CN109292982B - Modular composite advanced treatment system for low-concentration heavy metal wastewater and operation method - Google Patents

Modular composite advanced treatment system for low-concentration heavy metal wastewater and operation method Download PDF

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CN109292982B
CN109292982B CN201811055363.XA CN201811055363A CN109292982B CN 109292982 B CN109292982 B CN 109292982B CN 201811055363 A CN201811055363 A CN 201811055363A CN 109292982 B CN109292982 B CN 109292982B
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张志斌
王晓栋
张晓蕊
仇婷
张彦浩
邢梦龙
孙皓
闫大江
林建伟
张建
张向阳
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Shandong Jianzhu University
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Abstract

The utility model provides a compound advanced treatment system of modularization and operation method of low concentration heavy metal waste water, the system includes the water distribution system, water collection system and modularization adsorb the unit, water collection device includes water catch bowl and water catch buffer, the water catch bowl sets up two-layerly at least, water catch buffer sets up with each layer water catch bowl from bottom to top range upon range of, water distribution device includes inlet tube and wet return, advance the water inlet end of water piping connection other water catch bowls outside the bottom, the wet return sets up between the play water end of upper water catch bowl and the intake end of lower floor's water catch bowl, all set up modularization in each layer of water catch bowl and adsorb the unit. The low-concentration wastewater containing heavy metals is delivered into a water collecting device through a water distribution device, the heavy metals in the water are adsorbed and removed through modified zeolite, then the heavy metals on the adsorbent are enriched, transferred and removed through plants, and the deep treatment of the heavy metal wastewater is realized through regularly replacing the plants. The invention realizes the deep treatment of the low-concentration heavy metal wastewater, and has flexible application and obvious treatment effect.

Description

Modular composite advanced treatment system for low-concentration heavy metal wastewater and operation method
Technical Field
The invention relates to a system for carrying out advanced treatment on low-concentration heavy metal wastewater and an operation method of the system, belonging to the technical field of heavy metal pollution wastewater treatment.
Background
At present, for the supervision of sewage discharge of enterprises, the domestic and foreign generally implement the management mode of sewage discharge reaching standards, that is, the sewage pollutant concentration after treatment is reduced to the specified low concentration limit value, the sewage can be allowed to be discharged, and tail water discharged reaching the standards still contains pollutants with low concentration. Unlike organic pollutants, heavy metals are not degraded or volatilized in nature and continue to be enriched once they enter the environment. For enterprises involving heavy metals, after the low-concentration heavy metal wastewater is discharged into the environment, the wastewater can still bring significant harm to human health after entering a food chain through further enrichment in soil or plants.
The common heavy metal wastewater treatment methods include a chemical precipitation method, an ion exchange method, an adsorption method, an evaporation concentration method, a membrane separation technology and the like. The chemical precipitation method comprises the steps of adding a chemical agent into the wastewater to generate precipitation, and removing heavy metals in the wastewater through precipitation and filtration. Chinese patent document CN105800750 discloses a "heavy metal wastewater treatment apparatus and method", in which heavy metal wastewater is reacted with a basic agent and an auxiliary agent by a chemical precipitation method to obtain sludge containing heavy metal ions and residual auxiliary agent precipitated after the reaction, a part of the sludge is dissolved in untreated heavy metal wastewater, and the heavy metal wastewater in which the sludge is dissolved is reacted by the chemical precipitation method. The treatment technology can meet the standard emission requirements of the existing pollution source enterprises, but the effluent still contains heavy metals with certain low concentration. The ion exchange method and the adsorption method have low removal efficiency on low-concentration heavy metal wastewater, and the ion exchange resin and the adsorbent need to be frequently replaced, so that the treatment cost is high.
Evaporative concentration is a process in which water is evaporated by heating and the contaminants are finally crystallized out. For example, in "an electro-Fenton evaporation concentration treatment device for heavy metal-containing high-salt wastewater" disclosed in Chinese patent document CN206799350, the method is to sequentially pass the heavy metal-containing high-salt wastewater through a communicated water collecting tank, an electro-Fenton treatment device for removing organic matters in the wastewater and a concentration evaporation treatment unit for evaporating and concentrating heavy metals. This method is commonly used to treat high concentrations of recalcitrant contaminants.
The 'double-membrane process heavy metal wastewater treatment and recycling equipment' disclosed in Chinese patent document CN202430070 comprises a pretreatment system, an ultrafiltration system and a two-stage reverse osmosis system, and is used for treating heavy metal wastewater, so that harmful substances such as heavy metals in the wastewater can be effectively removed, and zero emission of the heavy metals is realized. The device investment that application membrane separation technique treatment waste water needs is great, and reverse osmosis membrane also blocks up the pollution easily, needs to change reverse osmosis membrane regularly, and in addition, ultrafiltration and reverse osmosis technique are only physical separation, can produce the high concentration heavy metal concentrate in its processing procedure, and the processing of concentrate adopts evaporative concentration to realize usually, and the treatment cost is unusually high, has restricted its popularization and application in actual engineering.
Therefore, it is necessary to develop a low-concentration heavy metal advanced treatment technology with good treatment effect and low investment and operation cost to reduce the emission of heavy metals.
Disclosure of Invention
Aiming at the problems of poor treatment capacity or overhigh treatment cost of low-concentration heavy metal wastewater and the like in the conventional heavy metal wastewater treatment technology at present, the invention provides a modular composite advanced treatment system for low-concentration heavy metal wastewater, which is low in cost, good in treatment effect, small in occupied area and flexible in application, based on the combination of an adsorbent and plant treatment, and also provides an operation method of the system in the composite advanced treatment of the low-concentration heavy metal wastewater.
The modular composite advanced treatment system for the low-concentration heavy metal wastewater adopts the following technical scheme:
the system comprises a water distribution system, a water collecting system and a modular adsorption unit;
the water collecting device comprises water collecting tanks and water collecting buffer tanks, wherein the water collecting tanks are at least provided with two layers, the water collecting buffer tanks and all layers of water collecting tanks are arranged from bottom to top in a stacked mode, one side, connected with the water collecting buffer tank, of the bottommost water collecting tank is provided with a bottom overflow weir, partition walls are arranged in all the other layers of water collecting tanks to form a partition unit, upper overflow weirs or bottom water passing holes are arranged on the partition walls, the partition walls provided with the overflow weirs and the partition walls provided with the water passing holes are arranged in the water collecting tanks at intervals along the length direction, water outlets are arranged on the outer sides of the water collecting buffer tanks, and the bottoms of the water collecting buffer;
the water distribution device comprises a water inlet pipe and a water return pipe, the water inlet pipe is connected with the water inlet ends of other water collecting tanks except the bottommost layer, the water return pipe is arranged between the water outlet end of the upper-layer water collecting tank and the water inlet end of the lower-layer water collecting tank, a water inlet valve is arranged on the water inlet pipe, and a water return valve is arranged on the water return pipe;
all set up the modularization in every layer of water catch bowl and adsorb the unit, the modularization adsorbs the unit and cultivates the tray including permeating water brick, absorption filling layer and plant, is provided with the slot in the brick that permeates water, places the absorption filling layer in the slot, is provided with the planting hole in the brick that permeates water. The top of the water permeable brick is provided with a plant culture tray. The permeable brick is wrapped with a mesh, and a handle is arranged on the mesh so as to be convenient to lift and replace. The adsorption filling layer comprises a support frame, and the support frame is filled with an adsorbent filled in mesh bags.
And the adsorbent of the adsorption filling layer in the modular adsorption units in the water collecting tank of the other layer except the water collecting tank of the bottom layer is modified zeolite. The preparation process of the modified zeolite is as follows:
crushing natural zeolite, sieving with 30-40 mesh sieve, adding 10% NH4Soaking in Cl solution for 3 hours, taking out and drying, and then roasting at a high temperature of 500 ℃ for 2 hours; then the calcined zeolite is treated with NH with the concentration of 10 percent4Soaking the Cl solution for 3 hours, drying and then roasting for 2 hours at 500 ℃; subjecting the twice calcined zeolite to a concentration of 10% NH4Soaking the Cl solution for 5 hours; finally, drying the soaked zeolite for 4 hours at the temperature of 40 ℃ to obtain NH4Cl modified zeolite.
The modified zeolite particles are placed in a mesh bag after being screened by a 60-mesh sieve, the maximum gap of the mesh bag is less than 0.2mm, and is determined by the minimum particle size of the filled modified zeolite, so that the modified zeolite particles do not penetrate through the adsorption filler.
The modified zeolite is prepared by roasting at high temperature and low temperature, so that zeolite adsorption and plant root system absorption are facilitated. The zeolite water and impurities in zeolite holes and channels can be effectively removed through the primary roasting treatment of the zeolite, the holes are dredged, recovered and reconstructed, and the adsorption capacity is increased; the secondary roasting process can further enlarge the holes of the zeolite, and the enlarged holes are beneficial to the growth of the capillary heels of the aquatic plants, so that the enrichment efficiency of the aquatic plants on the heavy metals is increased. By NH4Repeatedly soaking in Cl solution to make NH4 +Binding to the adsorption sites of the zeolite further increases the adsorption capacity of the zeolite. When the modified zeolite is soaked in boiling water, the heavy metal ions exchange NH in the modified zeolite4 +The exchanged ions are absorbed and utilized by the growth of plants, and the ammonium modified zeolite also plays a role in nitrogen preservation. The specific surface area of the zeolite is measured to be 2.15m before modification2Increase in g to 3.47m2G, heavy metal Cd in laboratory conditions2+The adsorption capacity of the modified zeolite is increased from 4.5mg/g to 12mg/g, and the modification effect is obvious.
And the adsorbent of the adsorption filling layer in the modular adsorption unit in the bottom water collecting tank is modified activated carbon. The preparation process of the modified activated carbon adsorbent is as follows:
(1) pretreatment of activated carbon: washing the granular activated carbon with deionized water, and drying for 10 hours at 100 ℃;
(2)HNO3oxidation modification:
preparing a 10% nitric acid solution, and mixing the solution according to the weight ratio of 1 g: 2ml of the pretreated activated carbon particles are taken and dissolved in nitric acid solution, and the solution is heated for 2 hours under the condition of water bath at the temperature of 75 ℃; after cooling, washing the mixture by deionized water; drying the washed sample in an oven at 120 ℃ for 6 hours; putting the dried activated carbon into a muffle furnace to activate for 2 hours at the temperature of 400 ℃ to obtain HNO3Modified activated carbon.
The modified activated carbon particles are put into a mesh bag, the maximum gap of the nylon mesh bag is less than 0.2mm, and the maximum gap is determined by the minimum particle size of the filled modified activated carbon, so that the modified activated carbon does not penetrate through the adsorption filler.
The modified active carbon is prepared by removing impurities on the surface and in micropores of the modified active carbon by adopting a pretreatment method and then passing through HNO3The modification and high-temperature activation treatment fully increase the specific surface area of the activated carbon and increase the adsorption activity and the adsorption capacity. The specific surface area of the activated carbon is measured to be 450m before modification2Increase/g to 615m2G, heavy metal Cd in laboratory conditions2+The adsorption capacity of the modified zeolite is increased from 98.2mg/g to 125.3mg/g, and the modification effect is obvious.
The operation method of the system in the composite advanced treatment of the low-concentration heavy metal wastewater comprises the following steps:
(1) for low-concentration (lower than the minimum discharge value of heavy metal in the current integrated wastewater discharge standard-GB 8978-1996), selecting plants with enrichment capacity aiming at different heavy metals according to the types of the heavy metals in the wastewater, cultivating the selected plants on a plant cultivation tray in advance, putting the plant cultivation tray on a water permeable brick, and aligning the plants to planting holes of the water permeable brick so as to be beneficial to the subsequent growth and absorption of the plants; simultaneously planting the selected plants in the water collecting buffer tank;
(2) in the initial operation stage, a valve on a water inlet pipe connected to the uppermost water collecting tank and valves on water return pipes are opened, so that wastewater turns back and flows in a dividing unit of the water collecting tank outside the bottom layer, the effluent of the upper water collecting tank enters the lower water collecting tank through the water return pipes, a modular adsorption unit in the water collecting tank is in a completely submerged state, the wastewater passes through the water collecting tanks layer by layer and then enters a water collecting buffer pool, and the wastewater is discharged from a water outlet of the water collecting buffer pool after further adsorption of natural zeolite and plants in the water collecting buffer pool;
(3) the valves on the water inlet pipes of other water collecting tanks except the bottommost layer are opened and closed alternately, the valve on the water inlet pipe of the upper water collecting tank and the valve on the water return pipe between the upper water collecting tank and the lower water collecting tank are opened for a certain time and then closed, and meanwhile, the valve on the water inlet pipe of the lower water collecting tank is opened to enable waste water to enter the lower water collecting tank, so that plants on the upper water collecting tank have enough time to enrich heavy metals on the adsorbent in the adsorption filling layer in the upper modularized adsorption unit.
The valve on the water inlet pipe of the water collecting tank is opened and closed for the following alternative time:
Figure GDA0002875240090000031
in the formula: q. q.seThe adsorption capacity at equilibrium (maximum adsorption capacity under low concentration conditions), in mg/g, is the mass mg of heavy metal adsorbed per g of modified zeolite;
Figure GDA0002875240090000032
wherein: ceThe concentration of heavy metal in water in unit mg/L during balancing;
Kmthe adsorption constant is 0.06-0.15;
qmthe saturated adsorption capacity is unit mg/g, and each g of modified zeolite adsorbs the mass mg of heavy metal;
t is the water temperature of the wastewater, unit ℃;
beta is the rate of adsorption and is,
Figure GDA0002875240090000033
wherein: q. q.seThe amount of adsorbed at equilibrium (mg/g, q)eAs in the previous meaning, maximum adsorption capacity at low energy); q. q.saThe actual adsorption capacity is unit mg/g, and each g of modified zeolite adsorbs the mass mg of the heavy metal;
v is the inlet flow of the wastewater in the layer of water collecting tank, m3/h；
M is the filling amount of the adsorbent in each module adsorption unit, kg;
n is the number of the module adsorption units in the layer of water collecting tank;
c is the concentration of heavy metal in the inlet water of the water collecting tank of the layer, g/m3。
The adsorbent can adsorb a large amount of pollutants under the condition of high-concentration pollutants, can adsorb a small amount of pollutants under the condition of low-concentration pollutants, and can be reused only by regeneration after adsorption balance. Plants are also, if the concentration of contaminants in the soil at the roots is low, the uptake is slow and minimal.
For heavy metal with low concentration, the heavy metal can be concentrated on the adsorbent after being absorbed by the adsorbent. The plant root system is more beneficial to plant absorption under high concentration. In addition, due to plant absorption, compared with the traditional adsorption, the physical and chemical method regeneration (the secondary pollution problem in the regeneration process) of the adsorbent is not needed.
The invention realizes the advanced treatment of the low-concentration heavy metal wastewater, and has the following characteristics:
(1) the rapid physicochemical adsorption and plant growth absorption are organically combined, heavy metals in water are adsorbed and removed through modified zeolite adsorption, then the heavy metals on the adsorbent are enriched and transferred and removed through plants, and the deep treatment of the heavy metal wastewater is realized through regularly replacing the plants. The zeolite adsorption speed is high, the heavy metal concentration is improved by the zeolite adsorption, plants can absorb and remove a large amount of heavy metals, the heavy metal amount absorbed by the zeolite can be reduced by the plant absorption, and the zeolite operation time is prolonged.
(2) Adopt the modularized design, wherein the brick that permeates water, but adsorption filling layer, the plant cultivation tray of pull replacement all adopt the modularized design, use in a flexible way.
(3) The intermittent water supply of each layer of water collecting tank can be realized by adjusting the valves arranged on the water distribution pipes, so that the maximum adsorption capacity of the physicochemical adsorbent is fully utilized, and the enrichment time of plants is ensured.
(4) The modified zeolite is subjected to secondary roasting and repeated soaking treatment, so that the adsorption activity and adsorption capacity of the zeolite are increased, the growth of the capillary roots of the aquatic plants is facilitated, and the plant enrichment efficiency is improved. The modified active carbon is pretreated to remove impurities on the surface and in micropores of the active carbon, and then the modified active carbon is subjected to HNO3The activation modification treatment fully increases the specific surface area of the activated carbon, and increases the adsorption activity and the adsorption capacityAmount of the compound (A).
(5) Different plants can be flexibly selected for treating different heavy metals contained in the water quality of the inlet water in the selection of the enrichment plants.
Drawings
FIG. 1 is a schematic structural principle diagram of the modular composite advanced treatment system for low-concentration heavy metal wastewater.
FIG. 2 is a schematic structural view of a modular adsorption unit according to the present invention.
FIG. 3 is a schematic structural diagram of an adsorption filling layer according to the present invention.
FIG. 4 is a scanning electron micrograph of a zeolite of the present invention before and after modification; (a) before modification, and (b) after modification.
FIG. 5 is a scanning electron microscope image of the activated carbon before and after modification in the present invention. (c) Before modification, and after modification.
In the figure: 1. the water inlet main pipe, 2, an upper layer water inlet pipe, 3, an upper layer water inlet valve, 4, a middle layer water inlet pipe, 5, a middle layer water inlet valve, 6, a first water return pipe, 7, a first water return valve, 8, a second water return pipe, 9, a second water return valve, 10, an upper layer water collecting tank, 11, a middle layer water collecting tank, 12, a bottom layer water collecting tank, 13, a steel frame, 14, an inspection ladder, 15, a water collecting buffer tank, 16, an overflow weir, 17, a water passing hole, 18, a lower layer overflow weir, 19, a water outlet, 20, natural zeolite, 21, enriched plants, 22, a modular adsorption unit, 23, permeable bricks, 24, permeable holes, 25 woven meshes, 26, a lifting rope, 27, an adsorption filling layer, 28, a plant culture tray, 29, plants, 30, a gap groove, 31, a hidden buckle handle, 32, a support frame, 33, an adsorbent, 34, a mesh bag and 35, a trapezoidal gradually shrinking head.
Detailed Description
The modular composite advanced treatment system for the low-concentration heavy metal wastewater is arranged at a discharge outlet at the tail end of a wastewater treatment facility so as to carry out modular composite remediation treatment on the low-concentration heavy metal wastewater. The system comprises a water collecting device, a water distribution device and a modular adsorption unit, and the specific structure of each part is shown in figure 1.
The water collecting device comprises a plurality of layers of water collecting grooves and a water collecting buffer pool 15, wherein an upper layer of water collecting groove 10, a middle layer of water collecting groove 11 and a bottom layer of water collecting groove 12 are arranged in fig. 1, the three layers of water collecting grooves are arranged on three steps of a step-shaped steel frame 13, and an overhaul ladder 14 is arranged on the steel frame 13. The water collection buffer tank 15 is provided in front of the bottom water collection tank 12, and the water collection buffer tank 15, the bottom water collection tank 12, the middle water collection tank 11, and the upper water collection tank 10 are sequentially raised to form a stacked state like a terrace. Each layer of the water collecting tank 14 and the water collecting buffer pool 15 can be made of steel plates by welding, the inner wall and the outer wall are sprayed with anticorrosive coatings, the inner wall can be sprayed with nontoxic epoxy resin for corrosion prevention, and the outer wall can be sprayed with zinc-rich high polymer paint for corrosion prevention. The upper layer water collecting tank 10 and the middle layer water collecting tank 11 are separated into a plurality of units by partition walls, an overflow weir 16 is arranged at the upper part of the partition wall, or a water passing hole 17 is arranged at the bottom of the partition wall, and the partition wall provided with the overflow weir and the partition wall provided with the water passing hole are arranged at intervals along the length direction in the water collecting tank, so that the wastewater forms a turn-back type flow. A lower overflow weir 18 is provided at one side of the lower water collection tank 12. A water outlet 19 is arranged at one side of the water collecting buffer pool 15.
And a water distribution device is arranged between the water collecting grooves of each layer. The water distribution device comprises a water inlet pipe and a water return pipe, the water inlet pipe is arranged in at least one layer of water collecting grooves, and the water return pipe is arranged between the adjacent water collecting grooves. An upper layer water inlet pipe 2 is arranged on one side of the upper layer water collecting tank 10, an upper layer water inlet valve 3 is arranged on the upper layer water inlet pipe 2, a middle layer water inlet pipe 4 is arranged on one side of the middle layer water collecting tank 11, and the water outlet of the middle layer water inlet pipe 4 is positioned at the water inlet end (the right end in fig. 1) of the middle layer water collecting tank 11. The upper layer water inlet pipe 2 and the middle layer water inlet pipe 4 are both connected with the water inlet main pipe 1. A first water return pipe 6 is connected between the water outlet end of the upper layer water collecting tank 10 and the water inlet end of the middle layer water collecting tank 11, and a first water return valve 7 is arranged on the first water return pipe 6. A second water return pipe 8 is connected between the water outlet end (the left end in fig. 1) of the middle water collecting tank 11 and the water inlet end of the bottom water collecting tank 12, and a second water return valve 9 is arranged on the second water return pipe 8.
The low-concentration heavy metal wastewater enters water from the bottom of one end of the upper-layer water collecting tank 10 through the water inlet header pipe 1, sequentially passes through the overflow weirs 16 and the water passing holes 17 of the partition walls in the upper-layer water collecting tank 10, flows up and down in the water collecting tank in a mode of turning over weir overflow and passing through the water passing holes, and flows into the middle-layer water collecting tank 11 from the first water return pipe 6 at the water outlet end. Flows into the bottom water collecting channel 12 in the same manner in the middle water collecting channel 11. No partition wall is provided in the lower water collecting tank 12, and the wastewater flows into the water collecting buffer tank 15 in an overflow manner through a lower overflow weir 18 at the upper portion of the lower water collecting tank 12. A layer of natural zeolite 20 is laid at the bottom of the water collecting buffer pool 15, and enrichment plants 21 are planted in the pool, so that stable water outlet at the tail end is ensured on one hand, and the safety of the water quality of the outlet water at the tail end is ensured on the other hand.
The modular adsorption units 22 are arranged in the partition units in each layer of the water collecting tank, and are in a completely submerged state in the water collecting tank.
As shown in fig. 2, the modular adsorption unit 22 includes water permeable bricks 23, an adsorption packing layer 27, and a plant cultivation tray 28. The water permeable brick 23 is made of light water permeable material, a layer of high-strength nylon woven net 25 wraps the water permeable brick 23, and a lifting handle 26 is arranged on the nylon woven net 25 so as to be convenient to lift and replace. The water permeable brick 23 is provided with a plurality of layers of transverse clearance grooves 30 (3 layers are arranged in figure 2), and the absorption filling layer 27 which can be replaced by drawing is arranged in the clearance grooves 30. The water permeable brick 23 is provided with a through water permeable hole 24 for planting a restoration plant 29. On top of the water permeable bricks 23 are placed plant cultivation trays 28 through which the enriched plants 29 are pre-cultivated and covered on top of the water permeable bricks 23, the roots of which during growth extend into the water permeable holes 24. As shown in fig. 3, the adsorption filling layer 27 includes a support frame 32, and the support frame 32 is filled with an adsorbent 33 held in a nylon mesh bag 34. The front end of the supporting frame 32 is provided with a trapezoidal tapering head 35, two sides of the trapezoidal tapering head are arranged in the hidden button handles 31,
the modularization adsorption unit is submerged to low concentration heavy metal waste water in the water catch bowl, adsorbs the heavy metal ion in the quick abundant adsorption waste water of adsorbent 33 in the filling layer 27, and the plant 29 in the hole 24 that permeates water of brick 23 slowly enriches the heavy metal on the adsorbent 33 in the growth process, cultivates tray 28 through the plant on the regular change brick 23 that permeates water and reaches the purpose of getting rid of the heavy metal.
The adsorbents 33 in the modular adsorption units arranged in the upper layer water collecting tank 10, the middle layer water collecting tank 11 and the bottom layer water collecting tank 12 are different, the adsorbents in the upper layer water collecting tank 10 and the middle layer water collecting tank 11 are modified zeolite, and the adsorbent in the bottom layer water collecting tank 12 is modified activated carbon.
The preparation process of the modified zeolite adsorbent in the upper layer water collecting tank 10 and the middle layer water collecting tank 11 is as follows:
crushing natural zeolite, sieving with 30-40 mesh sieve, adding 10% NH4Soaking in Cl solution for 3 hours, taking out and drying, and then roasting at a high temperature of 500 ℃ for 2 hours; then the calcined zeolite is treated with NH with the concentration of 10 percent4Soaking the Cl solution for 3 hours, drying and then roasting for 2 hours at 500 ℃; subjecting the twice calcined zeolite to a concentration of 10% NH4Soaking the Cl solution for 5 hours; finally, drying the soaked zeolite for 4 hours at the temperature of 40 ℃ to obtain NH4Cl modified zeolite.
The modified zeolite particles are respectively put into high-strength nylon mesh bags, the maximum gap of the nylon mesh bags is less than 0.2mm, and the maximum gap is determined by the minimum particle size of the filled modified zeolite, so that the zeolite particles do not penetrate through the adsorption filler.
FIG. 4 shows scanning electron micrographs of zeolite before and after modification. The specific surface area of the zeolite is measured to be 2.15m before modification2Increase in g to 3.47m2G, heavy metal Cd in laboratory conditions2+The adsorption capacity of the modified zeolite is increased from 4.5mg/g to 12mg/g, and the modification effect is obvious.
The modified activated carbon adsorbent in the bottom layer water collection tank 12 is prepared as follows:
(1) pretreatment of activated carbon: washing granular active carbon sold in the market with deionized water, and drying for 10 hours at 100 ℃;
(2)HNO3oxidation modification:
preparing a 10% nitric acid solution, and mixing the solution according to the weight ratio of 1 g: 2ml of the pretreated activated carbon particles are taken and dissolved in nitric acid solution, and the solution is heated for 2 hours under the condition of water bath at the temperature of 75 ℃; after cooling, washing the mixture by deionized water; drying the washed sample in an oven at 120 ℃ for 6 hours; putting the dried activated carbon into a muffle furnace to activate for 2 hours at the temperature of 400 ℃ to obtain HNO3Modified activated carbon.
The obtained HNO3The oxidation modified active carbon is used as an adsorbent filled in the adsorption filling layer after being screened by a 100-mesh sieve.
The modified activated carbon particles are placed in a high-strength nylon mesh bag, the maximum gap of the nylon mesh bag is less than 0.2mm, and the maximum gap is determined by the minimum particle size of the filled modified activated carbon, so that the activated carbon particles do not penetrate through the adsorption filler. FIG. 5 shows scanning electron micrographs of activated carbon before and after modification. The specific surface area of the activated carbon is measured to be 450m before modification2Increase/g to 615m2G, heavy metal Cd in laboratory conditions2+The adsorption capacity of the modified zeolite is increased from 98.2mg/g to 125.3mg/g, and the modification effect is obvious.
The operation process of the system for treating the low-concentration heavy metal wastewater is as follows.
According to the difference of the heavy metal types in the inlet water quality, plants with high enrichment capacity aiming at different heavy metals are selected, the selected plants are cultivated on a plant cultivation tray 28 in advance and then are placed at the upper end of the water permeable brick 23, and the plants are aligned to the water permeable holes 24 of the water permeable brick 23, so that the plants can be favorably absorbed by the following growth.
In the initial operation stage, the water inlet valve 3 at the upper layer and the valves on the water return pipes are opened, the water inlet valve 5 at the middle layer is closed, so that the wastewater turns back and flows in the dividing units of the water collecting tank outside the bottom layer, the effluent of the water collecting tank at the upper layer enters the water collecting tank at the lower layer through the water return pipes, the modular adsorption units in the water collecting tank are in a completely submerged state, the wastewater passes through the water collecting tanks layer by layer and then enters the water collecting buffer pool, and the wastewater is discharged from a water outlet of the water collecting buffer pool after being further adsorbed by natural zeolite and plants in the water collecting buffer pool.
Because the adsorption speed of the adsorbent is far higher than the plant enrichment speed, and the adsorption of the adsorbent is saturated after a period of time. And (3) reserving enough time for enriching the plants, closing the upper-layer water inlet valve 2 and the first water return valve 7 according to a certain time, opening the middle-layer water inlet valve 5, feeding the wastewater from the right end of the middle-layer water collecting tank 11 through the middle-layer water inlet pipe 4, allowing the heavy metal wastewater to preferentially enter the middle-layer water collecting tank 11, and leaving the upper-layer water collecting tank 10 empty to allow the plants thereon enough time for enriching the heavy metals on the adsorbent. And according to the concentration of the heavy metal in the inlet water, the inlet water flow and the adsorption capacity of the adsorbent, determining the opening or closing of the inlet water valves on the water collecting grooves of each layer and the return water valves on the return water pipes.
The opening and closing alternation time of the upper layer water inlet valve 2, the first water return valve 7 and the middle layer water inlet valve 5 is calculated according to the maximum adsorption capacity of the adsorbent, the concentration of the heavy metal of the inlet water, the water inflow and the filling amount of the adsorbent, and the specific calculation process is as follows.
Through experimental data analysis, the adsorption characteristics of the modified zeolite of the invention meet the following fitting formula
Figure GDA0002875240090000071
In the formula: q. q.seThe adsorption amount (mg/g, mass mg of heavy metal adsorbed per g of modified zeolite) at equilibrium (maximum adsorption amount under low concentration conditions);
Cethe concentration (mg/L) of heavy metals in water at equilibrium;
Kmthe adsorption constant is 0.06-0.15;
qmthe saturated adsorption capacity (mg/g, mass mg of heavy metal adsorbed per g of modified zeolite);
t is the water temperature (DEG C) of the wastewater;
efficiency of adsorption
Figure GDA0002875240090000072
In the formula: q. q.seTheoretical adsorption capacity at equilibrium (mg/g); (q iseAs in the previous meaning, the maximum adsorption capacity at low concentration);
qais the actual adsorption capacity (mg/g)
The valve is closed and opened alternatively for the following time:
Figure GDA0002875240090000073
in the formula: q. q.seThe amount of adsorbed substances in equilibrium (mg/g)
Beta is the adsorption rate;
v is the water collecting tank of the layerInflow of medium waste water, m3/h；
M is the filling amount of the adsorbent in each module adsorption unit, kg;
n is the number of the module adsorption units in the layer of water collecting tank;
c is the concentration of heavy metal in the inlet water of the water collecting tank of the layer, g/m3。
Examples
The effluent quality of a sewage discharge port of a certain electroplating plant reaches the standard and is discharged, and the concentration of the heavy metal Cd is 0.5 mg/L.
The system of the invention is adopted to carry out composite treatment with the treatment scale of 50m3And d. 7 adsorption units are arranged in each layer of water collecting tank, the size of the adsorption filling layer in each water collecting tank is 65cm multiplied by 5cm, and the filling amount of each adsorption unit is about 36 kg. Aquatic plants of common sowthistle and cattail are planted on the plant culture tray 28 in the three-layer water collecting tank in a matching way, and aquatic plants of reeds are planted in the water collecting buffer tank 15.
The effluent concentration of the wastewater containing low-concentration heavy metal Cd by the modular composite advanced treatment method reaches 0.002mg/L, and the effluent quality is stable and the treatment effect is obvious after the wastewater is continuously operated for 6 months.

Claims (10)

1. The utility model provides a compound advanced treatment system of modularization of low concentration heavy metal waste water, includes water distribution system, water collection system and modularization adsorption unit, characterized by:
the water collecting device comprises water collecting tanks and water collecting buffer tanks, wherein the water collecting tanks are at least provided with two layers, the water collecting buffer tanks and all layers of water collecting tanks are arranged from bottom to top in a stacked mode, one side, connected with the water collecting buffer tank, of the bottommost water collecting tank is provided with a bottom overflow weir, partition walls are arranged in all the other layers of water collecting tanks to form a partition unit, upper overflow weirs or bottom water passing holes are arranged on the partition walls, the partition walls provided with the overflow weirs and the partition walls provided with the water passing holes are arranged in the water collecting tanks at intervals along the length direction, water outlets are arranged on the outer sides of the water collecting buffer tanks, and the bottoms of the water collecting buffer;
the water distribution device comprises a water inlet pipe and a water return pipe, the water inlet pipe is connected with the water inlet ends of other water collecting tanks except the bottommost layer, the water return pipe is arranged between the water outlet end of the upper layer water collecting tank and the water inlet end of the lower layer water collecting tank of the two adjacent layers of water collecting tanks, a water inlet valve is arranged on the water inlet pipe, and a water return valve is arranged on the water return pipe;
all set up the modularization in every layer of water catch bowl and adsorb the unit, the modularization adsorbs the unit and cultivates the tray including permeating water brick, absorption filling layer and plant, is provided with the slot in the brick that permeates water, places the absorption filling layer in the slot, is provided with the planting hole in the brick that permeates water, and the top of the brick that permeates water sets up the plant and cultivates the tray.
2. The modular composite advanced treatment system for low-concentration heavy metal wastewater as claimed in claim 1, which is characterized in that: the water permeable bricks are wrapped with woven nets, and handles are arranged on the woven nets.
3. The modular composite advanced treatment system for low-concentration heavy metal wastewater as claimed in claim 1, which is characterized in that: the adsorption filling layer comprises a support frame, and the support frame is filled with an adsorbent filled in mesh bags.
4. The modular composite advanced treatment system for low-concentration heavy metal wastewater as claimed in claim 1, which is characterized in that: and the adsorbent of the adsorption filling layer in the modular adsorption units in the water collecting tank of the other layer except the water collecting tank of the bottom layer is modified zeolite.
5. The modular composite advanced treatment system for low-concentration heavy metal wastewater as claimed in claim 4, wherein: the preparation process of the modified zeolite is as follows:
crushing natural zeolite, sieving with 30-40 mesh sieve, adding 10% NH4Soaking in Cl solution for 3 hours, taking out and drying, and then roasting at a high temperature of 500 ℃ for 2 hours; then the calcined zeolite is treated with NH with the concentration of 10 percent4Soaking the Cl solution for 3 hours, drying and then roasting for 2 hours at 500 ℃; subjecting the twice calcined zeolite to a concentration of 10% NH4Soaking the Cl solution for 5 hours; finally drying the soaked zeolite at 40 deg.C for 4 hrTo obtain NH4Cl modified zeolite.
6. The modular composite advanced treatment system for low-concentration heavy metal wastewater as claimed in claim 4, wherein: the modified zeolite particles are placed into a mesh bag after being screened by a 60-mesh sieve, and the maximum gap of the mesh bag is less than 0.2 mm.
7. The modular composite advanced treatment system for low-concentration heavy metal wastewater as claimed in claim 1, which is characterized in that: and the adsorbent of the adsorption filling layer in the modular adsorption unit in the bottom water collecting tank is modified activated carbon.
8. The modular compound advanced treatment system for low-concentration heavy metal wastewater as claimed in claim 7, wherein: the preparation process of the modified activated carbon adsorbent is as follows:
(1) pretreatment of activated carbon: washing the granular activated carbon with deionized water, and drying for 10 hours at 100 ℃;
(2)HNO3oxidation modification:
preparing a 10% nitric acid solution, and mixing the solution according to the weight ratio of 1 g: 2ml of the pretreated activated carbon particles are taken and dissolved in nitric acid solution, and the solution is heated for 2 hours under the condition of water bath at the temperature of 75 ℃; after cooling, washing the mixture by deionized water; drying the washed sample in an oven at 120 ℃ for 6 hours; putting the dried activated carbon into a muffle furnace to activate for 2 hours at the temperature of 400 ℃ to obtain HNO3Modified activated carbon.
9. The operation method of the modular compound advanced treatment system for the low-concentration heavy metal wastewater in the claim 1 is characterized by comprising the following steps:
(1) for low-concentration heavy metal wastewater, selecting plants with enrichment capacity aiming at different heavy metals according to the types of the heavy metals in the wastewater, cultivating the selected plants on a plant cultivation tray in advance, putting the plant cultivation tray on a water permeable brick, and aligning the plants to planting holes of the water permeable brick so as to be beneficial to the subsequent growth and absorption of the plants; simultaneously planting the selected plants in the water collecting buffer tank;
(2) opening a valve on a water inlet pipe connected with the water collecting tank on the uppermost layer and valves on water return pipes to enable the wastewater to turn back and flow in the dividing units of the water collecting tanks outside the bottom layer, enabling the water outlet of the upper water collecting tank of two adjacent layers of water collecting tanks to enter the lower water collecting tank through the water return pipes, enabling the modular adsorption units in the water collecting tanks to be in a completely submerged state, enabling the wastewater to pass through the water collecting tanks layer by layer and then enter a water collecting buffer pool, and discharging the wastewater through a water outlet of the water collecting buffer pool after further adsorption of natural zeolite and plants in the water collecting buffer pool;
(3) the valves on the water inlet pipes of other water collecting tanks except the bottommost layer are opened and closed alternately, the valve on the water inlet pipe of the upper water collecting tank and the valve on the water return pipe between the upper water collecting tank and the lower water collecting tank are opened for a certain time and then closed, and meanwhile, the valve on the water inlet pipe of the lower water collecting tank is opened to enable waste water to enter the lower water collecting tank, so that plants on the upper water collecting tank have enough time to enrich heavy metals on the adsorbent in the adsorption filling layer in the upper modularized adsorption unit.
10. The operation method of the modular complex advanced treatment system for low concentration heavy metal wastewater of claim 9, wherein the valve on the inlet pipe of the water collecting tank is opened and closed alternately for the following time:
the valve on the water inlet pipe of the water collecting tank is opened and closed for the following alternative time:
Figure FDA0002898440430000021
in the formula: q. q.seThe unit mg/g is the adsorption quantity in equilibrium, and each g of modified zeolite adsorbs the mass mg of heavy metal;
Figure FDA0002898440430000022
wherein: ceThe concentration of heavy metal in water in unit mg/L during balancing;
Kmis adsorption constantThe value is 0.06-0.15;
qmthe saturated adsorption capacity is unit mg/g, and each g of modified zeolite adsorbs the mass mg of heavy metal;
t is the water temperature of the wastewater, unit ℃;
beta is the rate of adsorption and is,
Figure FDA0002898440430000023
wherein: q. q.seThe adsorption capacity in the unit of mg/g is the adsorption capacity in the equilibrium; q. q.saThe actual adsorption amount is unit mg/g;
v is the inlet flow of the wastewater in the layer of water collecting tank, m3/h；
M is the filling amount of the adsorbent in each module adsorption unit, kg;
n is the number of the module adsorption units in the layer of water collecting tank;
c is the concentration of heavy metal in the inlet water of the water collecting tank of the layer, g/m3。
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