CN113461181A - Method and device for relieving scale formation of concentrated solution evaporation equipment of landfill - Google Patents
Method and device for relieving scale formation of concentrated solution evaporation equipment of landfill Download PDFInfo
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- CN113461181A CN113461181A CN202110795442.XA CN202110795442A CN113461181A CN 113461181 A CN113461181 A CN 113461181A CN 202110795442 A CN202110795442 A CN 202110795442A CN 113461181 A CN113461181 A CN 113461181A
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
Abstract
The invention relates to a method and a device for relieving the scaling of concentrated solution evaporation equipment in a landfill. Comprises mixing and precipitating the medicament and the concentrated solution, wherein the medicament comprises sodium hydroxide solution, lime slurry, sodium carbonate solution and diatomite, and four medicaments are simultaneously added in the process of mixing and precipitating. Through the process of treating the concentrated solution by matching the medicament, calcium and magnesium ions and other metal ions can be effectively removed, the settling property of the sludge can be remarkably improved, and the settling time is shortened. And the scale formation is reduced.
Description
Technical Field
The invention belongs to the technical field of removal of calcium and magnesium ions in wastewater, and particularly relates to a method and a device for relieving scaling of concentrated solution evaporation equipment of a landfill.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, with the increasing urbanization process of China, the production amount of household garbage tends to increase gradually. At present, sanitary landfill is still the main disposal mode of domestic garbage due to the advantages of mature technology, low disposal cost and the like, particularly in the middle and western regions. Leachate is one of the main secondary pollutants of sanitary landfills, mainly coming from natural rainfall, water of the garbage itself and water produced by the degradation of the garbage. The landfill leachate is high-pollution organic wastewater and has the characteristics of multiple pollutant types, high COD concentration, high ammonia nitrogen concentration, heavy metal elements and the like. The main treatment and disposal modes of the percolate comprise a biological treatment method, a physical and chemical treatment method, a membrane technology and the like. In order to meet the strict leachate discharge standard, most leachate treatment plants adopt combined processes of pretreatment, biochemistry, membrane treatment and the like, such as pretreatment of MBR, NF and RO and the like. The membrane treatment processes of NF + RO and the like produce 25-40% concentrated solution (concentrated solution for short), the components of the concentrated solution are complex, and the concentration of organic matters, inorganic salts and metal ions are relatively high.
At present, the treatment methods of the concentrated solution mainly comprise a recharging method, an advanced oxidation method, a coagulating sedimentation method, mechanical compression evaporation and the like. The long-term recharging easily causes the concentration increase of soluble salts and organic pollutants, influences subsequent biochemical treatment units, and causes the serious scaling of the membrane to reduce the service life of the membrane. In recent years, mechanical compression evaporation technology is widely used for treating concentrated solution, and the principle of the technology is to convert mechanical energy into heat energy, increase the temperature by mechanically compressing steam, and reduce the concentrated solution. However, in engineering practice, it is found that a large amount of crystals are generated in the evaporation process due to the high salt content of the concentrated solution, and severe equipment corrosion and scaling phenomena occur in the evaporation process, which seriously affects the operation and service life of treatment equipment. The investigation shows that calcium and magnesium ions in the concentrated solution are one of the main causes of equipment corrosion and scaling.
At present, the method for removing calcium and magnesium ions in wastewater mainly comprises a medicament method, an ion exchange method, a membrane separation method, an electrochemical method, an adsorption method and the like. The medicament method mainly adds a large amount of organic scale inhibitor, but the components are sensitive to heat, and the components of the scale inhibitor change in the evaporation process to influence the effect of the scale inhibitor. Ion exchange methods are rarely used in engineering practice due to their high cost of consumption. At present, on the premise of considering economy, operability, high efficiency and the like, further development of concentrated solution calcium and magnesium ion removal technology with engineering application background is still needed.
Disclosure of Invention
In view of the above-described problems with the prior art, it is an object of the present invention to provide a method and apparatus for mitigating fouling of landfill concentrate evaporation equipment. The removal effect of calcium and magnesium ions is improved, and the evaporation scaling amount is reduced.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, a method for relieving the scaling of evaporation equipment of concentrated solution in a landfill comprises the steps of mixing and precipitating agents and the concentrated solution, wherein the agents comprise sodium hydroxide solution, lime slurry, sodium carbonate solution and diatomite, and four agents are added simultaneously in the process of mixing and precipitating.
According to the invention, calcium and magnesium ions and other metal ions can be effectively removed through the process of treating the concentrated solution by matching the medicament, the sedimentation performance of the sludge can be remarkably improved, and the sedimentation time can be shortened.
The sodium hydroxide contains hydroxide ions, can quickly improve the pH value of the liquid, and then is matched with sodium carbonate to effectively and quickly form precipitates of calcium ions and magnesium ions, wherein the calcium ions and the magnesium ions are mostly precipitated by basic magnesium carbonate, magnesium hydroxide, calcium carbonate and the like.
The added diatomite and lime slurry can increase the particle size and the physicochemical property of the sludge, remarkably improve the settling property of the precipitate and shorten the settling time.
The diatomite is introduced into the system, because the diatomite has a natural molecular sieve-shaped pore structure, the specific surface area is very high, which is 6000 times that of active carbon, and the diatomite is used as a carrier, and the generated calcium and magnesium precipitates can be attached to the surface of the diatomite to prevent the precipitates from existing in a free state.
On one hand, the lime slurry can remove excessive magnesium ions in the concentrated solution, in addition, the lime slurry also has good settling performance, and can generate a synergistic effect with diatomite to generate certain 'wrapping' and 'carrying' effects on basic magnesium carbonate, magnesium hydroxide, calcium carbonate and other precipitates, so that the settling of the precipitates is accelerated, and the settling time is shortened.
Therefore, the four medicaments are matched to quickly form precipitate, then the precipitate is quickly settled, the solid-liquid separation effect is good, and the removal effect of calcium and magnesium ions in the concentrated solution is improved. The corrosion and scaling of equipment caused by the deposition formed by calcium and magnesium ions are avoided. Compared with the solid-liquid separation effect of adding sodium hydroxide or sodium carbonate separately, the solid-liquid separation effect is improved by more than 50%.
In some embodiments of the invention, the diatomaceous earth comprises, by weight, 0.5 to 1% of the concentrate; further 0.8 to 1%. The combination of the diatomite and the sediment leads the sediment to gather together and enlarges the particles of the sludge, and the finally formed sludge contains a certain amount of diatomite, thus changing the physical and chemical properties of the sludge. If the amount of diatomaceous earth added exceeds the above range, the adsorption performance is lowered, and diatomaceous earth is suspended in the solution.
In some embodiments of the invention, the volume ratio of the sodium hydroxide solution, the lime slurry and the sodium carbonate solution is 10-20: 5-10 and 2-4. The adding speed of the sodium hydroxide solution, the lime slurry and the sodium carbonate solution influences the settling speed of ions in the concentrated solution, the solidification separation effect and the removal effect of calcium, magnesium ions and other toxic metal ions. Simultaneously, four medicaments are added, and the adding speed of each medicament is matched, so that the solid-liquid separation effect is improved.
In some embodiments of the invention, the sodium hydroxide solution has a mass concentration of 25-35%; further 28-32%; still further 30-32%. The pH of the mixed solution is increased by the sodium hydroxide, and the sodium hydroxide provides hydroxide radical which is generally used for the reaction of calcium, magnesium ions, hydroxide ions and bicarbonate radical to generate magnesium hydroxide and calcium carbonate precipitate (equation 1); or the reaction of magnesium ions, bicarbonate and hydroxide ions to generate basic magnesium carbonate (equation 2), wherein in the two reactions, the equation is as follows:
HCO3 -+3OH-+Ca2++Mg2+→Mg(OH)2↓+CaCO3↓+H2o (Eq.1)
4CO3 -+5Mg2++2OH-+4H2O→Mg5(CO3)4(OH)2·4H2O ↓ (equation 2)
In some embodiments of the invention, the lime slurry has a mass concentration of 70-80%. The main component of the lime slurry is hydrated lime, and the hydrated lime can remove magnesium ions and settle along with the precipitate.
In some embodiments of the invention, the sodium carbonate solution has a sodium carbonate mass concentration of 40-60%; further 50-55%. The sodium carbonate solution provides carbonate ions to form calcium carbonate, magnesium carbonate, basic magnesium carbonate, and the like.
In some embodiments of the invention, the pH control during the mixed precipitation is in the range of 12-12.5. The four agents are added while maintaining the pH of the mixed solution at 12-12.5 in an alkaline environment, so that calcium and magnesium ions are rapidly precipitated.
In some embodiments of the invention, the time of the mixed precipitation is 0.5 to 3 hours; further 1-2 h; further 1.2-1.8 h. The time for mixed precipitation is 50% shorter than that for adding sodium hydroxide or sodium carbonate alone. The existing method uses sodium carbonate or sodium hydroxide and flocculant to carry out precipitation, the flocculation principle of the flocculant is to destabilize particles, but the process is related to the properties of the particle surface and the running state of the particles. According to the invention, the sediment is directly driven by the adsorption, wrapping and carrying effects of the diatomite and the lime slurry, so that the solid-liquid separation effect is better, and the settling time is favorably shortened.
In some embodiments of the invention, a mixed solution is obtained after mixing and precipitation, the mixed solution is subjected to solid-liquid separation, and the supernatant after the solid-liquid separation is subjected to a pH adjustment process. The supernatant liquid of the solid-liquid separation mainly comprises sodium ions, chloride ions, potassium ions and partial hydroxide ions, the pH is adjusted back, and the evaporation scaling amount is reduced through the pH adjustment back.
In some embodiments of the invention, a hydrochloric acid solution is added to the pH adjustment, and the mass concentration of the hydrochloric acid solution is 10-20%. Hydrochloric acid is added to neutralize the remaining hydroxide ions.
In some embodiments of the invention, the pH is adjusted back to a pH of 4.0 to 5.0. The adjustment to the acidic condition can reduce the residue amount and the mineral characteristics in the subsequent evaporation process.
In a second aspect, the device for relieving the scaling of the concentrated solution evaporation equipment of the landfill comprises a stirring tank, a sedimentation tank and a pH adjusting tank which are sequentially connected.
In some embodiments of the invention, 10-20 sets of vertically arranged folding plates are arranged in the sedimentation tank; furthermore, the included angle theta of the folded plate is 90-120 degrees, the wave height h is 0.3-0.4m, and the plate width d is 0.5-0.8 m. The folded plates are arranged in the sedimentation tank to divide the sedimentation tank into a plurality of hydraulic areas, which is beneficial to separating sediments.
In some embodiments of the invention, the device further comprises a water storage tank, and the water outlet of the pH adjusting tank is connected with the water storage tank. And the pH value is adjusted back and then enters a water storage tank for storage.
In some embodiments of the invention, the agitation tank is connected to the medicament reservoir. The stirring teeth are used for mixing different medicaments, and the mixed medicaments are introduced into the sedimentation tank, so that the four medicaments uniformly enter the sedimentation tank.
One or more technical schemes of the invention have the following beneficial effects:
1) can effectively remove calcium and magnesium ions and other metal ions in the concentrated solution
The agent mixing unit of the invention respectively adds sodium hydroxide solution, lime slurry, diatomite and sodium carbonate solution into one unit, the pH value of the added sodium hydroxide solution can be rapidly increased, the pH value range is controlled to be 12-12.5 in the reaction process, calcium and magnesium ions under the conditions of different concentrations (such as Ca 400-. In addition, the invention can remove most of toxic metal ions, such as Ni, Sr, Mn, Cr, Cd, Zn and the like, while removing calcium and magnesium ions. Through the treatment of the unit, calcium and magnesium ions are mostly precipitated by basic magnesium carbonate, magnesium hydroxide, calcium carbonate and the like, the removal efficiency of the calcium and magnesium ions is over 99 percent, and the concentration of the calcium and magnesium ions in effluent is generally less than 2-5 mg/L.
2) Remarkably improves the sedimentation performance of the sludge and shortens the sedimentation time
The added diatomite and lime slurry can increase the particle size and the physicochemical property of the sludge, can obviously improve the settling property of the precipitate and shorten the settling time. The diatomite is introduced into the system, because the diatomite has a natural molecular sieve-shaped pore structure, the specific surface area is very high, which is 6000 times that of active carbon, and the diatomite is used as a carrier, and the generated calcium and magnesium precipitates can be attached to the surface of the diatomite to prevent the precipitates from existing in a free state. On one hand, the lime slurry can remove excessive magnesium ions in the concentrated solution, in addition, the lime slurry also has good settling performance, and can generate a synergistic effect with diatomite to generate certain 'wrapping' and 'carrying' effects on basic magnesium carbonate, magnesium hydroxide, calcium carbonate and other precipitates, so that the settling of the precipitates is accelerated, and the settling time is shortened. In addition, the existence of the carbonate can ensure that calcium ions form precipitates with calcium carbonate, and the removal efficiency of the calcium ions is improved. Overall, compared with a single alkaline solution method, the solid-liquid separation efficiency is improved by more than 50%, the settling time is shortened by more than 3h, and the settling effect is good.
3) Reduce the evaporation scale formation amount and change the mineral characteristics of evaporation residues
At present, low-temperature evaporation is an important unit for treating concentrated solution, and the normal operation of equipment is influenced by the scaling condition of the surface of the equipment in the evaporation process, and the corrosion and scaling condition of the equipment is also determined. After solid-liquid separation, the pH value of the effluent can be adjusted to 4.0-5.0, and the laboratory simulation evaporation results show that the treatment of the invention can reduce the scaling amount of the simulated evaporation of the concentrated solution. In addition, the invention can also change the chemical composition and mineral characteristics of the evaporation residue, avoid the generation of scaling minerals such as calcium sulfate and the like, convert the scaling minerals into chloride salts such as NaCl, KCl and the like, and slow down the scaling phenomenon of evaporation equipment.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a process flow diagram of a method of mitigating fouling of landfill concentrate evaporating equipment in accordance with the present invention;
FIG. 2 is a schematic diagram of an apparatus for mitigating fouling of a landfill concentrate evaporation plant in accordance with the present invention;
FIG. 3 is a graph showing the sludge settling performance in example 1 of the present invention;
FIG. 4 shows the change in the quality of scale formation in the simulated evaporation process before and after the treatment of the concentrated solution in example 1 of the present invention;
FIG. 5 is an X-ray diffraction pattern of a simulated evaporation scale product in example 1 of the present invention;
FIG. 6 is a transmission electron microscope microscopic structure diagram of a simulated evaporation fouling product in example 1 of the present invention: before (above) treatment; after treatment (below);
the device comprises a medicament storage tank 1, a stirrer 2, a stirring tank 3, a stirring tank 4, a sedimentation tank 5, a pH adjusting tank 6, a water storage tank 7 and an overflow valve.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As shown in fig. 2, the device for relieving the scale formation of the concentrated solution evaporation equipment of the landfill comprises a stirring tank 3, a sedimentation tank 4, a pH adjusting tank 5 and a water storage tank 6 which are connected in sequence. Stirring tank 3 is connected with medicament storage tank 1, and stirring tank 3 and pH readjust pond 5 are inside to set up agitator 2, set up the folded plate in the sedimentation tank 4, set up overflow valve 7 between sedimentation tank 4, pH readjust pond 5, the tank 6.
The invention will be further illustrated by the following examples
Example 1
The concrete water quality parameters of a certain landfill concentrated solution sample are pH 8.2, COD 1340mg/L and Ca2+＝212mg/L，Mg2+＝849mg/L。
The concentrated solution is treated by adopting the treatment method, 30% of sodium hydroxide solution, 75% of lime slurry, 50% of sodium carbonate solution and 0.8% of diatomite by mass are sequentially added into a stirring tank, a paddle type stirrer is started to stir for 3min, the pH value control range is controlled to be 12.5 in the reaction process, the mixed solution quickly enters a folded plate sedimentation tank and is precipitated for 1.5h, the supernatant moves upwards through an inclined plate and overflows through an overflow valve 1, a hydrochloric acid solution with the concentration of 15% is added into the tank body, the pH value is adjusted to be 5.0, and the effluent enters a water storage tank.
Examples of the experiments
The concentrate treatment of example 1 was compared to the concentrate treatment with the addition of sodium hydroxide solution alone.
The settling performance of the sludge in the embodiment 1 is obviously improved, the settling time is shortened by more than 50% compared with that of the single alkali liquor treatment (figure 3), and the removal efficiency of calcium and magnesium ions is more than 99.5%. The supernatant obtained in example 1 and the concentrate before the treatment were subjected to simulated evaporation under indoor conditions, and it was found from FIG. 4 that the amount of evaporation scale was significantly reduced from 5.38g/100mL before the treatment to 5.26g/100 mL. When the calcium and magnesium ions are more, the scale is calcium sulfate, and when the calcium and magnesium ions are not more, the scale is sodium chloride, and the latter is easy to remove.
XRD analysis results show (figure 5) that the simulated evaporation scaling products of the concentrate stock solution are mainly NaCl and CaSO4And the simulated evaporation scale products of the supernatant are mainly NaCl and KCl, and the crystal peaks near 32 degrees and 75 degrees in an XRD pattern disappear, and the crystal peak intensity near 45 degrees is obviously increased, which means that the crystal structure of the chlorine salt is different while the calcium and magnesium ions are removed. Mainly because the chloride salt in the stock solution of the concentrated solution also comprises calcium chloride, magnesium chloride and the like.
As can be seen from the TEM result of the transmission electron microscope in FIG. 6, the simulated evaporation scaling product of the stock solution of the concentrated solution (the upper graph in FIG. 6) is mainly a combination of various irregular minerals such as rectangle, trapezoid, triangle, and sphere-like, while the simulated evaporation scaling of the supernatant solution (the lower graph in FIG. 6) is different from the simulated evaporation scaling product of the stock solution, and is mostly a layered, elliptical, and compact mineral structure, which indicates that the mineral characteristics of the scaling product are significantly changed before and after the alkali solution treatment. The concentrated solution stock solution mainly contains a plurality of different components, most of the substances in the supernatant solution are sodium chloride and potassium chloride, and the components are single, so the mineral characteristics of the product are greatly different.
Example 2
The concrete water quality parameters of a certain landfill concentrated solution sample are that pH is 8.5, COD is 1980mg/L, Ca2+＝689mg/L，Mg2+＝182mg/L。
The concentrated solution is treated by adopting the treatment method, 32% of sodium hydroxide solution, 70% of lime slurry, 55% of sodium carbonate solution and 1% of diatomite by mass are sequentially added into a stirring tank, a paddle type stirrer is started to stir for 5min, the control range of the pH value is controlled to be 12.3 in the reaction process, a drain valve is started to enable the mixed solution to rapidly enter a folded plate sedimentation tank, the mixed solution is precipitated for 1.2h, the supernatant moves upwards through an inclined plate and overflows through an overflow valve 1, 18% of hydrochloric acid solution is added into a tank body, the pH is adjusted to 4.7, and the effluent enters a water storage tank. Through the treatment of the embodiment 2, the sedimentation performance of the sludge is obviously improved, and the removal efficiency of calcium and magnesium ions is over 99.4 percent.
Example 3
The concrete water quality parameters of a certain landfill concentrated solution sample are that pH is 8.0, COD is 1571mg/L, and Ca2+＝458mg/L，Mg2+＝484mg/L。
The concentrated solution is treated by adopting the treatment method, 32% of sodium hydroxide solution, 80% of lime slurry, 50% of sodium carbonate solution and 1% of diatomite by mass are sequentially added into a stirring tank, a paddle type stirrer is started to stir for 4min, the control range of the pH value is controlled to be 12.5 in the reaction process, a drain valve is started to enable the mixed solution to quickly enter a folded plate sedimentation tank, the mixed solution is precipitated for 1.8h, the supernatant moves upwards through an inclined plate and overflows through an overflow valve 1, a hydrochloric acid solution with the concentration of 15% is added into a tank body, the pH is adjusted to be 5.0, and the effluent enters a water storage tank. Through the treatment of the embodiment 3, the sedimentation performance of the sludge is obviously improved, and the removal efficiency of calcium and magnesium ions is over 99.8 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for relieving the scaling of concentrated solution evaporation equipment in a landfill is characterized by comprising the following steps: comprises mixing and precipitating the medicament and the concentrated solution, wherein the medicament comprises sodium hydroxide solution, lime slurry, sodium carbonate solution and diatomite, and four medicaments are simultaneously added in the process of mixing and precipitating.
2. The method of mitigating fouling of landfill concentrate evaporating equipment as recited in claim 1, further comprising: the diatomite accounts for 0.5 to 1 percent of the mass of the concentrated solution; further 0.8 to 1%.
3. The method of mitigating fouling of landfill concentrate evaporating equipment as recited in claim 1, further comprising: the volume ratio of the sodium hydroxide solution to the lime slurry to the sodium carbonate solution is 10-20: 5-10 and 2-4.
4. The method of mitigating fouling of landfill concentrate evaporating equipment as recited in claim 1, further comprising: the mass concentration of the sodium hydroxide solution is 25-35%; further 28-32%; still further 30-32%.
5. The method of mitigating fouling of landfill concentrate evaporating equipment as recited in claim 1, further comprising: and lime slurry with the mass concentration of 70-80%.
6. The method of mitigating fouling of landfill concentrate evaporating equipment as recited in claim 1, further comprising: the mass concentration of sodium carbonate in the sodium carbonate solution is 40-60%; further 50-55%.
7. The method of mitigating fouling of landfill concentrate evaporating equipment as recited in claim 1, further comprising: the pH value control range is 12-12.5 in the process of mixing and precipitating.
8. The method of mitigating fouling of landfill concentrate evaporating equipment as recited in claim 1, further comprising: the time of mixing and precipitating is 0.5-3 h; further 1-2 h; further 1.2-1.8 h.
9. The method of mitigating fouling of landfill concentrate evaporating equipment as recited in claim 1, further comprising: mixing and precipitating to obtain a mixed solution, carrying out solid-liquid separation on the mixed solution, and carrying out a pH (potential of hydrogen) adjustment process on a supernatant after the solid-liquid separation;
preferably, hydrochloric acid solution is added in the pH adjustment, and the mass concentration of the hydrochloric acid solution is 10-20%. Adding hydrochloric acid to neutralize residual hydroxide ions;
preferably, the pH is adjusted back to a pH of 4.0 to 5.0.
10. The utility model provides a alleviate device of landfill concentrate evaporation equipment scale deposit which characterized in that: comprises a stirring tank, a sedimentation tank and a pH adjusting tank which are connected in sequence;
preferably, 10-20 groups of vertically arranged folded plates are arranged in the sedimentation tank; furthermore, the included angle theta of the folded plate is 90-120 degrees, the wave height h is 0.3-0.4m, and the plate width d is 0.5-0.8 m.
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