CN219117212U - Ammonia nitrogen membrane crystallization recovery system for pharmaceutical wastewater - Google Patents
Ammonia nitrogen membrane crystallization recovery system for pharmaceutical wastewater Download PDFInfo
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- CN219117212U CN219117212U CN202223436838.4U CN202223436838U CN219117212U CN 219117212 U CN219117212 U CN 219117212U CN 202223436838 U CN202223436838 U CN 202223436838U CN 219117212 U CN219117212 U CN 219117212U
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Abstract
The utility model relates to a pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system, which comprises a wastewater primary cooling module, a wastewater secondary cooling module, an ammonia nitrogen recovery module and a crystallization separation module; the waste water primary cooling module is used for receiving the high-temperature waste water, regulating the pH value of the high-temperature waste water to be more than 10, inputting the high-temperature waste water with the regulated pH value into the heat exchanger to exchange heat with the low-temperature acid liquor, obtaining primary cooling waste water, and inputting the primary cooling waste water into the waste water secondary cooling module; the second-stage cooling module is used for distilling out part of ammonia water in the first-stage cooling wastewater through the first membrane component. The high-concentration acid liquor absorbs ammonia nitrogen in the secondary cooling wastewater in the second membrane component and inhibits water mass transfer. The ammonium salt is finally cooled in a crystallization separation module and recovered as crystals. The utility model can effectively solve the problems of high energy consumption and low product value in ammonia nitrogen resource recovery of pharmaceutical wastewater at high temperature, has stable process and is easy for industrial popularization.
Description
Technical Field
The utility model relates to the technical field of sewage treatment in environmental engineering, in particular to a pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system.
Background
According to the difference of target functions of pharmaceutical factories, the components of pharmaceutical wastewater are complex, but most of the pharmaceutical wastewater has the characteristics of high temperature, high ammonia nitrogen concentration, high COD content and the like.
The existing process for treating the pharmaceutical wastewater is characterized in that the pharmaceutical wastewater is subjected to cooling treatment firstly, and organic matters and toxic and harmful matters in the pharmaceutical wastewater are subjected to oxidative decomposition treatment by adopting an activated sludge method, so that a great amount of heat energy is wasted in the process, and a great amount of nutrient resources in the wastewater are wasted at the same time, but due to the limitation of technology, the pharmaceutical wastewater is difficult to recover resources, the temperature of the pharmaceutical wastewater can reach 80 ℃, the concentration of partial ammonia nitrogen can reach 4000mg/L, and the high temperature and the high ammonia nitrogen concentration of the pharmaceutical wastewater are important limiting factors for subsequent standard-reaching treatment.
At present, the feasible method for recycling ammonia nitrogen in pharmaceutical wastewater mainly comprises the following steps: a gas permeable membrane absorption method, a reduced pressure membrane distillation method, a gas stripping method, a chemical precipitation method, and the like. The method has the advantages that the air-permeable membrane absorption method adopts a hollow fiber membrane, ammonia nitrogen recovery is realized under the condition of consuming a small amount of acid liquor, the operation process is simplest and convenient, and the cost is lowest, but the ammonia nitrogen recovery product of the air-permeable membrane absorption method is an ammonium salt solution, so that the method is not beneficial to later transportation and sales, and cannot meet the market demand for ammonium salt crystal products; the crystallization treatment is carried out on the ammonium salt solution, so that a large amount of energy is consumed, and the cost of the product is increased; in theory, the ammonium salt crystals can be recovered by absorbing the high-concentration acid liquor in the absorption process of the breathable film, but the water in the wastewater is required to be transferred to the high-concentration acid liquor, so that the dilution effect of the water on the acid liquor is reduced; therefore, the utility model provides a cooling and water-blocking ammonia nitrogen crystallization recovery system for wastewater, which solves the problems.
Disclosure of Invention
Aiming at the defects, the utility model provides the ammonia nitrogen film crystallization recovery system for the pharmaceutical wastewater, which is used for improving the temperature of the acid liquor and reducing the temperature of the pharmaceutical wastewater by carrying out heat exchange on the acid liquor and the high-temperature pharmaceutical wastewater so as to prevent the transition mass transfer of moisture and strengthen the mass transfer of ammonia nitrogen and realize the acquisition of the mixed solution of the supersaturated ammonium salt and the acid.
In order to solve the technical problems, the utility model adopts the following technical scheme:
the pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system comprises a wastewater primary cooling module, a wastewater secondary cooling module, an ammonia nitrogen recovery module and a crystallization separation module;
the waste water primary cooling module is used for receiving the high-temperature waste water, regulating the pH value of the high-temperature waste water to be more than 10, inputting the high-temperature waste water with the regulated pH value into the heat exchanger to exchange heat with the low-temperature acid liquor, obtaining primary cooling waste water, and inputting the primary cooling waste water into the waste water secondary cooling module;
the second-stage cooling module is used for distilling part of ammonia water in the first-stage cooling wastewater through the first membrane assembly to obtain second-stage cooling wastewater and ammonia water, and is also used for storing the ammonia water and inputting the second-stage cooling wastewater into the second membrane assembly;
the ammonia nitrogen recovery module is used for inputting low-temperature acid liquor into the heat exchanger to enable the low-temperature acid liquor to exchange heat with the high-temperature wastewater, inputting the heated acid liquor into the second membrane module to absorb ammonia nitrogen in the second-stage cooling wastewater to obtain a mixed solution of ammonium salt and acid and deaminated wastewater, inputting the mixed solution of ammonium salt and acid into the crystallization separation module, and collecting and storing the deaminated wastewater;
the crystallization separation module is used for reducing the temperature of the mixed solution of the ammonium salt and the acid, and crystallizing and separating the cooled mixed solution of the ammonium salt and the acid to obtain ammonium salt crystals.
Further, the waste water primary cooling module comprises a waste water regulating tank, a waste water pump and a heat exchanger which are sequentially connected, wherein the waste water regulating tank is used for receiving high-temperature waste water, and the waste water pump is used for pumping the high-temperature waste water in the waste water regulating tank into the heat exchanger;
the waste water regulating tank is internally provided with a pH detection sensor which is used for detecting the pH value of high-temperature waste water in the waste water regulating tank.
Further, a stirring mechanism and a filtering mechanism are arranged in the wastewater regulating tank from top to bottom.
Further, the second grade cooling module includes first membrane module, vacuum pump and aqueous ammonia jar, first membrane module is tubular, the input of vacuum pump and the shell exit linkage of first membrane module, heat exchanger's output and the tube layer entry linkage of first membrane module, the output of vacuum pump is connected with the input of aqueous ammonia jar.
Further, the membranes in the first membrane component are made of hydrophobic hollow fiber membranes, and the tolerance pressure of the hydrophobic hollow fiber membranes is not less than 10kpa.
Further, the ammonia nitrogen recovery module comprises an acid liquid tank, an acid liquid pump, a second membrane component and a wastewater liquid storage tank, wherein the second membrane component is in a pipe shape, the output end of the acid liquid tank is connected with the input end of the acid liquid pump, the output end of the acid liquid pump is connected with a heat exchange inlet of the heat exchanger, and the acid liquid pump is used for pumping the acid liquid in the acid liquid tank into the heat exchanger;
the heat exchange outlet of the heat exchanger is connected with the shell layer inlet of the second membrane component, the tube layer outlet of the first membrane component is connected with the tube layer inlet of the second membrane component, the shell layer outlet of the second membrane component is connected with the input end of the acid liquor pond, and the tube layer outlet of the second membrane component is connected with the input end of the wastewater liquid storage tank.
Further, a pH detection sensor is arranged in the acid liquid pool and is used for detecting the pH value of the solution in the acid liquid pool.
Further, the crystallization separation module comprises a metering pump, a condenser, a crystallization reaction kettle and a filter, wherein the input end of the metering pump is connected with the acid liquor pond, the input end of the condenser is connected with the output end of the metering pump, the input end of the crystallization reaction kettle is connected with the output end of the condenser, the input end of the filter is connected with the output end of the crystallization reaction kettle, and the metering pump is used for sequentially pumping the solution in the acid liquor pond into the condenser, the crystallization reaction kettle and the filter.
After the technical scheme is adopted, compared with the prior art, the utility model has the following advantages:
the utility model can effectively solve the problems of overhigh ammonia nitrogen concentration and low ammonium salt recovery value in the pharmaceutical wastewater treatment process, can well realize ammonia nitrogen recovery through the membrane absorption process, can carry out secondary cooling on high-temperature pharmaceutical wastewater through the cooperation of the heat exchanger and the first membrane component, simultaneously permeate out part of ammonia water for storage, realize ammonia nitrogen recovery and cooling treatment, and greatly reduce the consumption of cooling water;
the method has the advantages that the method well realizes the minimization of water mass transfer in the ammonia nitrogen membrane absorption process by carrying out heat exchange heating on the acid liquor and the depressurization and cooling treatment on the wastewater, the most critical step in the recovery of the ammonium salt by membrane crystallization can greatly reduce the formation condition of the ammonium salt crystal, maintain higher saturation of the ammonium salt, and greatly reduce the recovery energy consumption of the ammonia nitrogen crystal on the aspect of the process result.
The utility model will now be described in detail with reference to the drawings and examples.
Drawings
Fig. 1 is a schematic diagram of the overall structure of the present utility model.
In the drawings, the list of components represented by the various numbers is as follows:
1. a waste water regulating tank; 12. a waste water pump; 13. a heat exchanger; 21. a first membrane module; 22. a vacuum pump; 23. an ammonia water tank; 31. an acid liquid pool; 32. an acid liquid pump; 33. a second membrane module; 34. a wastewater storage tank; 41. a metering pump; 42. a condenser; 43. a crystallization reaction kettle; 44. and (3) a filter.
Detailed Description
The principles and features of the present utility model are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the utility model and are not to be construed as limiting the scope of the utility model.
In the description of the present utility model, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", "clockwise", "counterclockwise", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, merely to facilitate description of the present utility model and simplify description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present utility model.
As shown in fig. 1, the pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system comprises a wastewater primary cooling module, a wastewater secondary cooling module, an ammonia nitrogen recovery module and a crystallization separation module;
the waste water primary cooling module is used for receiving the high-temperature waste water, regulating the pH value of the high-temperature waste water to be more than 10, inputting the high-temperature waste water with the regulated pH value into the heat exchanger 13 to exchange heat with the low-temperature acid liquid, obtaining primary cooling waste water, and inputting the primary cooling waste water into the waste water secondary cooling module;
the second-stage cooling module is used for distilling part of ammonia water in the first-stage cooling wastewater through the first membrane module 21 to obtain second-stage cooling wastewater and ammonia water, and is also used for storing the ammonia water and inputting the second-stage cooling wastewater into the second membrane module 33;
the ammonia nitrogen recovery module is used for inputting low-temperature acid liquid into the heat exchanger 13 to enable the low-temperature acid liquid to exchange heat with the high-temperature wastewater, inputting the heated acid liquid into the second membrane module 33 to absorb ammonia nitrogen in the secondary cooling wastewater to obtain a mixed solution of ammonium salt and acid and deaminated wastewater, inputting the mixed solution of ammonium salt and acid into the crystallization separation module, and collecting and storing the deaminated wastewater;
the crystallization separation module is used for reducing the temperature of the mixed solution of the ammonium salt and the acid, and crystallizing and separating the cooled mixed solution of the ammonium salt and the acid to obtain ammonium salt crystals.
As one embodiment, the first-stage cooling module for wastewater comprises a wastewater regulating tank 11, a wastewater pump 12 and a heat exchanger 13 which are sequentially connected, wherein the wastewater regulating tank 11 is used for receiving high-temperature wastewater, and the wastewater pump 12 is used for pumping the high-temperature wastewater in the wastewater regulating tank 11 into the heat exchanger 13;
the waste water regulating tank 11 is internally provided with a pH detection sensor, the pH detection sensor is used for detecting the pH value of high-temperature waste water in the waste water regulating tank 11, and the model of the pH detection sensor can be a pH sensor InPro3100/120Pt100.
As an implementation mode, the stirring mechanism and the filtering mechanism are arranged in the wastewater regulating tank 11 from top to bottom, so that interception of large particles in wastewater can be realized, and pollution of the particles to a membrane and pipeline blockage in a subsequent membrane process are reduced.
Specifically, the wastewater pump 12 is made of alkali-resistant and high-temperature-resistant materials.
As an implementation manner, the secondary cooling module comprises a first membrane assembly 21, a vacuum pump 22 and an ammonia water tank 23, wherein the first membrane assembly 21 is tubular, the input end of the vacuum pump 22 is connected with the shell layer outlet of the first membrane assembly 21, the output end of the heat exchanger 13 is connected with the pipe layer inlet of the first membrane assembly 21, and the output end of the vacuum pump 22 is connected with the input end of the ammonia water tank 23.
As one embodiment, the membranes in the first membrane module 21 are made of hydrophobic hollow fiber membranes, and the pressure resistance of the hydrophobic hollow fiber membranes is not less than 10kpa.
As an implementation manner, the ammonia nitrogen recovery module comprises an acid liquid tank 31, an acid liquid pump 32, a second membrane assembly 33 and a wastewater liquid storage tank 34, wherein the second membrane assembly 33 is in a pipe shape, the output end of the acid liquid tank 31 is connected with the input end of the acid liquid pump 32, the output end of the acid liquid pump 32 is connected with the heat exchange inlet of the heat exchanger 13, and the acid liquid pump 32 is used for pumping the acid liquid in the acid liquid tank 31 into the heat exchanger 13;
the heat exchange outlet of the heat exchanger 13 is connected with the shell inlet of the second membrane assembly 33, the tube layer outlet of the first membrane assembly 21 is connected with the tube layer inlet of the second membrane assembly 33, the shell outlet of the second membrane assembly 33 is connected with the input end of the acid liquor tank 31, and the tube layer outlet of the second membrane assembly 33 is connected with the input end of the wastewater storage tank 34.
Specifically, the acid pump 32 is made of acid-resistant and high-temperature-resistant materials, and the heat exchanger 13 and the second membrane module 33 are made of acid-resistant and high-temperature-resistant materials.
As an embodiment, a pH detection sensor is disposed in the acid tank 31, and the pH detection sensor is used for detecting the pH value of the solution in the acid tank 31.
As an embodiment, the crystallization separation module includes a metering pump 41, a condenser 42, a crystallization reaction kettle 43 and a filter 44, wherein an input end of the metering pump 41 is connected with the acid liquor tank 31, an input end of the condenser 42 is connected with an output end of the metering pump 41, an input end of the crystallization reaction kettle 43 is connected with an output end of the condenser 42, an input end of the filter 44 is connected with an output end of the crystallization reaction kettle 43, and the metering pump 41 is used for sequentially pumping a solution in the acid liquor tank 31 into the condenser 42, the crystallization reaction kettle 43 and the filter 44.
The process flow of the utility model comprises the following steps:
(1) Inputting high-temperature wastewater into the wastewater regulating tank 1, and stirring and filtering the high-temperature wastewater through a stirring mechanism and a filtering mechanism to filter out large particles in the high-temperature wastewater, so as to prevent the large particles from polluting or reading a film component;
inputting high-concentration acid liquor into an acid liquor pool;
(2) The waste water pump 12 inputs the stirred and filtered high-temperature waste water into the heat exchanger 13, the acid liquid pump 32 inputs the acid liquid in the acid liquid pool into the heat exchange end of the heat exchanger 13, the high-temperature waste water exchanges heat with the acid liquid in the heat exchanger 13, so that the acid liquid is heated, the high-temperature waste water is cooled, first-stage cooling waste water and heated acid liquid are obtained, the first-stage cooling waste water is input into the pipe layer of the first membrane module 21, and the heated acid liquid is input into the shell layer of the second membrane module 33;
(3) The vacuum pump 22 causes negative pressure on the shell layer of the first membrane module 21 so that ammonia water in the first-stage cooling wastewater permeates through the membrane tubes and enters the shell layer to obtain ammonia water and second-stage cooling wastewater, then the ammonia water is input into the ammonia water tank 23 by the vacuum pump 22 for storage, and the second-stage cooling wastewater enters the tube layer of the second membrane module 33 after passing through the membrane tubes of the first membrane module 21;
(4) In the process of passing through the membrane tube of the second membrane assembly 33, the second-stage cooling wastewater and the heated acid liquor are subjected to direct contact reaction in the second membrane assembly 33 (after the heat exchange step, the temperature of the acid liquor is 10-15 ℃ higher than that of the wastewater due to the temperature difference of the two, even if high-concentration acid liquor is adopted to absorb ammonia nitrogen, the water mass transfer can be inhibited to the greatest extent, the higher operation concentration of the acid liquor is ensured), ammonium ions in the second-stage cooling wastewater pass through the membrane tube and are absorbed by the heated acid liquor to obtain a mixed solution of ammonium salt and acid and deamination wastewater, the deamination wastewater passes through the membrane tube of the second membrane assembly 33 and then enters the wastewater liquid storage tank 34 to be stored, and the mixed solution of ammonium salt and acid is input into the acid liquid pool 31 from the shell outlet of the second membrane assembly 33;
(5) When the pH value of the solution in the acid liquor pond 31 is increased to more than 6, pumping the solution in the acid liquor pond 31 into a condenser 42 through a metering pump 41 for cooling, reducing the temperature of the solution to below 10 ℃, then inputting the solution into a crystallization reaction kettle for crystallization to obtain ammonium salt and residual acid liquor, after the crystallization of the ammonium salt is completed, realizing the recovery of the ammonium salt crystal in a form of combining precipitation and filtration, and inputting the residual acid liquor into the acid liquor pond 31 again after the filtration of a filter 44 for recycling.
The foregoing is illustrative of the best mode of carrying out the utility model, and is not presented in any detail as is known to those of ordinary skill in the art. The protection scope of the utility model is defined by the claims, and any equivalent transformation based on the technical teaching of the utility model is also within the protection scope of the utility model.
Claims (8)
1. The pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system is characterized by comprising a wastewater primary cooling module, a wastewater secondary cooling module, an ammonia nitrogen recovery module and a crystallization separation module;
the waste water primary cooling module is used for receiving high-temperature waste water and inputting the high-temperature waste water into the heat exchanger (13), and the output end of the waste water primary cooling module is connected with the input end of the waste water secondary cooling module;
the output end of the secondary cooling module is connected with the input end of the second membrane assembly (33);
the ammonia nitrogen recovery module is used for inputting low-temperature acid liquor into the heat exchanger (13) so as to enable the low-temperature acid liquor and the high-temperature wastewater to exchange heat, and inputting the heated acid liquor into the second membrane assembly (33), and the output end of the ammonia nitrogen recovery module is connected with the input end of the crystallization separation module;
the crystallization separation module is used for reducing the temperature of the mixed solution of ammonium salt and acid and performing crystallization separation.
2. The pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system according to claim 1, wherein the wastewater primary cooling module comprises a wastewater regulating tank (11), a wastewater pump (12) and a heat exchanger (13) which are sequentially connected, the wastewater regulating tank (11) is used for receiving high-temperature wastewater, and the wastewater pump (12) is used for pumping the high-temperature wastewater in the wastewater regulating tank (11) into the heat exchanger (13);
the waste water regulating tank (11) is internally provided with a pH detection sensor, and the pH detection sensor is used for detecting the pH value of high-temperature waste water in the waste water regulating tank (11).
3. The pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system according to claim 2, wherein a stirring mechanism and a filtering mechanism are arranged in the wastewater regulating tank (11).
4. The pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system according to claim 2, wherein the secondary cooling module comprises a first membrane component (21), a vacuum pump (22) and an ammonia water tank (23), a plurality of membrane pipes are arranged in the first membrane component (21), the input end of the vacuum pump (22) is connected with the shell outlet of the first membrane component (21), the output end of the heat exchanger (13) is connected with the inlet of the pipe layer of the first membrane component (21), and the output end of the vacuum pump (22) is connected with the input end of the ammonia water tank (23).
5. The pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system according to claim 4, wherein the membrane tube is made of a hydrophobic hollow fiber membrane, and the withstand pressure of the membrane tube is not less than 10kpa.
6. The pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system according to claim 4, wherein the ammonia nitrogen recovery module comprises an acid liquid tank (31), an acid liquid pump (32), a second membrane assembly (33) and a wastewater liquid storage tank (34), a plurality of membrane pipes are arranged in the second membrane assembly (33), the output end of the acid liquid tank (31) is connected with the input end of the acid liquid pump (32), the output end of the acid liquid pump (32) is connected with the heat exchange inlet of the heat exchanger (13), and the acid liquid pump (32) is used for pumping the acid liquid in the acid liquid tank (31) into the heat exchanger (13);
the heat exchange outlet of the heat exchanger (13) is connected with the shell inlet of the second membrane component (33), the pipe layer outlet of the first membrane component (21) is connected with the pipe layer inlet of the second membrane component (33), the shell outlet of the second membrane component (33) is connected with the input end of the acid liquor pond (31), and the pipe layer outlet of the second membrane component (33) is connected with the input end of the wastewater liquid storage tank (34).
7. The ammonia nitrogen membrane crystallization recovery system of pharmaceutical wastewater according to claim 6, wherein a pH detection sensor is arranged in the acid liquid tank (31), and the pH detection sensor is used for detecting the pH value of the solution in the acid liquid tank (31).
8. The pharmaceutical wastewater ammonia nitrogen membrane crystallization recovery system according to claim 1, wherein the crystallization separation module comprises a metering pump (41), a condenser (42), a crystallization reaction kettle (43) and a filter (44), wherein the input end of the metering pump (41) is connected with an acid liquor pond (31), the input end of the condenser (42) is connected with the output end of the metering pump (41), the input end of the crystallization reaction kettle (43) is connected with the output end of the condenser (42), the input end of the filter (44) is connected with the output end of the crystallization reaction kettle (43), and the metering pump (41) is used for sequentially pumping a solution in the acid liquor pond (31) into the condenser (42), the crystallization reaction kettle (43) and the filter (44).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202223436838.4U CN219117212U (en) | 2022-12-21 | 2022-12-21 | Ammonia nitrogen membrane crystallization recovery system for pharmaceutical wastewater |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202223436838.4U CN219117212U (en) | 2022-12-21 | 2022-12-21 | Ammonia nitrogen membrane crystallization recovery system for pharmaceutical wastewater |
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| CN219117212U true CN219117212U (en) | 2023-06-02 |
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| CN202223436838.4U Active CN219117212U (en) | 2022-12-21 | 2022-12-21 | Ammonia nitrogen membrane crystallization recovery system for pharmaceutical wastewater |
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