CN113387527A - Treatment method of heavy metal and organic matter combined pollution bottom mud - Google Patents
Treatment method of heavy metal and organic matter combined pollution bottom mud Download PDFInfo
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- CN113387527A CN113387527A CN202110738965.0A CN202110738965A CN113387527A CN 113387527 A CN113387527 A CN 113387527A CN 202110738965 A CN202110738965 A CN 202110738965A CN 113387527 A CN113387527 A CN 113387527A
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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
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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
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/125—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using screw filters
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
Abstract
The invention discloses a method for treating heavy metal and organic matter combined pollution bottom mud, which comprises the following steps: adding an leacheate into the pretreated bottom sludge at a preset flow rate for leaching for a preset time to remove heavy metals and phthalate organic pollutants in the bottom sludge, wherein the leacheate comprises the following components in percentage by mass: 6 to 10 percent of chitosan oligosaccharide, 0.8 to 2 percent of rhamnolipid and the balance of water. The invention can remove heavy metals such as Cu, Cr and the like and organic pollutants of phthalic acid ester in the polluted bottom mud in an enhanced manner.
Description
Technical Field
The invention relates to the technical field of treatment and restoration of polluted bottom mud, in particular to a treatment method of heavy metal and organic matter composite polluted bottom mud.
Background
In recent years, the treatment work of urban black and odorous water bodies is accelerated and promoted in various places of China. Wherein, dredging and treating the polluted bottom mud are the main means for endogenous control of the black odor of rivers and lakes. However, the large amount of dredged sediment is facing a lot of problems, such as huge volume, high ecological risk, etc. The dredging bottom mud is used for ceramic grains, permeable bricks and roadbed building materials in a small amount, and most of the dredging bottom mud is not consumed everywhere. The bottom mud contains sufficient nitrogen and phosphorus, is a high-quality fertilizer source, and can not only solve the problem of the destination of the bottom mud but also realize the resource recycling if being used for farmlands or greenbelts. However, in the industrial urban and urban drainage basin sediment, the safe disposal and the reutilization of the sediment are greatly limited due to the fact that the sediment contains excessive heavy metals and compound organic pollutants, and therefore, the harmless treatment of the pollutants such as the heavy metals, the organic matters and the like in the sediment is a key step for realizing the reutilization of the sediment.
The traditional eluting agents such as inorganic acid and chemical complexing agent can be used for removing heavy metals in the bottom mud to a certain extent, but the ecological and nutritional characteristics of the bottom mud are easily damaged, the reutilization of the bottom mud is influenced, and the effect of removing organic pollutants in the bottom mud by the eluting agents is poor. Meanwhile, the bottom mud has complex components and obvious sequence structure, and a large amount of clay substances wrap and adsorb pollutants, so that the mass transfer efficiency of the pollutants between two phases in the leaching process is limited, and the removal effect of heavy metals and organic matters is poor.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a method for treating the bottom mud compositely polluted by heavy metals and organic matters, which can synchronously and efficiently remove the heavy metals and the organic pollutants in the bottom mud.
The technical problem of the invention is solved by the following technical scheme:
a method for treating heavy metal and organic compound polluted bottom mud comprises the following steps: adding an leacheate into the pretreated bottom sludge at a preset flow rate for leaching for a preset time to remove heavy metals and phthalate organic pollutants in the bottom sludge, wherein the leacheate comprises the following components in percentage by mass: 6 to 10 percent of chitosan oligosaccharide, 0.8 to 2 percent of rhamnolipid and the balance of water.
Preferably, the processing method comprises the following steps:
s1, preprocessing the dredged river and lake bottom mud;
s2, leaching the pretreated bottom mud with leacheate at a preset flow rate for preset time, and carrying out solid-liquid separation;
s3, dehydrating and drying the bottom sludge processed in the step S2;
and S4, adjusting the pH value of the liquid phase obtained after the treatment in the step S2, and then performing sedimentation separation and purification to complete the recovery of heavy metals and the regeneration of the leacheate.
Preferably, 10L to 30L of the leacheate is leached into 1kg of the pretreated bottom mud.
Preferably, the degree of polymerization of the chitosan oligosaccharide is 4-10.
Preferably, after removing garbage, gravel, animal and plant residues and other components in the dredged river and lake bottom mud, the dredged river and lake bottom mud is air-dried, crushed and ground to pass through a 100-target standard sample sieve.
Preferably, the predetermined time is 1h-5h, and the predetermined flow rate is 36-40L/h/dm2。
Preferably, the rhamnolipid consists of 50-75 wt% of mono and 25-50 wt% of bis rhamnolipids, preferably, the rhamnolipid consists of 75 wt% of mono and 25 wt% of bis rhamnolipids.
Preferably, the purging in step S4 includes: and D113 resin exchange columns are adopted to adsorb and remove heavy metal ions, and powdered activated carbon is adopted to adsorb and remove the phthalate organic pollutants dispersed in the liquid phase.
Preferably, the method further comprises the following steps: adjusting the mass fraction of chitosan oligosaccharide in the eluent after regeneration in the step S4 to be 6-10% and the mass fraction of rhamnolipid to be 0.8-2%, and reusing the eluent in the step S2.
Preferably, the dewatering and drying in the step S3 are performed in a stack-screw filter press; and in the step S4, the pH value is adjusted to 5-9.
Compared with the prior art, the invention has the advantages that: aiming at the characteristic that the laminar slime structure of the substrate sludge has strong pollutant adsorption capacity, the substrate sludge is leached synergistically by adopting the chitosan oligosaccharide and the rhamnolipid. The chitosan oligosaccharide is a natural micromolecular chelating agent and can form a stable water-soluble chelate with various metal ions through chelation; by utilizing the desorption strengthening and micelle loading effects of rhamnolipid, heavy metals and organic pollutants in the sediment are rapidly desorbed, and the migration capability to the leacheate is greatly strengthened. Meanwhile, compared with the traditional inorganic acid eluent, the chitosan oligosaccharide and rhamnolipid have good biodegradability and environmental compatibility, and can not cause secondary pollution to bottom mud. The method can remove heavy metals such as Cu and Cr and organic pollutants such as Phthalic Acid Esters (PAEs) in the polluted bottom mud in an enhanced mode, has stronger practicability in the fields of river and lake bottom mud treatment and restoration, has good environmental and social benefits, and has wide market popularization prospect.
Drawings
FIG. 1 is a schematic view of an experimental apparatus used in example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings and preferred embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The embodiment of the invention provides a method for treating heavy metal and organic matter combined pollution bottom mud, which comprises the following steps: adding an leacheate into the pretreated bottom sludge at a preset flow rate for leaching for a preset time to remove heavy metals and phthalate ester (PAEs) organic pollutants in the bottom sludge, wherein the leacheate comprises the following components in percentage by mass: 6 to 10 percent of chitosan oligosaccharide, 0.8 to 2 percent of rhamnolipid and the balance of water.
In the technical scheme, heavy metals in the sediment are released from the sediment and enter the leacheate to form stability with chitosan oligosaccharide through induced desorption, interphase mass transfer and high-efficiency chelationAnd (3) determining a chelate, wherein pollutants in the bottom mud are mainly eluted into the leacheate under the action of rhamnolipid. Specifically, the chitosan oligosaccharide in the leacheate is fully contacted with the polluted bottom sediment, and the-OH and-NH of the chitosan oligosaccharide2Forms stable chelate bonds with heavy metal ions on the surface of the sediment and in pore water, so that the heavy metal ions are desorbed from the surface of the sediment and enter leacheate, meanwhile, the rhamnolipid in the leacheate promotes the release of pollutants from the sediment by reducing the interfacial tension of liquid and solid phases and forming competitive adsorption sites, and when the concentration of rhamnolipid in the leacheate is higher than CMC (critical micelle concentration, 22.5mg/L), a micelle is formed to wrap the pollutants on the surface of the sediment and wrap the pollutants into the leacheate, namely, it can be used as a mass transfer carrier to carry heavy metal ions to carry out chelation adsorption reaction with the chitosan oligosaccharide, solves the problem of low mass transfer efficiency of bottom mud leaching, simultaneously, the desorption of PAEs organic pollutants in the bottom mud can be promoted, the migration of the two pollutants into the leacheate is effectively accelerated, the chitosan oligosaccharide then forms stable chelates with heavy metals dissociated into solution continuously by chelation.
In a preferred embodiment, the processing method comprises the steps of:
s1, preprocessing the dredged river and lake bottom mud;
s2, leaching the pretreated bottom mud with leacheate at a preset flow rate for preset time, and carrying out solid-liquid separation;
s3, dehydrating and drying the bottom sludge processed in the step S2;
s4, adjusting pH of the liquid phase treated in step S2 (HCl or Ca (OH) can be used)2Etc. to adjust the pH) for settling separation, purification, to complete the recovery of heavy metals and the regeneration of the leacheate.
Wherein, the structural formula of the chitosan oligosaccharide is shown as follows, and in a preferred embodiment, the polymerization degree n is 4-10.
In a preferred embodiment, the rhamnolipid consists of 50-75 wt% of mono and 25-50 wt% of bis rhamnolipids, the rhamnolipid employed in example 1 below consists of mono (75 wt%, m ═ n ═ 6) and bis (25 wt%, m ═ n ═ 6) rhamnolipids of the formula:
in a preferred embodiment, 10L-30L of the leacheate is leached into 1kg of the pretreated bottom mud, namely, the liquid-solid ratio (L: kg) is 10: 1-30: 1.
In a preferred embodiment, after removing garbage, gravel, animal and plant residues and other components in the dredged river and lake bottom mud, the dredged river and lake bottom mud is air-dried, crushed and ground through a 100-target standard sample sieve.
In a preferred embodiment, said predetermined time is 1h-5h and said predetermined flow rate is 36-40L/h/dm2(i.e. every 1dm of washing apparatus (e.g. washing column)2Sections were rinsed with 36-40L of rinse per hour).
In a preferred embodiment, the pH value in the step S4 is adjusted to 5-9.
In a preferred embodiment, the purging in step S4 includes: and D113 resin (macroporous weak acid phenyl propylene cation exchange resin) is adopted for adsorption and removal of heavy metal ions, and Powdered Activated Carbon (PAC) is adopted for adsorption and removal of phthalate organic pollutants dispersed in the liquid phase. And after settling separation, the leacheate after the bottom mud is treated enters an ion exchange column and an active carbon exchange column to regenerate the leacheate.
In a preferred embodiment, the method further comprises the following steps: adjusting the mass fraction of chitosan oligosaccharide in the eluent after regeneration in the step S4 to be 6-10% and the mass fraction of rhamnolipid to be 0.8-2%, and reusing the eluent in the step S2.
In a preferred embodiment, the dewatering and drying in step S3 are performed in a stack-screw filter press. The sediment can be safely disposed or reused after being dehydrated and dried by a screw-stacking filter press.
The heavy metal and organic matter composite pollution bottom mud mainly refers to river and lake bottom mud compositely polluted by heavy metals such as Cu and Cr and organic pollutants such as Phthalic Acid Esters (PAEs), and is more typical river and lake bottom mud in or near rapidly developing cities. In order to make the technical means, operation steps and implementation effect of the present invention easy to understand, the following method for treating heavy metal and organic compound polluted bottom mud is explained with reference to the examples and the attached drawings.
Example 1
As shown in figure 1, the treatment method of the heavy metal and organic matter combined polluted bottom mud comprises the following steps:
1. naturally air-drying the bottom sludge dredged from rivers and lakes, carrying out pretreatment such as garbage sorting, mud-sand separation, stone and animal and plant residue removal and the like, conveying the dried bottom sludge to an air-extracting and drying site, crushing and grinding the dried bottom sludge, and screening the dried bottom sludge through a 100-mesh sample sieve for later use to obtain the pretreated bottom sludge 4.
2. Filling the pretreated bottom mud 4 into leaching equipment; in this example, 50g of pretreated bottom sludge particles are filled into the leaching column 1 at 25 ℃ and room temperature. In the leaching column (diameter D is 60mm, column height H is 400mm), arranged from top to bottom are coarse water distribution sand 2(D is 5mm, H1 is 3cm), nylon fabric 3, bottom mud 4 (filling height H2 is 90mm), nylon fabric 3, fine sand 5(D is 1mm, H3 is 2cm) and G3 sand core 6. 3. 1L of eluent containing 8.5 percent of chitosan oligosaccharide and 1.5 percent of rhamnolipid is prepared in a beaker 11 with stirring, the flow rate of a liquid inlet peristaltic pump 10 is adjusted to be 250ml/h, and continuous leaching operation is carried out on the sediment 4 in a leaching column. In the leaching process, heavy metals and PAEs in the bottom sediment 4 are continuously released from the bottom sediment and enter the leaching solution, and flow out from the lower end of the column through a solid-liquid separation layer (fine sand 5 and a G3 sand core 6) along with the leaching solution, so that bottom sediment pollutants are removed.
4. And after the continuous leaching is carried out for 4 hours, the leaching process is finished, and the load leacheate continuously generated in the process is filtered by the sand core 6 at the bottom of the leaching column and then is continuously pumped out by the vacuum pump 7 to be collected to obtain the load leacheate. For detection, a part of the load leacheate is filtered by a microporous filter membrane to obtain a solution A to be detected.
5. And after the leaching is finished, the solid collected in the leaching column is the treated bottom mud B.
And respectively analyzing the contents of Cu, Cr and DEHP (one of PAEs organic pollutants) in the liquid A to be detected, the bottom sediment 4 and the bottom sediment B. The concentration of the heavy metals in the solution A to be detected is analyzed by an inductively coupled plasma spectrometer (ICP), the total content of the heavy metals in the sediment 4 and the sediment B is obtained by carrying out microwave complete digestion-acid removal treatment on the sediment and then measuring by the ICP, and the content of the metals in each form in the sediment is obtained by a Tensier five-step extraction method-ICP.
Through detection and analysis, the removal rates of the heavy metals in the bottom mud are respectively 60.5 percent of Cu and 36 percent of Cr, and the removal rates of the two heavy metals in an effective state (a water-soluble state, an ion exchange state and carbonate) are more than 98 percent; the removal rate of DEHP in the bottom mud reaches more than 82 percent. The removal rate of the heavy metal in the bottom sediment is calculated by dividing the content of a single element in the liquid A to be detected by the total content of the metal in the bottom sediment 4, the removal rate of the heavy metal in each form is calculated by subtracting the content of the heavy metal in each form in the bottom sediment B from the content of the heavy metal in each form in the bottom sediment 4 and then dividing the subtracted result by the content of the heavy metal in each form in the bottom sediment 4, and the removal rate of the DEHP is calculated by dividing the content of the DEHP in the liquid A to be detected by the total content of the DEHP in the bottom sediment 4.
6. And dewatering, drying and conditioning the treated bottom mud B in a spiral filter press, and then carrying out soil formation and recycling.
7. Adjusting the pH value of all collected load leacheate to 5-9, then carrying out sedimentation separation, enabling a liquid phase to enter D113 resin for purification treatment, adsorbing heavy metal ions onto a column to realize enrichment and recovery of heavy metals, adding the remaining liquid phase into a powdered activated carbon adsorption column to remove phthalate organic pollutants dispersed in the liquid phase, thus obtaining regenerated leacheate, adjusting the mass fraction of chitosan oligosaccharide in the regenerated leacheate to 6% -10%, and adjusting the mass fraction of rhamnolipid to 0.8% -2%, and then recycling the regenerated leacheate in the step 3.
The preferred embodiment of the invention has the following advantages:
1. the chitosan oligosaccharide has high environmental compatibility and more-OH and-NH2Has flexible sites, strong heavy metal chelating adsorption and no K adsorption+、Na+、Ca2+、Cl-、NO3-And mineral nutrients are added, so that the mineral nutrients in the bottom mud can be effectively reserved while the efficient heavy metal chelating and bottom mud detoxification are realized, the leached bottom mud can be used for planting after conditioning (the chitosan oligosaccharide remained in the bottom mud can be converted into a plant growth regulator), the environmental risk of bottom mud pollution can be effectively solved, and the resource waste is avoided.
2. The characteristics of the substrate of the bottom sediment are considered, the desorption strengthening and micelle loading effects of rhamnolipid are utilized, so that the desorption and migration capabilities of heavy metals and organic pollutants in the bottom sediment are greatly enhanced, the restriction of slow mass transfer process of the traditional bottom sediment leaching technology is broken through, and the synergistic elution restoration of the polluted bottom sediment is realized. The leacheate provided by the embodiment of the invention realizes the optimization of the leaching efficiency and the function complementation of the bottom mud composite pollutants.
3. Heavy metals are adsorbed to the leaching solution after mud-water separation through a heavy metal ion exchange column, so that the enrichment and recovery of the heavy metals are realized; and the PAEs organic pollutants dispersed in the water solution are removed by utilizing Powdered Activated Carbon (PAC) adsorption, and the regenerated leacheate can be recycled in the leaching step after being conditioned, so that the consumption of the raw materials of the leacheate can be effectively reduced, and the process cost is reduced.
The example proves that the leacheate has a high effect of removing the heavy metals Cu, Cr, DEHP and other pollutants in the bottom sludge, more than 98% of the heavy metals in the effective state and more than 70% of the DEHP can be removed, and therefore synchronous leaching removal of the heavy metals in the bottom sludge and organic matter composite pollutants is effectively achieved. The method for leaching the river and lake bottom mud polluted by the heavy metals can remove the heavy metals and the organic pollutants in the bottom mud efficiently, does not cause environmental pollution, can realize recycling of the leacheate, has the advantages of simplicity and convenience in operation, no environmental hazard, reasonable cost and high benefit, and can effectively realize harmless treatment of the river and lake composite polluted bottom mud.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.
Claims (10)
1. A treatment method of heavy metal and organic compound polluted bottom mud is characterized by comprising the following steps: adding an leacheate into the pretreated bottom sludge at a preset flow rate for leaching for a preset time to remove heavy metals and phthalate organic pollutants in the bottom sludge, wherein the leacheate comprises the following components in percentage by mass: 6 to 10 percent of chitosan oligosaccharide, 0.8 to 2 percent of rhamnolipid and the balance of water.
2. The method for treating the bottom mud compositely polluted by the heavy metals and the organic matters according to claim 1, wherein the method comprises the following steps:
s1, preprocessing the dredged river and lake bottom mud;
s2, leaching the pretreated bottom mud with leacheate at a preset flow rate for preset time, and carrying out solid-liquid separation;
s3, dehydrating and drying the bottom sludge processed in the step S2;
and S4, adjusting the pH value of the liquid phase obtained after the treatment in the step S2, and then performing sedimentation separation and purification to complete the recovery of heavy metals and the regeneration of the leacheate.
3. The method for treating the bottom sludge compositely polluted by the heavy metals and the organic matters as claimed in claim 1 or 2, characterized in that: and 10L-30L of the leacheate is sprayed into each 1kg of the pretreated bottom mud.
4. The method for treating the bottom sludge compositely polluted by the heavy metals and the organic matters as claimed in claim 1 or 2, characterized in that: the polymerization degree of the chitosan oligosaccharide is 4-10.
5. The method for treating the bottom sludge compositely polluted by the heavy metals and the organic matters as claimed in claim 1 or 2, characterized in that: the pretreatment process of the bottom mud comprises the following steps: after removing garbage, gravel, animal and plant residues and other components in the dredged river and lake bottom mud, air-drying, crushing and grinding the mixture to pass through a 100-target standard sample sieve.
6. The method for treating the bottom sludge compositely polluted by the heavy metals and the organic matters as claimed in claim 1 or 2, characterized in that: the preset time is 1h-5h, and the preset flow rate range is 36-40L/h/dm2。
7. The method for treating the bottom sludge compositely polluted by the heavy metals and the organic matters as claimed in claim 2, characterized in that: the rhamnolipid consists of 50-75 wt% of mono and 25-50 wt% of bis rhamnolipids, preferably the rhamnolipid consists of 75 wt% of mono and 25 wt% of bis rhamnolipids.
8. The method for treating the bottom sludge compositely polluted by the heavy metals and the organic matters as claimed in claim 2, characterized in that: the purging in step S4 includes: and D113 resin exchange columns are adopted to adsorb and remove heavy metal ions, and powdered activated carbon is adopted to adsorb and remove the phthalate organic pollutants dispersed in the liquid phase.
9. The method for treating the bottom sludge compositely polluted by the heavy metals and the organic matters as claimed in claim 2, characterized in that: also comprises the following steps: adjusting the mass fraction of chitosan oligosaccharide in the eluent after regeneration in the step S4 to be 6-10% and the mass fraction of rhamnolipid to be 0.8-2%, and reusing the eluent in the step S2.
10. The method for treating the bottom sludge compositely polluted by the heavy metals and the organic matters as claimed in claim 2, characterized in that: the dehydration and drying in the step S3 are carried out in a stack-screw filter press; and in the step S4, the pH value is adjusted to 5-9.
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