CN107235590B - Treatment process for zero discharge and resource recycling of catalyst wastewater - Google Patents
Treatment process for zero discharge and resource recycling of catalyst wastewater Download PDFInfo
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Abstract
The invention relates to a treatment process for zero discharge and resource recycling of catalyst wastewater. The process mainly comprises a high-efficiency softening and desiliconizing system, a medium filtering system, an ultrafiltration system, an ion exchange system, a nanofiltration system, a nitrate separation membrane system, a reverse osmosis system, an electrodialysis system, a deamination evaporative crystallization system and a nitrate co-production evaporative crystallization system. The treatment process is used for treating the comprehensive wastewater with characteristics of high ammonia nitrogen, high silicon and high salt discharged in the production and preparation process of the catalyst, effectively solves the problems of high content of silicon dioxide, difficult removal, low quality of crystallized salt, large amount of miscellaneous salt and the like, finally forms the water for the production process of the catalyst, sodium chloride products and sodium sulfate products, and effectively achieves the purposes of zero discharge and recycling after the wastewater is treated.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a treatment process for realizing zero discharge and resource recycling of comprehensive wastewater with high ammonia nitrogen, high silicon and high salt characteristics discharged in a catalyst production process.
Background
The catalyst has important and wide application in the industries of petroleum processing, chemical fertilizer industry, chemical synthesis, high polymer material preparation, environmental protection and the like. The development and innovation of the catalyst can promote the development of the industry and generate great social and economic benefits. China pays great attention to the development of catalyst production technology and has a certain production scale. However, a large amount of wastewater is discharged in the catalyst production process, which not only pollutes the environment, but also causes a large amount of resource waste. Therefore, the research on the treatment technology of the catalyst production wastewater is urgent, and especially the research on the wastewater zero discharge technology and the resource recycling technology and the realization of industrialization have very important practical significance, and are the solid foundation for the sustainable development of the catalyst industry in China.
The wastewater discharged by the production of part of catalysts (which are oil refining catalysts used in devices such as catalytic cracking, catalytic reforming, hydrofining and the like) mainly has the following characteristics:
(1) the ammonia nitrogen content is high, and is usually 100-2000mg/L;
(2) the salt content is high, mainly sulfate, chloride and the like, and the concentration can reach more than 10000 mg/L;
(3) the concentration of suspended matters is high, and is usually 50-1000 mg/L;
(4) the silicon content is higher, and is usually 20-120 mg/L;
(5) the TOC content is very low, substantially less than 10 mg/L.
At present, the treatment process aiming at the wastewater mainly comprises the following steps:
(1) by biological methods (A/O, A)2The process comprises the steps of/O, oxidation ditch, improved SBR, short-cut nitrification and denitrification, and the like), directly discharging the ammonia nitrogen after removing the ammonia nitrogen, and increasing the biodegradability by adding a carbon source due to the serious unbalance of the C/N ratio in the wastewater, so that the conditions of high operation cost and unqualified total nitrogen in produced water are often caused;
(2) the ammonia nitrogen is removed by adopting processes such as a physical chemical method (adsorption, ion exchange, oxidation, stripping and the like) or a thermal method and the like and then is directly discharged, or the wastewater is mixed with high-concentration organic wastewater and then is directly discharged after coupling treatment of a physical method (flocculation precipitation) and a biological method, although the treatment process can reach the discharge standard in the early stage, the defects that the existing process cannot reach the new discharge standard and wastes a large amount of water resources are highlighted along with the stricter environmental protection discharge standard (especially the control on the salt content index in the discharged wastewater) and the continuous enhancement of the control and the management of enterprises on the water resources;
(3) after pollutants such as suspended matters, silicon, ammonia nitrogen and the like are removed, the wastewater is concentrated through a reverse osmosis membrane and treated through an evaporative crystallization process, the process can basically achieve zero emission of the wastewater, but the evaporation capacity of the whole process is large, the evaporation investment cost is high, and the burden of treating solid waste or hazardous waste of an enterprise is increased due to the fact that the amount of formed impurity salt is large.
In recent years, some sewage treatment processes are developed rapidly, the innovative coupling of the traditional wastewater treatment process and the improved wastewater treatment process technology is adopted, and the development direction of the treatment process is to realize zero emission and resource recycling of the catalyst production wastewater with the characteristics of high ammonia nitrogen, high silicon and high salt.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a treatment process for zero discharge and resource recycling of catalyst wastewater, and can realize zero discharge and resource recycling of comprehensive wastewater with high ammonia nitrogen, high silicon and high salt characteristics discharged in the catalyst production process. The invention adopts the following scheme:
a treatment process for zero discharge and resource recycling of catalyst wastewater comprises the following treatment steps:
(1) discharging high ammonia nitrogen, high silicon and high salt wastewater formed in the production process of the catalyst into a regulating water tank and staying for more than 20 hours, wherein the step is used for regulating the water quality and the water quantity of the comprehensive wastewater of the catalyst;
(2) regulating the effluent of the water tank, lifting the effluent by a pump, and then entering a high-efficiency softening and silicon-removing system, wherein part of pollutants such as hardness, alkalinity, suspended matters, organic matters, silicon dioxide and the like in the wastewater are effectively removed;
(3) the produced water of the high-efficiency softening and silicon-removing system enters a medium filtering system and is used as a pretreatment system for membrane concentration treatment to remove pollutants such as partial suspended matters in the wastewater;
(4) the water produced by the medium filtering system enters an ultrafiltration system, and the ultrafiltration system further removes pollutants such as suspended matters, colloid, bacteria and the like in the wastewater, so that the pollution degree of a nanofiltration membrane, a nitrate separation membrane, a reverse osmosis membrane and an ion exchange membrane is reduced;
(5) the water produced by the ultrafiltration system enters an ion exchange system to further remove calcium and magnesium ions and prevent a subsequent treatment system from scaling;
(6) the water produced by the ion exchange system enters a nanofiltration system, the wastewater is separated into concentrated water mainly containing sodium sulfate and produced water mainly containing sodium chloride under the action of the nanofiltration membrane, the concentrated water enters the step (7) for treatment, and the produced water enters the step (8) for treatment;
(7) the concentrated water treated in the step (6) enters a nitrate separation membrane system, the concentration of sodium sulfate is further improved to be used as concentrated water under the action of the nitrate separation membrane, the concentrated water enters a nitrate co-production evaporation system, namely, the treatment in the step (12), and the produced water of the nitrate separation membrane system and the nanofiltration produced water are mixed and then enter the treatment in the step (8);
(8) the produced water treated in the step (6) enters a first-stage reverse osmosis system, the concentration of sodium chloride in the wastewater is increased through the concentration effect of the first-stage reverse osmosis membrane to be used as concentrated water, the concentrated water is treated in the step (9), and the first-stage reverse osmosis produced water is treated in the step (10);
(9) the concentrated water treated in the step (8) enters an electrodialysis system, the concentration of sodium chloride in the concentrated water is further increased to more than 23% under the action of anion and cation exchange membranes in an electrodialysis device to form high-concentration brine, the high-concentration brine enters the step (11) for treatment, meanwhile, the electrodialysis system can also form desalted light brine, and the diluted light brine returns to the step (8) for treatment;
(10) the produced water treated in the step (8) enters a secondary reverse osmosis system, is separated into concentrated water and produced water again under the action of the secondary reverse osmosis membrane, the concentrated water of the secondary reverse osmosis system returns to the step (8) for treatment, and the produced water of the secondary reverse osmosis system enters a reuse water tank;
(11) the high-concentration brine processed in the step (9) and a part of mother liquor in the step (12) enter a deamination evaporation crystallization system, the high-concentration brine is evaporated and concentrated into sodium chloride supersaturated mother liquor after deamination, one part of the mother liquor enters a crystallizer to form sodium chloride crystal salt, the other part of the mother liquor enters the step (12) for processing, and condensate formed in the evaporation process is conveyed to a water consumption point;
(12) and (4) enabling the concentrated water treated in the step (7) and a part of mother liquor in the step (11) to enter a nitrate co-production evaporation system, evaporating and crystallizing to form anhydrous sodium sulfate crystal salt, and enabling a part of mother liquor in the nitrate co-production evaporation system to enter the deamination evaporation crystallization system in the step (11).
Preferably, the ascending flow rate of the high-efficiency softening and silicon-removing system in the step (2) is set to be 5-10m/h, magnesium chloride is used as a silicon-removing agent, and the pH is adjusted to be 10.5-11.5.
More preferably, the efficient softening silicon removal system in the step (2) is provided with an ammonia gas collecting device, and ammonia gas is introduced to the absorption tower.
Preferably, the recovery rate of the ultrafiltration system in the step (4) is set to be 90-93%, and PVDF is preferably used as the membrane material.
Preferably, the ion exchange system in the step (5) adopts macroporous sodium type weak acid cation resin, the regeneration mode of the resin is acid regeneration base conversion, and the regeneration wastewater of the ion exchange system flows back to the regulating tank.
Preferably, the concentration of the sulfate in the concentrated water after concentration in the nanofiltration system in the step (6) is more than 50000 mg/L.
Preferably, the cut-off molecular weight of the nitrate separation membrane system in the step (7) is 150-300 daltons, and the cut-off rate for sulfate is more than 99%.
More preferably, the TDS of the concentrated water of the nitrate salt separation membrane system in the step (7) is more than 180000 mg/L.
Preferably, the recovery rate of the primary reverse osmosis system in step (8) is set to 50% to 70%.
Preferably, the electrodialysis system in the step (9) adopts a homogeneous anion-cation exchange membrane, and the mass concentration of sodium chloride in the finally formed high-concentration brine is more than 23%.
Preferably, the recovery rate of the secondary reverse osmosis system in step (10) is set to 80% -90%.
Preferably, the deamination evaporation system in the step (11) adopts stripping deamination and evaporation integrated equipment, and part of mother liquor is discharged to a nitrate co-production crystallization system in the evaporation crystallization process.
Preferably, an MVR + multi-effect evaporation process is adopted in the process of co-production, evaporation and crystallization of the nitrate in the step (12), and the pH value is set to be 12 in the process of evaporation.
More preferably, part of mother liquor in the process of co-producing, evaporating and crystallizing the nitrate and the salt in the step (12) is returned to the deamination, evaporating and crystallizing system.
The treatment process has the following beneficial effects:
(1) the pretreatment, the membrane integration technology and the evaporative crystallization are combined to treat the high-ammonia-nitrogen high-silicon high-salt catalyst wastewater, so that the defects of large discharge capacity, unqualified salt content, large treatment capacity of mixed salt, unstable process and the like in the traditional treatment process of the wastewater are overcome, the zero discharge of the wastewater is realized, and the targets of reclaimed water recycling and salt resource recycling are realized.
(2) The process combining nanofiltration, nitrate separation membrane, reverse osmosis, electrodialysis, sodium chloride evaporative crystallization and nitrate coproduction evaporative crystallization realizes the recovery of sodium chloride and anhydrous sodium sulfate crystal salt in the wastewater under high efficiency and high quality, can adapt to the condition of large fluctuation of total salt amount and different salt concentrations in the water quality of raw water, and overcomes the defect of strict requirement of the traditional salt-nitrate coproduction evaporative crystallization system on the nitrate ratio in the water.
(3) The sodium chloride evaporation system adopts a stripping deamination and evaporation integrated process, and effectively combines the evaporation and ammonia recovery processes.
(4) By adopting a mode of controlling part of mother liquor to circularly reflux between the sodium chloride deamination evaporation system and the salt and nitrate co-production evaporation system, the quality of sodium chloride crystal salt is ensured, and the defect of impurity salt discharge in the wastewater zero discharge process is overcome.
(5) Electrodialysis is used as a pretreatment process of the deamination evaporation crystallization system, so that the mass concentration of sodium chloride before entering the evaporation system can reach more than 23%, and the investment scale of the evaporation system is greatly reduced.
(6) The mode of combining the nanofiltration system, the nitrate separation membrane system and the reverse osmosis system is adopted, so that the operation stability and high recovery rate of the whole membrane concentration process are ensured, the amount of evaporated waste water is reduced, the quality of reuse water and salt products is improved, and the whole process is ensured to operate reliably at low investment cost.
(7) The ion exchange resin is regenerated by acid regeneration and alkali transformation, so that the exchange capacity of the resin is ensured, and the stability and the reliability of the subsequent treatment process are improved.
(8) The high-efficiency softening and silicon-removing system is adopted as a pretreatment system of the whole integrated process, so that the softening and silicon-removing efficiency is high, the chemical adding amount can be flexibly adjusted to remove part of pollutants such as hardness, alkalinity, suspended matters, organic matters, silicon dioxide and the like in the wastewater, and the stability of the subsequent process is ensured.
Drawings
FIG. 1: the invention relates to a process flow chart for zero discharge and resource recycling of high ammonia nitrogen, high silicon and high salt catalyst wastewater.
Detailed Description
The invention will be further illustrated with reference to the following examples:
example 1
1. The specific water quality data of the raw water of this example using the catalyst wastewater discharged from a certain catalyst manufacturing company are shown in table 1:
TABLE 1 quality of influent water
2. And discharging the wastewater into a regulating water tank, and staying for 21 hours for regulating the water quality and water quantity of the comprehensive wastewater of the catalyst.
3. Adjusting the water outlet of the water tank, lifting the water outlet by a pump, then entering a high-efficiency softening and silicon-removing system, adding sodium hydroxide, sodium carbonate, PAM, PAC and magnesium chloride medicaments, adjusting the rising flow rate to 10m/h and the pH value to 10.8-11, and adjusting the water quality of the produced water after the high-efficiency softening and silicon-removing system to be shown in Table 2;
TABLE 2 high efficiency softening of the effluent quality of the desiliconization system
4. The water produced by the high-efficiency softening and silicon-removing system enters a medium filtering system and an ultrafiltration system, the recovery rate of the ultrafiltration system is set to be 93%, and the water is used as a pretreatment system for membrane concentration treatment to remove pollutants such as partial suspended matters in the wastewater.
5. And (3) the water produced by ultrafiltration enters an ion exchange system, and the ion exchange system adopts macroporous sodium type weak acid cation resin to further remove calcium and magnesium ions.
6. The ion exchange system enters a nanofiltration system, the concentration of sulfate in concentrated water is more than 50000mg/L, the concentrated water of the nanofiltration system enters a nitrate separation membrane system, produced water enters a first-stage reverse osmosis system, and the recovery rate of the first-stage reverse osmosis system is set to be 60%.
7. And (3) enabling concentrated water of the nitrate separation membrane system to enter a nitrate co-production evaporation system of MVR and triple effect evaporation, and returning produced water to a regulating tank for retreatment.
8. Concentrated water of the first-stage reverse osmosis enters the electrodialysis system, produced water enters the second-stage reverse osmosis system, the recovery rate of the second-stage reverse osmosis system is set to be 90%, the concentrated water of the second-stage reverse osmosis returns to the first-stage reverse osmosis for retreatment, and the produced water of the second-stage reverse osmosis is recycled.
9. Concentrated water of the electrodialysis system enters a deamination MVR evaporation crystallization system, and light salt water returns to the first-stage reverse osmosis system for retreatment; mother liquor circulation and fixed discharge of 2-3t/h in the control of the deamination MVR evaporative crystallization system and the nitrate co-production evaporative system.
10. The water quality of the final reuse water is shown in table 3; the quality of the final sodium chloride and anhydrous sodium sulfate crystalline salts are shown in table 4.
TABLE 3 quality of reuse water
TABLE 4 quality of sodium chloride and sodium sulfate crystalline salts
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (7)
1. A treatment process for zero emission and resource recycling of catalyst wastewater is characterized by comprising the following treatment steps:
(1) discharging high-ammonia nitrogen high-silicon high-salt wastewater generated in the production of the catalyst into a regulating water tank, and staying for more than 20 hours for regulating the water quality and water quantity of the comprehensive wastewater of the catalyst;
(2) regulating the water outlet of the water tank, lifting the water outlet by a pump, and then entering a high-efficiency softening and silicon-removing system to remove partial hardness, alkalinity, silicon dioxide, suspended matters and organic pollutants in the wastewater;
(3) the water produced by the high-efficiency softening and desiliconizing system enters a medium filtering system and is used for removing part of suspended pollutant in the wastewater;
(4) the water produced by the medium filtering system enters an ultrafiltration system to further remove suspended matters, colloids and bacteria in the wastewater;
(5) the water produced by the ultrafiltration system enters an ion exchange system to further remove calcium and magnesium ions;
(6) the water produced by the ion exchange system enters a nanofiltration system, the wastewater is separated into concentrated water mainly containing sodium sulfate and produced water mainly containing sodium chloride under the action of the nanofiltration membrane, the concentrated water enters the step (7) for treatment, and the produced water enters the step (8) for treatment;
(7) the concentrated water treated in the step (6) enters a nitrate separation membrane system, monovalent ions are removed under the action of the nitrate separation membrane, the concentration of sodium sulfate is further increased to be used as concentrated water, the concentrated water enters a nitrate co-production evaporation system, namely, the concentrated water is treated in the step (12), and the produced water of the nitrate separation membrane system is mixed with nanofiltration produced water and then enters a step (8) for treatment;
(8) the produced water treated in the step (6) enters a first-stage reverse osmosis system, the concentration of sodium chloride in the wastewater is increased through the concentration effect of the first-stage reverse osmosis membrane to be used as concentrated water, the concentrated water is treated in the step (9), and the first-stage reverse osmosis produced water is treated in the step (10);
(9) enabling the concentrated water treated in the step (8) to enter an electrodialysis system, further improving the mass concentration of sodium chloride in the concentrated water to be more than 23% under the action of anion and cation exchange membranes in an electrodialysis device to form high-concentration brine, enabling the high-concentration brine to enter the step (11) for treatment, enabling the electrodialysis system to form desalted light brine, and returning the diluted light brine to the step (8) for treatment;
(10) the produced water treated in the step (8) enters a secondary reverse osmosis system, is separated into concentrated water and produced water again under the action of the secondary reverse osmosis membrane, the concentrated water of the secondary reverse osmosis system returns to the step (8) for treatment, and the produced water of the secondary reverse osmosis system enters a reuse water tank;
(11) the high-concentration brine processed in the step (9) and a part of mother liquor in the step (12) enter a deamination evaporation crystallization system, the high-concentration brine is evaporated and concentrated into sodium chloride supersaturated mother liquor after deamination, one part of the mother liquor enters a crystallizer to form sodium chloride crystal salt, the other part of the mother liquor enters the step (12) for processing, and condensate formed in the evaporation process is conveyed to a water consumption point;
(12) enabling the concentrated water treated in the step (7) and a part of mother liquor in the step (11) to enter a nitrate co-production evaporation system, evaporating and crystallizing to form anhydrous sodium sulfate crystal salt, and enabling a part of mother liquor in the nitrate co-production evaporation system to enter the deamination evaporation crystallization system in the step (11);
setting the rising flow rate of the reaction zone of the high-efficiency softening and silicon-removing system in the step (2) to be 5-10m/h, adding magnesium chloride as a silicon-removing agent into the reaction zone of the high-efficiency softening and silicon-removing system, and adjusting the pH value to 10.5-11.5; the efficient softening and silicon-removing system is provided with an ammonia gas collecting device, and ammonia gas is introduced to the absorption tower; the recovery rate of the first-stage reverse osmosis system in the step (8) is set to be 50% -70%; the recovery rate of the secondary reverse osmosis system in the step (10) is set to be 80-90%; in the step (12), an MVR + multi-effect evaporation process is adopted in the co-production evaporation crystallization process of the nitrate, and the pH value is set to be 12 in the evaporation process; and (3) returning a part of mother liquor in the process of evaporative crystallization for co-production of nitrate to the deamination evaporative crystallization system in the step (11).
2. The process according to claim 1, wherein the recovery rate of the ultrafiltration system in step (4) is set to 90% to 93%, and the membrane material is preferably PVDF.
3. The treatment process of claim 1, wherein the ion exchange system in the step (5) adopts macroporous sodium type weak acid cation resin, the regeneration mode of the resin is acid regeneration base conversion, and the regeneration wastewater of the ion exchange system flows back to the regulating tank.
4. The process of claim 1, wherein the concentration of sulfate in the concentrated water of the nanofiltration system in step (6) is more than 50000 mg/L.
5. The treatment process as claimed in claim 1, wherein the nitrate separation membrane in step (7) has a molecular weight cut-off of 150-300 daltons and a sulfate cut-off of more than 99%; the TDS of the concentrated water in the nitrate salt separation membrane system is more than 180000 mg/L.
6. A process as claimed in claim 1, wherein the electrodialysis system in step (9) employs homogeneous anion and cation exchange membranes, and the final high-concentration brine has a sodium chloride mass concentration of more than 23%.
7. The treatment process of claim 1, wherein the deamination evaporation system in the step (11) adopts a stripping deamination and evaporation integrated device, and a part of mother liquor is discharged to the nitrate co-production crystallization system in the step (12) in the evaporation crystallization process.
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