CN111233231A - Complete ammonium phosphate condensate treatment device and treatment and recycling method - Google Patents
Complete ammonium phosphate condensate treatment device and treatment and recycling method Download PDFInfo
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Abstract
The invention relates to a complete set of treatment device and a treatment and recycling method for ammonium phosphate condensate, which structurally comprises a plate heat exchanger, a buffer tank, a security filter, a deamination system, a primary defluorination and dephosphorization sedimentation tank, a secondary defluorination and dephosphorization sedimentation tank, a sedimentation water outlet tank, a multi-medium filter and a reuse water tank which are sequentially connected through pipelines, wherein the plate heat exchanger is connected with an ammonium phosphate condensate inlet pipe. A method of treatment and reuse comprising: deamination; primary fluorine and phosphorus removal precipitation; secondary fluorine and phosphorus removal precipitation; and (4) filtering by using a plurality of media. The invention has the advantages that: (1) the main pollutants in the ammonium phosphate condensate are effectively removed, and the requirement of the water quality of the make-up water of the open type circulating cooling water system is met when the ammonium phosphate condensate is recycled. (2) The resin regeneration waste liquid and the sedimentation tank sludge generated in the treatment process are reasonably utilized. (3) The recovery rate of the system is up to more than 95%. (4) The deamination system adopts the mode of connecting three resin tanks in series two by two to operate, and ensures that the ammonia nitrogen in the effluent can be always kept below 1 mg/L.
Description
Technical Field
The invention relates to a complete set of treatment device and a treatment and recycling method for ammonium phosphate condensate, in particular to a complete set of treatment device for ammonium phosphate concentrated condensate generated in the production process of ammonium phosphate fertilizer and a treatment and recycling method for the ammonium phosphate concentrated condensate, belonging to the technical field of wastewater treatment, in particular to the technical field of wastewater treatment in the phosphate fertilizer industry.
Background
The phosphate fertilizer industry in China is rapidly developed in the last ten years, the phosphate fertilizer industry is increasingly powerful both in capacity scale and in comprehensive strength of monomer enterprises, and the international market competitiveness is gradually improved. The yield and consumption of phosphate fertilizer in China are the first place in the world. The ammonium phosphate as basic fertilizer is one of the main products in phosphate fertilizer industry in China, is a high-quality, high-efficiency and high-concentration nitrogen-phosphorus compound fertilizer, and is an important production material necessary for agriculture modernization in China. At present, the ammonium phosphate production process in China mainly adopts a 'neutralization slurry concentration method', namely dilute phosphoric acid is firstly neutralized with ammonia to prepare dilute neutralization slurry, then the slurry is evaporated and concentrated, most of water in materials is removed, and then the concentrated slurry is granulated and dried.
However, with the increasing productivity of the phosphate fertilizer industry, the problem of wastewater treatment and discharge is also aggravated. Wherein the waste water generated in the ammonium phosphate production process is mainly steam condensate generated by concentrating ammonium phosphate slurry. Ammonium phosphate condensate contains a large amount of pollutants such as ammonia nitrogen, fluoride, phosphate and the like, and can cause serious public health and environmental problems. At present, ammonium phosphate condensate is mainly digested in a production device, and if the ammonium phosphate condensate is directly recycled as ore grinding water supplement, pollutants in the ammonium phosphate condensate are not effectively removed, and certain influence is generated on the stable operation of a system through long-period enrichment. The ammonia nitrogen wastewater enters the phosphogypsum reservoir when the ammonia nitrogen wastewater is reused for washing the wet-process phosphoric acid filter, so that the ammonia nitrogen concentration of accumulated water in the phosphogypsum reservoir is higher, the ammonia nitrogen of circulating water of a phosphoric acid device is increased, the stable operation of the phosphoric acid device is influenced, and the production of a downstream device is influenced.
According to the requirements of the discharge standard of pollutants for phosphate fertilizer industrial water (GB 15580-2011), the three pollutants in the wastewater need to be completely treated and then can be discharged or recycled. At present, ammonium phosphate condensate is generally treated by uniformly feeding the ammonium phosphate condensate, sulfuric acid device indirect cooling wastewater, equipment ground cleaning wastewater, phosphate fertilizer device equipment ground cleaning wastewater and the like into an acid wastewater treatment station for treatment and adopting a neutralizer for multi-section neutralization and coagulating sedimentation treatment. The process has the functions of neutralization, precipitation, fluorine removal and phosphorus removal, but basically does not remove ammonia nitrogen, the ammonium phosphate condensate has high ammonia nitrogen concentration, and the physicochemical treatment process of the coagulating precipitation is difficult to ensure that the effluent quality meets the requirements of the discharge standard of phosphate fertilizer industrial water pollutants (GB 15580-2011).
Chinese patent CN101734955 discloses a method for treating ammonia nitrogen wastewater of phosphate fertilizer enterprises, which comprises the main process flow of using ammonium phosphate condensate to wash the total ammonia-containing tail gas in the ammonium sulfate production process, dissolving the ammonia gas in the tail gas into the ammonium phosphate condensate containing ammonia nitrogen, and allowing the washing liquid to enter an ammonium sulfate reactor to produce ammonium sulfate fertilizer containing phosphorus. The process mainly aims at ammonia nitrogen wastewater in the ammonium phosphate production process, and treatment of pollutants such as fluoride, phosphate and the like in the wastewater is not considered.
Chinese patent CN101928046, comprehensive utilization method of ammonium phosphate production wastewater, respectively mixes the wastewater into other production links for recycling according to different ammonia nitrogen contents in the wastewater by wastewater diversion. Wherein, one part of the double-effect steam condensate is used as tail gas washing water of the ammonium phosphate device; one part of the water is sent to a circulating system of the ammonium phosphate device and is used as sealing water or added water of transmission equipment; and one part of the water is used as filter cloth washing water of the phosphoric acid device. Although the method realizes zero emission of the ammonium phosphate condensate, the ammonia nitrogen in the circulating water is increased because pollutants in the ammonium phosphate condensate are not effectively removed, and the stable operation of the device is influenced.
Chinese patent CN11014827, a phosphate fertilizer sewage treatment process, the main process is a two-stage neutralization coagulation precipitation combined agent deep fluorine and phosphorus removal process, and fluoride and phosphate in wastewater can be treated to a lower level. However, the process mainly aims at the wastewater containing fluorine and phosphorus generated in the production process of the phosphate fertilizer, and does not consider the removal of ammonia nitrogen pollutants in the wastewater.
Therefore, the ammonium phosphate condensate treatment process with high efficiency, good treatment effect and stable operation is provided, pollutants such as ammonia nitrogen, fluoride, phosphate and the like in the ammonium phosphate condensate are effectively removed, the water quality during recycling is improved, and the process has important significance for efficient comprehensive utilization and stable production of the ammonium phosphate condensate.
Disclosure of Invention
The invention provides a complete set of ammonium phosphate condensate treatment device and a treatment and recycling method, aiming at overcoming the defects in the prior art, realizing the treatment and recycling of double-effect secondary steam condensate generated in the ammonium phosphate production process, effectively removing pollutants such as ammonia nitrogen, phosphate, fluoride and the like in the ammonium phosphate condensate, finally realizing high-standard recycling of wastewater and high recycling efficiency.
The technical solution of the invention is as follows: the ammonium phosphate condensate complete processing device structurally comprises a plate heat exchanger, a buffer tank, a security filter, a deamination system, a primary defluorination and dephosphorization sedimentation tank, a secondary defluorination and dephosphorization sedimentation tank, a sedimentation water outlet tank, a multi-media filter and a reuse water tank which are sequentially connected through a pipeline, wherein the plate heat exchanger is connected with an ammonium phosphate condensate inlet pipe, a buffer tank lifting pump is arranged on the pipeline between the buffer tank and the security filter, and a sedimentation water outlet tank lifting pump is arranged on the pipeline between the sedimentation water outlet tank and the multi-media filter.
Preferably, the deamination system comprises a first deamination resin tank, a second deamination resin tank and a third deamination resin tank which are connected in series pairwise.
Preferably, No. one deamination resin jar, No. two deamination resin jars and No. three deamination resin jars all are furnished with inlet valve, outlet valve and regeneration/backwash's business turn over water valve respectively, are connected through the series connection valve between the export of every deamination resin jar of a deamination resin jar, No. two deamination resin jars and No. three deamination resin jars according to the order and the import of next deamination resin jar.
Preferably, the first-stage defluorination and dephosphorization sedimentation tank comprises a first-stage coagulation tank, a first-stage flocculation tank and a first-stage sedimentation tank which are sequentially connected, the second-stage defluorination and dephosphorization sedimentation tank comprises a second-stage coagulation tank, a second-stage flocculation tank and a second-stage sedimentation tank which are sequentially connected, and the first-stage coagulation tank and the second-stage coagulation tankOne side of the pool body is provided with a NaOH dosing port and CaCl2Add medicine mouth and PAC and add the medicine mouth, all be equipped with PAM in one-level flocculation basin and the second grade flocculation basin and add the medicine mouth, the one-level is coagulated pond, one-level flocculation pond, one-level sedimentation tank, second grade and is coagulated pond, second grade flocculation pond and second grade sedimentation tank cell body inside all is equipped with the mixer.
The ammonium phosphate condensate treating and reusing method includes the following steps:
step one, deamination: cooling ammonium phosphate condensate with 200-400 mg/L of ammonia nitrogen from 80-90 ℃ to 30-40 ℃ through a heat exchanger, then feeding the ammonium phosphate condensate into a buffer tank, adjusting the pH to 6-7, feeding the ammonium phosphate condensate into a deamination system through a lift pump, and treating the ammonium phosphate condensate with deamination resin to reduce the ammonia nitrogen to below 1 mg/L;
the second step, the first-stage fluorine and phosphorus removal and precipitation: the method comprises the following steps that (1) water discharged from a deamination system with the pH of 1-3 enters a primary defluorination and dephosphorization sedimentation tank, the fluoride content is 50-110 mg/L, the phosphate content is 15-70 mg/L, the pH of the wastewater is adjusted to 7-9 in a primary coagulation tank, calcium chloride is added according to the calcium-fluorine molar ratio of 1.2-2: 1, 50-100 mg/LPAC is added, the retention time is 15-30 min, the water discharged from the primary coagulation tank enters a primary flocculation tank, 1-3 mg/L PAM is added, the retention time is 15-30 min, the water enters the primary sedimentation tank, and the retention time is 2-4 h;
step three, secondary fluorine and phosphorus removal and precipitation: the effluent of the first-stage defluorination and dephosphorization sedimentation tank enters a second-stage defluorination and dephosphorization sedimentation tank, the pH is firstly adjusted to 7-9 in a second-stage coagulation tank, and the molar ratio of calcium to fluorine is 1.2-2: 1, adding calcium chloride and 50-100 mg/LPAC, allowing the mixture to stay for 15-30 min, allowing the effluent of a secondary coagulation tank to enter a secondary flocculation tank, adding 1-3 mg/L PAM, allowing the effluent to stay for 15-30 min, allowing the effluent to enter a secondary sedimentation tank, allowing the effluent to stay for 2-4 h, and allowing the effluent to overflow to a sedimentation effluent tank;
step four, multi-medium filtration: and the wastewater in the precipitation water outlet tank enters a multi-media filter through a lifting pump for filtration treatment, suspended matters in the wastewater are intercepted, the multi-media filter cleaning water flows back to a secondary coagulation tank of a secondary fluorine and phosphorus removal sedimentation tank, the multi-media filter outlet water enters a reuse water tank, and the multi-media filter outlet water is pumped to a sulfuric acid plant circulating water system for reuse.
Preferably, in the first deamination step, a gel-type homogeneous strong acid cation exchange resin is adopted as deamination resin, the ion form is hydrogen form, the functional group is sulfonic group, the uniformity coefficient is less than 1.25, and the total exchange capacity is 1.80 meq/mL.
Preferably, in the first step deamination, the two liang of series connection mode operations of three the same resin tank are adopted to the deamination system, and resin velocity of flow 5 ~ 10BV/h, three resin tank are furnished with the business turn over water valve of inlet valve, outlet valve and regeneration/backwash respectively, still are connected through the series connection valve between the export of every resin tank and the import of next resin tank simultaneously, drop into two resin tank series connection operations at every turn, and the third resin tank is then regenerated for subsequent use: when the first deamination resin tank and the second deamination resin tank are connected in series, the third deamination resin tank is regenerated; after the first deamination resin tank is saturated, switching to a second deamination resin tank and a third deamination resin tank to operate in series, and regenerating the first deamination resin tank; and after the second deamination resin tank is saturated, switching to the third deamination resin tank and the first deamination resin tank to operate in series, regenerating the second deamination resin tank, and performing reciprocating switching operation.
Preferably, in the first step of deamination, after resin in the resin tank is saturated, the resin tank is regenerated by sulfuric acid with the mass concentration of 5% at the flow rate of 2BV/h, soft water is used for backwashing at the flow rate of 4BV/h, and the regeneration waste liquid containing ammonium sulfate is sent to a tail gas washing system of an ammonium phosphate section for comprehensive utilization.
Preferably, the sludge in the two sedimentation tanks in the first-stage fluorine and phosphorus removal sedimentation of the second step and the second-stage fluorine and phosphorus removal sedimentation of the third step is discharged to a phosphogypsum comprehensive utilization section.
The invention has the advantages that: (1) the main pollutants of ammonia nitrogen, phosphate and fluoride in the ammonium phosphate condensate are effectively removed, and the requirement of the quality of the make-up water of an open type circulating cooling water system in the water quality control index of reclaimed water as cooling water (GB/T19923-2005) is met during recycling.
(2) And respectively sending the resin regeneration waste liquid and the sedimentation tank sludge generated in the treatment process to a tail gas washing system of an ammonium phosphate working section and a comprehensive utilization working section of phosphogypsum, and reasonably utilizing the resin regeneration waste liquid and the sedimentation tank sludge.
(3) The recovery rate of the system is up to more than 95%, and except a small part of waste water discharged along with a resin regeneration system and a sedimentation tank sludge discharge system, the rest waste water is effectively recovered.
(4) The deamination system preferably adopts the mode of connecting three resin tanks in series two by two to operate, and can ensure that the waste water is continuously treated with high efficiency by connecting two resin tanks in series even if the resin is saturated and needs to be regenerated, thereby ensuring that the ammonia nitrogen in the effluent water can be always kept below 1 mg/L.
Drawings
FIG. 1 is a flow chart of the ammonium phosphate condensate treatment and recycling method of the present invention.
FIG. 2 is a system block diagram of one embodiment of the ammonium phosphate condensate polishing plant of the present invention.
Fig. 3 is a schematic diagram of a pipeline connection structure of the deamination system in fig. 1.
In the figure, A is a buffer tank, B is a first-stage coagulation tank, C is a first-stage flocculation tank, D is a first-stage sedimentation tank, E is a second-stage coagulation tank, F is a second-stage flocculation tank, G is a second-stage sedimentation tank, H is a sedimentation water outlet tank, I is a reuse water tank, 1 is a first deamination resin tank, 2 is a second deamination resin tank, 3 is a third deamination resin tank, 4 is a multi-medium filter, 5 is a plate heat exchanger, 6 is a buffer tank lifting pump, 7 is a sedimentation water outlet tank lifting pump, and 8 is a security filter.
Detailed Description
The present invention will be described in further detail with reference to examples and specific embodiments.
As shown in figure 2, the complete set of ammonium phosphate condensate treatment device structurally comprises a plate heat exchanger 5, a buffer pool A, a security filter 8, a deamination system, a primary defluorination and dephosphorization sedimentation pool, a secondary defluorination and dephosphorization sedimentation pool, a sedimentation water outlet pool H, a multi-media filter 4 and a reuse water pool I which are sequentially connected through pipelines, wherein the plate heat exchanger 5 is connected with an ammonium phosphate condensate inlet pipe, a buffer pool lifting pump 6 is arranged on the pipeline between the buffer pool A and the security filter 8, and a sedimentation water outlet pool lifting pump 7 is arranged on the pipeline between the sedimentation water outlet pool H and the multi-media filter 4.
As shown in figures 2 and 3, the deamination system comprises three resin tanks which are connected in series two by two, namely a first deamination resin tank 1, a second deamination resin tank 2 and a third deamination resin tank 3, and the running flow rate is 5-10 BV/h.
No. 1 deamination resin jar, No. 2 deamination resin jar and No. 3 deamination resin jar all are furnished with the business turn over water valve of inlet valve, outlet valve and regeneration/backwash respectively, are connected through the series connection valve between the export of every deamination resin jar in proper order and the import of next deamination resin jar in a deamination resin jar 1 deamination resin jar, No. 2 deamination resin jar and No. 3 deamination resin jar.
No. one deamination resin jar 1, No. two deamination resin jar 2 and No. three deamination resin jar 3 are through the external ammonium phosphate workshop section tail gas washing system of regeneration waste liquid pipe.
The one-level defluorination dephosphorization sedimentation tank comprises a one-level coagulation tank B, a one-level flocculation tank C and a one-level sedimentation tank D which are sequentially connected, the second-level defluorination dephosphorization sedimentation tank comprises a second-level coagulation tank E, a second-level flocculation tank F and a second-level sedimentation tank G which are sequentially connected, and one side of each of the one-level coagulation tank B and the second-level coagulation tank E is provided with a NaOH dosing port and CaCl2The dosing port and PAC (coagulant polyaluminium chloride) dosing port are respectively provided with PAM (flocculant polyacrylamide) dosing ports in the first-level flocculation tank C and the second-level flocculation tank F, and the inside of each of the first-level coagulation tank B, the first-level flocculation tank C, the first-level sedimentation tank D, the second-level coagulation tank E, the second-level flocculation tank F and the second-level sedimentation tank G is provided with a stirrer.
The primary defluorination and dephosphorization sedimentation tank and the secondary defluorination and dephosphorization sedimentation tank are externally connected with a phosphogypsum comprehensive utilization working section through a sludge outlet pipe.
As shown in fig. 1, the ammonium phosphate condensate treating and recycling method comprises the following steps:
step one, deamination: after being cooled by a heat exchanger (from 80-90 ℃ to 30-40 ℃), the ammonium phosphate condensate enters a buffer tank, the ammonia nitrogen content is 200-400 mg/L, the pH value is adjusted to 6-7, then the ammonium phosphate condensate enters a deamination system through a lifting pump, and the ammonia nitrogen is reduced to below 1mg/L through deamination resin treatment.
The deamination resin adopts homogeneous particle gel type strong acid cation exchange resin, the ion form is hydrogen type, the functional group is sulfonic group, the uniformity coefficient is less than 1.25, and the full exchange capacity is 1.80 meq/mL.
Three same resin tanks are connected in series two by two to operate, and the working flow speed of the resin is 5-10 BV/h.
As shown in figure 3, the three resin tanks are respectively provided with a water inlet valve, a water outlet valve and a water inlet and outlet valve for regeneration/backwashing, and the outlet of each resin tank is connected with the inlet of the next resin tank through a series valve.
Two resin tanks are put into operation in series each time, and the third resin tank is regenerated for standby. When raw water passes through two resin tanks which are operated in series, more than 90% of ammonia nitrogen is removed in the first resin tank; the second resin tank can further improve and ensure the effluent quality, and the effluent ammonia nitrogen can be ensured to be at an extremely low level even if the previous resin tank is saturated, so that the system has extremely high effluent stability. And after the previous resin tank is saturated, immediately switching to the next resin tank and the regenerated and standby resin tank to operate in series.
The specific operation mode is as follows: when the first deamination resin tank and the second deamination resin tank are connected in series, the third deamination resin tank is regenerated; after the first deamination resin tank is saturated, switching to a second deamination resin tank and a third deamination resin tank to operate in series, and regenerating the first deamination resin tank; and after the second deamination resin tank is saturated, the third deamination resin tank and the first deamination resin tank are switched to operate in series, and the second deamination resin tank is regenerated. The operation is switched in a reciprocating way, so that the effective treatment on the ammonia nitrogen is ensured continuously.
After the resin is saturated, the resin is regenerated by sulfuric acid with the mass concentration of 5% at the flow rate of 2BV/h, soft water is used for backwashing at the flow rate of 4BV/h, and the regenerated waste liquid containing a large amount of ammonium sulfate is sent to a tail gas washing system of an ammonium phosphate working section for comprehensive utilization.
The second step, the first-stage fluorine and phosphorus removal and precipitation: and (3) the effluent (pH 1-3) of the deamination system enters a first-stage fluorine and phosphorus removal sedimentation tank, wherein the fluoride content is 50-110 mg/L, and the phosphate content is 15-70 mg/L. Firstly, adjusting the pH value of wastewater to 7-9 in a primary coagulation tank, adding calcium chloride according to the calcium-fluorine molar ratio of 1.2-2: 1, adding 50-100 mg/LPAC, allowing the mixture to stay for 15-30 min, allowing the effluent of the primary coagulation tank to enter the primary coagulation tank, adding 1-3 mg/L PAM, allowing the effluent to stay for 15-30 min, and allowing the effluent to enter a primary sedimentation tank, and allowing the effluent to stay for 2-4 h. More than 80% of phosphate and fluoride ions are removed by adding calcium for coagulating sedimentation.
Step three, secondary fluorine and phosphorus removal and precipitation: the effluent of the first-stage defluorination and dephosphorization sedimentation tank enters a second-stage defluorination and dephosphorization sedimentation tank, the pH is firstly adjusted to 7-9 in a second-stage coagulation tank, and the molar ratio of calcium to fluorine is 1.2-2: 1, adding calcium chloride and 50-100 mg/LPAC, allowing the mixture to stay for 15-30 min, allowing the effluent of the secondary coagulation tank to enter a secondary flocculation tank, adding 1-3 mg/L PAM, allowing the effluent to stay for 15-30 min, allowing the effluent to enter a secondary sedimentation tank, allowing the effluent to stay for 2-4 h, and allowing the effluent to overflow to a sedimentation effluent tank. Phosphate is further removed to be below 0.5mg/L and fluoride is removed to be below 5mg/L through secondary calcium adding coagulation sedimentation.
And discharging the sludge in the two sedimentation tanks to a comprehensive utilization working section of the phosphogypsum.
Step four, multi-medium filtration: and the wastewater in the sedimentation water outlet tank enters a multi-media filter through a lift pump for filtration treatment, suspended matters in the wastewater are intercepted, and the multi-media filter cleaning water flows back to a secondary coagulation tank of a secondary fluorine and phosphorus removal sedimentation tank. The effluent of the multi-media filter enters a reuse water tank and is pumped to a circulating water system of a sulfuric acid plant for reuse, and the overall recovery rate of the system is over 95 percent.
Example 1
The quality of ammonium phosphate concentrated double-effect steam condensate in a certain fertilizer plant is as follows: pH is 9.5-10.0, fluoride is 50-80 mg/L, ammonia nitrogen is 200-300 mg/L, total phosphorus is 20-45 mg/L, and water temperature is 80-85 ℃. The wastewater flow rate was 100t/h, and the operation was 24h per day. The implementation of the embodiment comprises the following steps:
(1) and (3) deamination: and cooling the ammonium phosphate condensate to 35-40 ℃ through a heat exchanger, and then feeding the ammonium phosphate condensate into a buffer tank to adjust the pH to 6-7. The ammonia nitrogen content is 200-300 mg/L, and the ammonia nitrogen enters a deamination system through a lift pump and is reduced to 0.84mg/L through deamination resin treatment. The working flow rate of the resin is 10BV/h, and the regeneration operation is switched in a reciprocating mode by connecting three same resin tanks in a pairwise serial mode, so that the continuous effective treatment on the ammonia nitrogen is ensured. After the resin is saturated, regenerating by using 5 percent sulfuric acid and backwashing by using soft water, and sending the regenerated waste liquid to a tail gas washing system of an ammonium phosphate working section for comprehensive utilization;
(2) primary fluorine and phosphorus removal and precipitation: and (3) enabling the effluent of the deamination system to enter a first-stage fluorine and phosphorus removal coagulation tank, wherein the fluoride content is 50-80 mg/L, and the phosphate content is 20-45 mg/L. Because the deamination ion exchange resin is strong acid type resin, the effluent is acidic, the pH value of the wastewater is adjusted to 7-9 by sodium hydroxide, and the molar ratio of calcium to fluorine is 1.2: 1, adding calcium chloride and 50mg/L PAC, standing for 15min, allowing the effluent of the primary coagulation tank to enter a primary flocculation tank, adding 1mg/L PAM, standing for 15min, and allowing the effluent to enter a primary sedimentation tank, and standing for 2 h. More than 80% of phosphate and fluoride ions are removed through calcium-adding coagulation sedimentation, the phosphate is reduced to 1.67mg/L, and the fluoride is reduced to 8.24 mg/L;
(3) secondary fluorine and phosphorus removal and precipitation: and (3) enabling effluent of the first-stage fluorine and phosphorus removal sedimentation tank to enter a second-stage fluorine and phosphorus removal coagulation tank, adjusting the pH to 7-9, and mixing the effluent according to the calcium-fluorine molar ratio of 1.3: 1, adding calcium chloride and 50mg/L PAC, standing for 15min, allowing the effluent of the secondary coagulation tank to enter a secondary flocculation tank, adding 1mg/L PAM, standing for 15min, allowing the effluent to enter a secondary sedimentation tank, standing for 2h, and overflowing the effluent to a sedimentation effluent tank. The phosphate is further removed to 0.05mg/L and the fluoride is removed to 2.17mg/L by secondary calcium-adding coagulating sedimentation. And discharging the sludge in the two sedimentation tanks to a comprehensive utilization working section of the phosphogypsum.
(4) Filtering by using multiple media: and the wastewater in the sedimentation water outlet tank enters a multi-media filter through a lift pump for filtration treatment, suspended matters in the wastewater are intercepted, the multi-media filter adopts produced water of the multi-media filter for backwashing and forward washing, and the washing water flows back to a coagulation tank of the secondary fluorine and phosphorus removal sedimentation tank. The effluent of the multi-media filter enters a reuse water tank and is pumped to a circulating water system of a sulfuric acid plant for reuse, and the overall recovery rate of the system is over 95 percent. The quality of the outlet water meets the requirement of the quality of the make-up water of an open circulating cooling water system in the Water quality control index of reclaimed water as cooling water (GB/T19923-2005).
Example 2
The quality of ammonium phosphate concentrated double-effect steam condensate in a certain ammonium phosphate plant is as follows: pH is 9.0-9.5, fluoride is 80-110 mg/L, ammonia nitrogen is 300-400 mg/L, total phosphorus is 45-70 mg/L, and the water temperature is 85-90 ℃. The wastewater flow was 50t/h and was run for 22h per day. The implementation of the embodiment comprises the following steps:
(1) and (3) deamination: and cooling the ammonium phosphate condensate to 35-40 ℃ through a heat exchanger, and then feeding the ammonium phosphate condensate into a buffer tank to adjust the pH to 6-7. The ammonia nitrogen content is 300-400 mg/L, the ammonia nitrogen enters a deamination system through a lifting pump, and the ammonia nitrogen is reduced to 0.57mg/L through deamination resin treatment. The resin working flow rate is 5BV/h, and the regeneration operation is switched in a reciprocating mode by connecting three same resin tanks in a pairwise serial mode, so that the continuous effective treatment on ammonia nitrogen is ensured. After the resin is saturated, regenerating by using 5 percent sulfuric acid and backwashing by using soft water, and sending the regenerated waste liquid to a tail gas washing system of an ammonium phosphate working section for comprehensive utilization;
(2) primary fluorine and phosphorus removal and precipitation: the effluent of the deamination system enters a first-stage fluorine and phosphorus removal coagulation tank, the fluoride content is 80-110 mg/L, the phosphate content is 45-70 mg/L, the pH of the wastewater is adjusted to 7-9 by sodium hydroxide, and the ratio of calcium to fluorine is 1.2: 1, adding calcium chloride and 100mg/LPAC, standing for 30min, allowing the effluent of the primary coagulation tank to enter a primary flocculation tank, adding 3mg/L PAM, standing for 30min, allowing the effluent to enter a primary sedimentation tank, and standing for 4 h. More than 80% of phosphate and fluoride ions are removed through calcium-adding coagulation sedimentation, the phosphate is reduced to 1.83mg/L, and the fluoride is reduced to 10.15 mg/L;
(3) secondary fluorine and phosphorus removal and precipitation: and (3) enabling effluent of the first-stage fluorine and phosphorus removal sedimentation tank to enter a second-stage fluorine and phosphorus removal coagulation tank, adjusting the pH to 7-9, and mixing the effluent according to the calcium-fluorine molar ratio of 1.3: 1, adding calcium chloride and 100mg/L PAC, standing for 30min, allowing the effluent of the secondary coagulation tank to enter a secondary flocculation tank, adding 3mg/L PAM, standing for 30min, allowing the effluent to enter a secondary sedimentation tank, standing for 4h, and overflowing the effluent to a sedimentation effluent tank. The phosphate is further removed to 0.08mg/L and the fluoride is removed to 2.46mg/L through secondary calcium adding coagulation sedimentation. And discharging the sludge in the two sedimentation tanks to a comprehensive utilization working section of the phosphogypsum.
(4) Filtering by using multiple media: and the wastewater in the sedimentation water outlet tank enters a multi-media filter through a lift pump for filtration treatment, suspended matters in the wastewater are intercepted, the multi-media filter adopts produced water of the multi-media filter for backwashing and forward washing, and the washing water flows back to a coagulation tank of the secondary fluorine and phosphorus removal sedimentation tank. The effluent of the multi-media filter enters a reuse water tank and is pumped to a circulating water system of a sulfuric acid plant for reuse, and the overall recovery rate of the system is over 95 percent. The water quality of the outlet water meets the requirement of the water quality of the make-up water of an open circulating cooling water system in the Water quality control index of reclaimed water used as cooling water (GB/T19923-.
The above is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. Ammonium phosphate condensate complete set processing apparatus, a serial communication port, include plate heat exchanger (5) that connects gradually through the pipeline, buffer pool (A), safety filter ware (8), deamination system, one-level defluorination dephosphorization sedimentation tank, second grade defluorination dephosphorization sedimentation tank, sediment effluent pool (H), multimedium filter (4) and reuse water pool (I), ammonium phosphate condensate inlet pipe is connected in plate heat exchanger (5), establish buffer pool elevator pump (6) on the pipeline between buffer pool (A) and safety filter ware (8), establish sediment effluent pool elevator pump (7) on the pipeline between sediment effluent pool (H) and multimedium filter ware (4).
2. The ammonium phosphate condensate complete treatment device of claim 1, wherein the deamination system comprises a first deamination resin tank (1), a second deamination resin tank (2) and a third deamination resin tank (3) which are connected in series with each other two by two.
3. The ammonium phosphate condensate complete treatment device of claim 2, wherein the first deamination resin tank (1), the second deamination resin tank (2) and the third deamination resin tank (3) are respectively provided with a water inlet valve, a water outlet valve and a regeneration/backwashing water inlet and outlet valve, and the outlet of each deamination resin tank is connected with the inlet of the next deamination resin tank through a series valve in sequence in the first deamination resin tank (1), the second deamination resin tank (2) and the third deamination resin tank (3).
4. The complete ammonium phosphate condensate treatment device of claim 1, wherein the primary defluorination and dephosphorization sedimentation tank comprises a primary coagulation tank (B), a primary flocculation tank (C) and a primary sedimentation tank (D) which are connected in sequence, the secondary defluorination and dephosphorization sedimentation tank comprises a secondary coagulation tank (E), a secondary flocculation tank (F) and a secondary sedimentation tank (G) which are connected in sequence, and the primary coagulation tank (B) and the secondary coagulation tank (G)E) One side of the pool body is provided with a NaOH dosing port and CaCl2Add medicine mouth and PAC and add the medicine mouth, all be equipped with PAM in one-level flocculation basin (C) and the second grade flocculation basin (F) and add the medicine mouth, one-level coagulation basin (B), one-level flocculation basin (C), one-level sedimentation tank (D), second grade coagulation basin (E), second grade flocculation basin (F) and second grade sedimentation tank (G) cell body inside all is equipped with the mixer.
5. The ammonium phosphate condensate treating and recycling method is characterized by comprising the following steps:
step one, deamination: cooling ammonium phosphate condensate with 200-400 mg/L of ammonia nitrogen from 80-90 ℃ to 30-40 ℃ through a heat exchanger, then feeding the ammonium phosphate condensate into a buffer tank, adjusting the pH to 6-7, feeding the ammonium phosphate condensate into a deamination system through a lift pump, and treating the ammonium phosphate condensate with deamination resin to reduce the ammonia nitrogen to below 1 mg/L;
the second step, the first-stage fluorine and phosphorus removal and precipitation: the method comprises the following steps that (1) water discharged from a deamination system with the pH of 1-3 enters a primary defluorination and dephosphorization sedimentation tank, the fluoride content is 50-110 mg/L, the phosphate content is 15-70 mg/L, the pH of the wastewater is adjusted to 7-9 in a primary coagulation tank, calcium chloride is added according to the calcium-fluorine molar ratio of 1.2-2: 1, 50-100 mg/LPAC is added, the retention time is 15-30 min, the water discharged from the primary coagulation tank enters a primary flocculation tank, 1-3 mg/L PAM is added, the retention time is 15-30 min, the water enters the primary sedimentation tank, and the retention time is 2-4 h;
step three, secondary fluorine and phosphorus removal and precipitation: the effluent of the first-stage defluorination and dephosphorization sedimentation tank enters a second-stage defluorination and dephosphorization sedimentation tank, the pH is firstly adjusted to 7-9 in a second-stage coagulation tank, and the molar ratio of calcium to fluorine is 1.2-2: 1, adding calcium chloride and 50-100 mg/LPAC, allowing the mixture to stay for 15-30 min, allowing the effluent of a secondary coagulation tank to enter a secondary flocculation tank, adding 1-3 mg/L PAM, allowing the effluent to stay for 15-30 min, allowing the effluent to enter a secondary sedimentation tank, allowing the effluent to stay for 2-4 h, and allowing the effluent to overflow to a sedimentation effluent tank;
step four, multi-medium filtration: and the wastewater in the precipitation water outlet tank enters a multi-media filter through a lifting pump for filtration treatment, suspended matters in the wastewater are intercepted, the multi-media filter cleaning water flows back to a secondary coagulation tank of a secondary fluorine and phosphorus removal sedimentation tank, the multi-media filter outlet water enters a reuse water tank, and the multi-media filter outlet water is pumped to a sulfuric acid plant circulating water system for reuse.
6. The method for treating and recycling ammonium phosphate condensate as claimed in claim 5, wherein in the first step of deamination, a homogeneous gel type strong acid cation exchange resin is adopted as deamination resin, the ion form is hydrogen form, the functional group is sulfonic group, the uniformity coefficient is less than 1.25, and the total exchange capacity is 1.80 meq/mL.
7. The ammonium phosphate condensate treatment and recycling method of claim 6, wherein in the first step of deamination, a deamination system is operated by two-by-two series connection of three same resin tanks, the working flow rate of resin is 5-10BV/h, the three resin tanks are respectively provided with a water inlet valve, a water outlet valve and a regeneration/backwashing water inlet and outlet valve, meanwhile, the outlet of each resin tank is connected with the inlet of the next resin tank through a series valve, two resin tanks are put into series operation each time, and the third resin tank is regenerated for later use: when the first deamination resin tank and the second deamination resin tank are connected in series, the third deamination resin tank is regenerated; after the first deamination resin tank is saturated, switching to a second deamination resin tank and a third deamination resin tank to operate in series, and regenerating the first deamination resin tank; and after the second deamination resin tank is saturated, switching to the third deamination resin tank and the first deamination resin tank to operate in series, regenerating the second deamination resin tank, and performing reciprocating switching operation.
8. The ammonium phosphate condensate treatment and recycling method of claim 7, wherein in the first step of deamination, after resin saturation of a resin tank, regeneration is carried out by using sulfuric acid with the mass concentration of 5% at the flow rate of 2BV/h, backwashing is carried out by using soft water at the flow rate of 4BV/h, and the regeneration waste liquid containing ammonium sulfate is sent to a tail gas washing system of an ammonium phosphate section for comprehensive utilization.
9. The method for treating and recycling the ammonium phosphate condensate of claim 5, wherein the sludge in the two sedimentation tanks in the first-stage fluorine and phosphorus removal sedimentation and the second-stage fluorine and phosphorus removal sedimentation in the second step is discharged to the comprehensive utilization section of the phosphogypsum.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112390450A (en) * | 2020-11-26 | 2021-02-23 | 新洋丰农业科技股份有限公司 | High-efficiency treatment process for ammonium phosphate condensate industrial sewage |
| CN117447007A (en) * | 2023-10-26 | 2024-01-26 | 湖北美辰环保股份有限公司 | Process for separating ammonium sulfate and ammonium phosphate from iron phosphate production wastewater |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112390450A (en) * | 2020-11-26 | 2021-02-23 | 新洋丰农业科技股份有限公司 | High-efficiency treatment process for ammonium phosphate condensate industrial sewage |
| CN117447007A (en) * | 2023-10-26 | 2024-01-26 | 湖北美辰环保股份有限公司 | Process for separating ammonium sulfate and ammonium phosphate from iron phosphate production wastewater |
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