratio of the organic solvent to the natural cellulose is 2:1, adding a 30 wt% sodium hydroxide solution while stirring, uniformly stirring at the temperature of 30 ℃, and carrying out alkalization reaction for 30 min.
After alkalization, 1000 parts by weight of natural aluminosilicate, 10 parts by weight of calcium oxide, 10 parts by weight of magnesium sulfate, 10 parts by weight of sodium hydrogencarbonate, 20 parts by weight of polyacrylic acid, and 5 parts by weight of polyester resin were added to the resulting modified cellulose (dry matter) as 10 parts by weight. A sediment remediation gel was then prepared in the same manner as in example 1.
The obtained gel was tested, wherein the gel value was 1800mL/15g, the swelling factor was 125mL/g, the number of revolutions was 60r/min at 4% concentration, and the viscosity was 1300 mPas.
Example 4
A sediment remediation gel was prepared in the same manner as in example 2, except that a 35% by weight potassium hydroxide solution was used in place of the sodium hydroxide solution.
The obtained gel was tested, wherein the gel value was 2750mL/15g, the swelling factor was 440mL/g, the concentration was 4% and the viscosity was 5100 mPas at 60 r/min.
Example 5
A bottom sediment repair gel was prepared in the same manner as in example 2, except that the obtained modified cellulose (dry content) was used as 15 parts by weight to add other substances accordingly.
The resulting gel was tested, wherein the gel value was 2900mL/15g, the swelling factor was 420mL/g, the concentration was 4% and the viscosity was 5900 mPas at 60r/min of revolution.
Example 6
Adding powdered natural cellulose into an alkalizer, taking an isopropanol solution as an organic solvent, wherein the weight ratio of the organic solvent to the natural cellulose is 2:1, adding 35 wt% of sodium hydroxide solution while stirring, uniformly stirring at the temperature of 35 ℃, and carrying out alkalization reaction for 30 min.
And (3) transferring the alkalized cellulose obtained by solid-liquid separation into a vertical etherification machine, adding 0.1 equivalent of trimethyl (3-chloro-2-hydroxypropyl) ammonium chloride and 0.1 equivalent of chloroacetic acid, controlling the pH of a reaction system at 6.8-7.0, controlling the reaction temperature at 70 ℃ and controlling the reaction time to be 70 min. And after the reaction is finished, carrying out solid-liquid separation to obtain dry etherified modified cellulose.
The etherified modified cellulose (dry component) was taken as 12 parts by weight, and 1000 parts by weight of natural aluminosilicate, 5 parts by weight of calcium salt, 5 parts by weight of magnesium salt, 5 parts by weight of sodium salt, 22.5 parts by weight of polyacrylic acid, and 7.5 parts by weight of drying alkyd resin were added. A sediment repair material was subsequently prepared in the same manner as in example 1.
The gel obtained was tested, with a gel value of 3000mL/15g, a swelling factor of 470mL/g, a rotation number of 60r/min at 4% concentration and a viscosity of 5500 mPas.
Comparative example 1
A bottom sediment repair gel was prepared in the same manner as in example 2, except that the obtained modified cellulose (dry content) was used as 2 parts by weight, and other substances were added accordingly.
The gel obtained in comparative example 1 was measured to have a gel value of 700mL/15g, a swelling factor of 125mL/g, a rotation number of 60r/min at 4% concentration and a viscosity of 800 mPas.
Comparative example 2
A bottom sediment repair gel was prepared in the same manner as in example 2, except that the obtained modified cellulose (dry content) was taken as 30 parts by weight, to which other substances were added accordingly.
The repairing agent material obtained in comparative example 2 was found to have a colloidal value of 2300mL/15g, a swelling factor of 425mL/g, a 4% rotation number of 60r/min and a viscosity of 7500 mPas.
Comparative example 3
A sediment repair material was prepared in the same manner as in example 2, except that polyacrylic acid was not used.
Comparative example 4
A substrate sludge repairing material was prepared by the same manner as in example 2, except that the drying alkyd resin was not used.
Test example
The sediment-modifying materials obtained in examples 1 to 6 and the sediment repairing materials obtained in comparative examples 1 to 4 were each prepared as a 10% suspension. After high speed shearing in a high speed mechanical emulsifying machine at the rotating speed of 110000r/min, the material is pumped into the bottom of an urban river channel, and the time for the material to form gel on the river channel is monitored, as shown in table 1.
Measurements of the total volume of sediment sludge were taken one week after treatment of the channel with the above materials, as shown in table 1. And simultaneously detecting pollutants in the water area near the bottom sediment. All indexes are detected by using a national standard method and the unit is ppm. As shown in table 2.
TABLE 1
TABLE 2
As can be seen from the above table 1, after the sediment remediation material disclosed by the invention is covered on a river channel, the sediment is solidified on the surface of the sediment within 15 minutes, so that the odor of the exposed sediment is isolated from being emitted, the loss of the exposed sediment and the pollution of the exposed sediment to a watershed embankment and the surrounding environment are prevented, and thus, good water inlet conditions in the later period of a treatment area are ensured.
Furthermore, as can be seen from table 2, the sediment remediation materials of examples 1 to 6 can isolate about 90% of organic pollutants and inorganic pollutants such as fluoride, sulfide, and chloride in the sediment, and non-degradable macromolecular organic pollutants (such as PVA, heterocycles, and phenols), especially heavy metal pollution, from releasing into the river. In addition, the bottom sediment repairing agent disclosed by the invention is in close contact with a water body, and meanwhile, effective components in the bottom sediment repairing agent adsorb water body pollutants, so that the water body is purified, and indexes such as COD (chemical oxygen demand), ammonia nitrogen, total phosphorus and the like are effectively reduced. Therefore, the bottom mud repairing material with specific composition and specific content can effectively purify water quality while performing in-situ repair on the bottom mud, realizes in-situ repair and simultaneously treats mud and water.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The sediment remediation material is prepared by fully mixing the following raw materials in proportion, stirring at a high speed for 2 hours at a temperature of 70-80 ℃ to fully react, and then cooling, filtering, drying and ball-milling the mixture into powder:
2. the sediment remediation material of claim 1, wherein the natural aluminosilicate is selected from one or more of a bauxite and silica mixed powder, tourmaline powder, mica powder, montmorillonite powder, bentonite, and clay powder, preferably from one or more of montmorillonite powder, clay powder, and mica powder; the calcium salt is selected from calcium chloride and calcium oxide; the magnesium salt is selected from magnesium sulfate and magnesium oxide; the sodium salt is selected from sodium carbonate, sodium bicarbonate and sodium percarbonate; the acrylic polymer has a weight average molecular weight of 3000-5000; and the polyhydroxy polymer is selected from drying alkyd resin and polyester resin, preferably with a weight average molecular weight of 1500-2500.
3. The sediment remediation material of claim 1, wherein the sediment remediation material has a gel titer of 1800 to 3000mL/15g, a swelling factor of 125 to 450mL/g, and a viscosity of 1300 to 6000 mPa-s.
4. A method of preparing a substrate sludge repair material, wherein the method comprises the steps of:
step 1), completely mixing 1000 parts by weight of natural aluminosilicate, 5 to 10 parts by weight of calcium salt, 5 to 10 parts by weight of magnesium salt, 5 to 10 parts by weight of sodium salt, 10 to 15 parts by weight of modified cellulose, 20 to 25 parts by weight of acrylic acid polymer, and 5 to 10 parts by weight of polyhydroxy polymer, and then adding water, preferably deionized water, to prepare a 20 wt% suspension, for example;
step 2), stirring the suspension at a high speed for 2 hours at a temperature of 70-80 ℃ to fully react;
step 3), cooling, filtering and drying the mixture obtained in the step 2);
and 4) ball-milling the mixture obtained in the step 3) into powder of preferably 150-350 meshes, more preferably 200 meshes.
5. The method of claim 4, wherein the method further comprises, prior to step 1), preparing the modified cellulose by:
grinding natural cellulose into powder, adding the powder into an alkalizer, and then adding organic alcohol as a solvent;
adding 30-35 wt% of alkaline solution at the temperature of 30-35 ℃ and at the stirring speed of 200-300 r/min;
continuously stirring for at least 30 minutes to obtain the alkalized cellulose; and
optionally, transferring the obtained alkalized cellulose to an etherification machine, and adding an etherifying agent to obtain etherified modified cellulose, wherein the pH of a reaction system is controlled to be 6.8-7.0, and the reaction temperature is controlled to be 70 ℃.
6. The method according to claim 5, wherein the alkaline solution is selected from a solution of sodium hydroxide and/or potassium hydroxide.
7. The method according to claim 4 or 5, wherein the natural aluminosilicate is selected from bauxite and silica mixed powder, tourmaline powder, mica powder, montmorillonite powder, bentonite and clay powder, preferably one or any combination of montmorillonite powder, clay powder and mica powder; the calcium salt is selected from calcium chloride and calcium oxide; the magnesium salt is selected from magnesium sulfate and magnesium oxide; the sodium salt is selected from sodium carbonate, sodium bicarbonate and sodium percarbonate; the acrylic polymer has a weight average molecular weight of 3000-5000; and the polyhydroxy polymer is selected from drying alkyd resin and polyester resin, preferably with a weight average molecular weight of 1500-2500.
8. The method according to claim 4 or 5, wherein the sediment repair material has a gel titer of 1800 to 3000mL/15g, a swelling factor of 125 to 450mL/g, and a viscosity of 1300 to 6000 mPa-s.
9. A method of applying the substrate sludge remediation material of any one of claims 1 to 3 or prepared by the method of any one of claims 4 to 8, wherein the method comprises:
preparing the substrate sludge repairing material and water into a 10% suspension for example;
carrying out high-speed shearing emulsification on the suspension in a high-speed mechanical emulsifying machine at the rotating speed of 10000r/min to 13000r/min to uniformly disperse solids to obtain colloid;
the colloid is cooled automatically in natural environment to form a repair material with stable viscosity;
the repairing material with stable viscosity is directly thrown into the water body environment to be treated, the repairing material with stable viscosity forms off-white gel within a short time, such as 30 minutes, preferably 15 minutes, more preferably 5 minutes, covers the bottom sediment, and the pH value is stabilized at 6.0-9.0.
10. The method of claim 9, wherein the aqueous environment to be treated comprises: river channels with exposed bottom mud, riverbeds after artificial dredging, urban river channels, natural rivers and ecological wetlands treated in the early stage are caused by river water depletion.
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| CN116354566B (en) * | 2023-02-07 | 2024-11-05 | 中国长江三峡集团有限公司 | Sludge heavy metal fixing agent and preparation method thereof |
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