CN216336747U - Device for preparing calcium chloride concentrated solution by ammonia distillation wastewater - Google Patents
Device for preparing calcium chloride concentrated solution by ammonia distillation wastewater Download PDFInfo
- Publication number
- CN216336747U CN216336747U CN202122985968.2U CN202122985968U CN216336747U CN 216336747 U CN216336747 U CN 216336747U CN 202122985968 U CN202122985968 U CN 202122985968U CN 216336747 U CN216336747 U CN 216336747U
- Authority
- CN
- China
- Prior art keywords
- nanofiltration
- water
- unit
- pipeline
- concentrated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The utility model discloses a device for preparing calcium chloride concentrated solution by ammonia distillation wastewater, which comprises a pretreatment unit, a first-stage nanofiltration unit, a second-stage nanofiltration unit and a third-stage nanofiltration unit which are connected in sequence by pipelinesThe device comprises a stage nanofiltration unit and a reverse osmosis unit, wherein a water production pipeline of the previous unit is used as a water inlet pipeline of the next unit; the pretreatment unit and the primary nanofiltration unit are both provided with concentrated water outlets and are respectively connected to a concentrated water tank through pipelines; the second-stage nanofiltration unit is provided with a concentrated water outlet and is connected to a concentrated liquid tank through a concentrated water pipeline; the third-stage nanofiltration unit is provided with a concentrated water reflux pipeline which is communicated with a second-stage nanofiltration water inlet pipeline; the water production pipeline of the reverse osmosis unit is connected to the fresh water tank, a branch line is further arranged on the reverse osmosis water production pipeline and serves as a fresh water backflow pipeline to be communicated with the primary nanofiltration water inlet pipeline, and the reverse osmosis concentrated water pipeline is connected to the brine tank. The utility model leads CaCl in the ammonia distillation wastewater2And NaCl, the high-efficiency separation and concentration are realized, and the high-concentration calcium chloride, the high-concentration sodium chloride concentrated solution and the fresh water are finally obtained, so that the method has good environmental protection and economic benefits.
Description
Technical Field
The utility model relates to a device for preparing calcium chloride concentrated solution from ammonia evaporation wastewater, in particular to a device for preparing calcium chloride concentrated solution from ammonia evaporation wastewater generated in an ammonia-soda process soda ash process by utilizing membrane separation and concentration.
Background
The soda ash is used as an important inorganic chemical raw material, the annual domestic capacity is over 3000 ten thousand tons, and the ammonia-soda process has the capacity ratio of 45 percent in China. About 10m can be generated for each 1 ton of soda ash produced by ammonia-soda process3The discharge amount of the ammonia distillation wastewater in China is more than 1 billion cubic meters every year. The discharge of ammonia distillation wastewater not only causes environmental pollution, but also wastes resources, and the clear liquid is mainly usedThe essential component is CaCl2(8-10%) and NaCl (4-6%), and has recycling value. Typical composition of ammonia distillation waste liquor:
| composition (I) | Ca2+ | Mg2+ | Na+ | Cl- | SO4 2- |
| Content (mg/L) | 37219 | 1.2 | 19313 | 95564 | 418 |
At present, the mainstream process for resource utilization of ammonia distillation wastewater at home and abroad comprises the steps of preparing calcium chloride by an evaporative crystallization process and preparing calcium sulfate by taking sodium sulfate as a raw material. The first process is that the ammonia evaporation waste water is subjected to solid-liquid separation, then the clear liquid is subjected to evaporation crystallization to produce solid calcium chloride, in order to save steam consumption, the traditional method of domestic enterprises is to send the clear liquid to a salt pan for natural evaporation, and the concentration of the clear liquid is increased to about 20 Be for producing calcium chlorideThe method has instability, and cannot ensure the quality and the supply quantity of the calcium chloride concentrated solution, so that the fluctuation of the production cost of the calcium chloride is large. The second process is a chemical process, and the reaction of sodium sulfate and clear liquid is used for producing calcium sulfate, so that a large amount of raw material sodium sulfate is consumed, and the residual mother liquor still contains more impurities. Chinese patent CN111559753A discloses a method and a device for utilizing ammonia distillation waste liquid in a soda plant, in the method, sodium sulfate is added into the ammonia distillation waste liquid, and Ca in the waste liquid is utilized2+Preparation of CaSO4And adding sodium carbonate to further remove calcium, and finally further removing impurities by using a membrane method to obtain a relatively pure sodium chloride solution.
SUMMERY OF THE UTILITY MODEL
The technical problem to be solved by the utility model is to provide a device for preparing a concentrated calcium chloride solution from ammonia distillation wastewater, which can provide a high-concentration raw material solution for producing solid calcium chloride by an evaporative crystallization method, overcome the problems of large occupied area, high raw material consumption, low output efficiency, unstable quality and yield of the traditional tedding method, overcome the problems of high energy consumption, easy scaling of the device and poor economic benefit of a direct evaporative concentration process, and realize the efficient utilization of ammonia distillation wastewater resources by an all-membrane method.
In order to solve the technical problem, the utility model comprises a pretreatment unit, a first-stage nanofiltration unit, a second-stage nanofiltration unit, a third-stage nanofiltration unit and a reverse osmosis unit which are connected in sequence by pipelines, wherein a water production pipeline of the previous unit is used as a water inlet pipeline of the next unit; the pretreatment unit and the primary nanofiltration unit are both provided with concentrated water outlets and are respectively connected to a concentrated water tank through pipelines; the second-stage nanofiltration unit is provided with a concentrated water outlet and is connected to a concentrated liquid tank through a concentrated water pipeline; the third-stage nanofiltration unit is provided with a concentrated water reflux pipeline which is communicated with a second-stage nanofiltration water inlet pipeline; the water production pipeline of the reverse osmosis unit is connected to the fresh water tank, a branch line is further arranged on the reverse osmosis water production pipeline and serves as a fresh water backflow pipeline to be communicated with the primary nanofiltration water inlet pipeline, and the reverse osmosis concentrated water pipeline is connected to the brine tank.
The pretreatment, primary nanofiltration, secondary nanofiltration and tertiary nanofiltration water production pipelines are respectively provided with a clear liquid tank, a primary nanofiltration water production tank, a secondary nanofiltration water production tank and a tertiary nanofiltration water production tank.
The pretreatment unit adopts microfiltration and/or ultrafiltration, and comprises one or a combination of a ceramic membrane, a hollow fiber ultrafiltration membrane and an organic tubular membrane.
The first-stage nanofiltration unit adopts SO4 2-A retention rate of 81-92%, Ca2+The rejection rate is 8-46%, and Na+A nanofiltration membrane with the rejection rate of-12-8%, the operating pressure of 2.0-5.5 MPa and the recovery rate of 45-85%; a hydrochloric acid adding port is arranged on the primary nanofiltration water production pipeline; the second-stage nanofiltration unit adopts Ca2+Rejection rate is 63-91%, Na+A nanofiltration membrane with the retention rate of-21 to-5 percent, the operating pressure of 5.5 to 8.8 MPa and the recovery rate of 55 to 85 percent; the second-stage nanofiltration adopts a sectional design, and a booster pump is arranged between sections; the third-stage nanofiltration unit adopts Ca2+The rejection rate is 72-89%, and Na+A nanofiltration membrane with the rejection rate of 15-32%, the operating pressure of 2.0-5.8 MPa and the recovery rate of 55-85%; the reverse osmosis unit adopts a reverse osmosis membrane with the desalination rate of 92-98%, the operating pressure is 4.5-7.9 MPa, and the recovery rate is 32-65%.
The water inlet pipelines of the pretreatment, primary nanofiltration, secondary nanofiltration, tertiary nanofiltration and reverse osmosis units are all provided with water inlet pumps, the water inlet pipelines of the primary nanofiltration, secondary nanofiltration, tertiary nanofiltration and reverse osmosis units are simultaneously provided with security filters, the tertiary nanofiltration concentrated water return pipeline is provided with a booster pump, and the reverse osmosis produced water fresh water return pipeline is provided with a return pump.
The clear liquid tank is provided with a pretreatment water production inlet, a hydrochloric acid adding inlet and a reverse osmosis water production backflow inlet, and the clear liquid tank is provided with stirring or aeration.
The joint position of the three-stage nanofiltration concentrated water reflux pipeline which is pressurized and then merged into the second-stage nanofiltration water inlet pipeline is arranged at the water outlet side of the second-stage nanofiltration water inlet pump, and the downstream of the joint position is provided with a pipeline mixer.
And energy recovery devices including a turbine type energy recovery device or a PX energy recovery device are arranged on the primary nanofiltration water pipe, the secondary nanofiltration water pipe and the reverse osmosis concentrated water pipe.
The water inlet pipeline, the water production pipeline, the concentrated water pipeline and the return pipeline are all provided with an online flowmeter, an online water quality analyzer is also provided with an automatic control valve, and the hydrochloric acid adding pipeline is provided with an online flowmeter.
The utility model can realize CaCl in the ammonia distillation wastewater2And NaCl are effectively separated, and Na in the calcium chloride concentrated solution with the concentration of 18-20 wt% is finally obtained+The concentration is less than or equal to 17g/L, and Ca in the obtained 6-14 wt% sodium chloride concentrated solution2+The concentration is less than or equal to 1.5g/L, the calcium chloride concentrated solution can be directly used for producing calcium chloride by evaporation crystallization, the sodium chloride concentrated solution can be used for producing soda/chloride salt, and in addition, part of fresh water is produced.
The first-stage nanofiltration scaling risk can be effectively reduced through reverse osmosis produced water backflow, and the addition of a scale inhibitor is reduced or even not required; through the arrangement and combination of membranes with different performances, the recovery rate of each device and the retention rate of ions are controlled, and CaCl can be effectively controlled2And NaCl is separated and concentrated; the utilization rate of the ammonia distillation waste clear liquid can be further improved through the three-stage nanofiltration concentrated water reflux, and the comprehensive utilization rate can reach more than 65 percent.
Compared with the prior art, the utility model adopts the full-film process to lead CaCl in the ammonia distillation wastewater2And NaCl, the high-efficiency separation and concentration are realized, other components are not introduced, and the high-concentration calcium chloride, sodium chloride concentrated solution and fresh water are finally obtained, so that the utilization rate of the ammonia evaporation wastewater is improved, the high-efficiency green clean recovery of the ammonia evaporation wastewater is realized, compared with the traditional calcium chloride evaporative crystallization production process, the concentrated land is reduced, the concentration efficiency is improved, the quality of the calcium chloride concentrated solution and the stability of the supply are ensured, and the environment-friendly and economic benefits are good.
Drawings
The utility model is further illustrated with reference to the following figures and examples:
FIG. 1 is a schematic view of the apparatus of the present invention.
In the figure: 1. a raw water tank; 2. pre-treating a water inlet pipeline; 3. pre-treating a water inlet pump; 4. a pre-processing unit; 5. a pre-treatment concentrate line; 6. a clear liquid tank; 7. a primary nanofiltration water inlet pipeline; 8. a first-stage nanofiltration water inlet pump; 9. a first-stage nanofiltration unit; 10. a first-stage nanofiltration concentrated water pipeline; 11. a concentrated water tank; 12. a first-stage nanofiltration water production tank; 13. a secondary nanofiltration water inlet pump; 14. a secondary nanofiltration water inlet pipeline; 15. a pipeline mixer; 16. a secondary nanofiltration unit; 17. a second stage nanofiltration concentrated water pipeline; 18. a concentrated solution tank; 19. a secondary nanofiltration water production tank; 20. a three-stage nanofiltration water inlet pump; 21. a third nanofiltration unit; 22. a three-stage nanofiltration concentrated water booster pump; 23. a three-stage nanofiltration concentrated water reflux pipeline; 24. a three-stage nanofiltration water production tank; 25. a reverse osmosis water intake pump; 26. a reverse osmosis unit; 27. a reverse osmosis concentrate line; 28. a brine tank; 29. a reverse osmosis water production line; 30. a fresh water tank; 31. a fresh water reflux pump; 32. a fresh water return line; 33. and (5) a hydrochloric acid tank.
Detailed Description
Example 1
Referring to fig. 1, the device for preparing the calcium chloride concentrated solution from the ammonia distillation wastewater comprises a pretreatment unit 4, a first-stage nanofiltration unit 9, a second-stage nanofiltration unit 16, a third-stage nanofiltration unit 21 and a reverse osmosis unit 26 which are connected in sequence by pipelines, wherein a water production pipeline of the previous unit is used as a water inlet pipeline of the next unit; the pretreatment unit 4 and the primary nanofiltration unit 9 are both provided with concentrated water outlets and are respectively connected to a concentrated water tank 11 through pipelines; the second-stage nanofiltration unit 16 is provided with a concentrated water outlet and is connected to a concentrated liquid tank 18 through a second-stage nanofiltration concentrated water pipeline 17; the third nanofiltration unit 21 is provided with a third nanofiltration concentrated water return pipeline 23 which is communicated with a second nanofiltration water inlet pipeline 14; of the reverse osmosis unit 26; the reverse osmosis water production line 29 is connected to a fresh water tank 30, and a branch line 32 is provided as a fresh water return line communicating with the clear water tank 6, and the reverse osmosis concentrated water line 27 is connected to a brine tank 28. The structures of the pretreatment unit 4, the primary nanofiltration unit 9, the secondary nanofiltration unit 16, the tertiary nanofiltration unit 21 and the reverse osmosis unit 26 are known per se.
Wherein, the water production pipelines of the pretreatment unit 4, the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16 and the third-stage nanofiltration unit 21 are respectively provided with a clear liquid tank 6, a first-stage nanofiltration water production tank 12, a second-stage nanofiltration water production tank 19 and a third-stage nanofiltration water production tank 24. The pretreatment unit 4 adopts microfiltration and/or ultrafiltration, and can select one or a combination of a ceramic membrane, a hollow fiber ultrafiltration membrane and an organic tubular membrane, wherein the ceramic membrane is adopted in the embodiment.
SO is adopted as the first-stage nanofiltration unit 94 2-A retention rate of 81-92%, Ca2+The rejection rate is 8-46%, and Na+A nanofiltration membrane with the rejection rate of-12-8%, the operating pressure of 2.0-5.5 MPa and the recovery rate of 45-85%; a hydrochloric acid adding port is arranged on the first-stage nanofiltration water production pipeline, and in the embodiment, the hydrochloric acid adding port is arranged on the clear liquid tank 6 and is communicated with the hydrochloric acid tank 33 through a pipeline. The second-stage nanofiltration unit 16 adopts Ca2+Rejection rate is 63-91%, Na+A nanofiltration membrane with the retention rate of-21 to-5 percent, the operating pressure of 5.5 to 8.8 MPa and the recovery rate of 55 to 85 percent; according to the concentration requirement of the final calcium chloride concentrated solution, the secondary nanofiltration adopts a three-stage design, and a booster pump is arranged between the stages. The three-stage nanofiltration unit 21 adopts Ca2+The rejection rate is 72-89%, and Na+The rejection rate of the nanofiltration membrane is 15-32%, the operating pressure is 2.0-5.8 MPa, and the recovery rate is 55-85%. The reverse osmosis unit 26 adopts a reverse osmosis membrane with the desalination rate of 92-98%, the operating pressure is 4.5-7.9 MPa, and the recovery rate is 32-65%.
The water inlet pipelines of the pretreatment unit 4, the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16, the third-stage nanofiltration unit 21 and the reverse osmosis unit 26 are all provided with water inlet pumps, the water inlet pipelines of the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16, the third-stage nanofiltration unit 21 and the reverse osmosis unit 26 are simultaneously provided with security filters, the third-stage nanofiltration concentrated water reflux pipeline 23 is provided with a third-stage nanofiltration concentrated water booster pump 22, and the reverse osmosis produced water fresh water reflux pipeline 32 is provided with a fresh water reflux pump 31. The clear liquid tank 6 is provided with a pretreatment water production inlet, a hydrochloric acid feeding inlet and a reverse osmosis water production backflow inlet, and the clear liquid tank 6 is provided with stirring or aeration. The interface position of the third nanofiltration concentrated water reflux pipeline 23 merged into the second nanofiltration water inlet pipeline 14 is arranged at the water outlet side of the second nanofiltration water inlet pump 13, and the downstream of the interface position is provided with a pipeline mixer 15. PX energy recovery devices are arranged on the concentrated water pipelines of the primary nanofiltration unit 9, the secondary nanofiltration unit 16 and the reverse osmosis unit 26. The water inlet pipeline, the water production pipeline, the concentrated water pipeline and the return pipeline are all provided with an online flowmeter, an online water quality analyzer and an automatic control valve, and the hydrochloric acid adding pipeline is provided with the online flowmeter, so that remote monitoring and operation can be realized.
The working process of the utility model is as follows:
(1) pre-precipitating the ammonia distillation wastewater, and taking supernatant liquid 159m3The ammonia distillation wastewater is sent into a raw water tank 1, then sent into a pretreatment unit 4 through a pretreatment water inlet pipeline 2 and a pretreatment water inlet pump 3 to remove large solid particles and insoluble substances, the pretreatment in the embodiment adopts a ceramic membrane, the ammonia distillation wastewater after impurity removal is adjusted to pH 6.5 in a clear liquid tank 6 by hydrochloric acid from a hydrochloric acid tank 33, and simultaneously, fresh water is added through a fresh water backflow pipeline 32 for dilution, the dilution ratio is that the fresh water accounts for 13% of the volume of the ammonia distillation wastewater, and the clear liquid tank 6 is stirred by itself to obtain ammonia distillation wastewater with turbidity of 1.6 NTU;
(2) the ammonia distillation waste clear liquid obtained in the step (1) passes through a primary nanofiltration water inlet pipeline 7, is pressurized by a primary nanofiltration water inlet pump 8 and enters a primary nanofiltration unit 9 to obtain primary nanofiltration water and primary nanofiltration concentrated water, the primary nanofiltration water enters a primary nanofiltration water tank 12, the primary nanofiltration concentrated water enters a concentrated water tank 11 through a primary nanofiltration concentrated water pipeline 10, and the primary nanofiltration unit 9 is used for treating SO4 2-A retention rate of 84% for Ca2+The retention rate of (1) to Na is 10.3%+The rejection rate is-3%, the operation pressure is 3.8 MPa, the recovery rate is 71%, the first-stage nanofiltration unit 9 is not added with scale inhibitor, and the concentrated water side has no scaling phenomenon;
(3) the first stage nanofiltration water product obtained in the step (2) is pressurized by a second stage nanofiltration water inlet pump 13 through a second stage nanofiltration water inlet pipeline 14 to enter a second stage nanofiltration unit 16, a third stage nanofiltration concentrated water reflux inlet is arranged on the second stage nanofiltration water inlet pipeline 14, a pipeline mixer 15 is arranged at the downstream of the inlet to obtain second stage nanofiltration water product and second stage nanofiltration concentrated water, the second stage nanofiltration water product enters a second stage nanofiltration water production tank 19, the second stage nanofiltration concentrated water is the concentrated calcium chloride solution product and is sent to a concentrated solution tank 18, the second stage nanofiltration unit 16 is divided into three sections, a booster pump is arranged between the sections, and Ca is treated by the booster pump2+A retention rate of 81% for Na+The retention rate is-9%, the operation pressure is 7.8 MPa, and the recovery rate is 74%;
(4) pressurizing the second-stage nanofiltration product water obtained in the step (3) by a third-stage nanofiltration water inlet pump 20 to enter a third-stage nanofiltration unit 21 to obtain third-stage nanofiltration product water and third-stage nanofiltration concentrated water, feeding the third-stage nanofiltration product water into a third-stage nanofiltration water production tank 24, and feeding the third-stage nanofiltration concentrated water into the third-stage nanofiltration concentrated waterAfter being pressurized by a booster pump 22, the water is connected into a secondary nanofiltration water inlet pipeline 14 through a tertiary nanofiltration concentrated water return pipeline 23 and then enters a secondary nanofiltration unit 16 again, and the tertiary nanofiltration unit 21 is used for Ca separation2+A retention rate of 89% for Na+The retention rate is 30 percent, the operation pressure is 4.4MPa, and the recovery rate is 70 percent;
(5) pressurizing the three-stage nanofiltration product water obtained in the step (4) by a reverse osmosis water inlet pump 25 to enter a reverse osmosis unit 26 to obtain reverse osmosis product water and reverse osmosis concentrated water, pressurizing 50% of the reverse osmosis product water by a fresh water reflux pump 31, and refluxing to a clear liquid tank 6 as dilution water, wherein the reflux amount is 20.5m3And h, the rest reverse osmosis produced water is taken as product fresh water to enter a fresh water tank 30, reverse osmosis concentrated water is taken as product sodium chloride concentrated solution to enter a brine tank 28, the desalination rate of the reverse osmosis unit 26 is 98%, the recovery rate is 52%, and the operation pressure is 5.6 MPa.
In this embodiment, a security filter is disposed in front of the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16, the third-stage nanofiltration unit 21 and the reverse osmosis unit 26, PX energy recovery devices are disposed on the concentrated water lines of the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16 and the reverse osmosis unit 26, online flow meters and online water quality analyzers are disposed on the concentrated water lines, and automatic control valves are disposed on the concentrated water lines to realize automatic control.
Finally obtain 42m3A 240g/L (20 wt%) calcium chloride concentrate of Na+The concentration was 16g/L to obtain 41m3H a concentrate of 89.5g/L (8.5 wt%) sodium chloride, wherein Ca is2+The concentration was 1g/L, and 20.5m was additionally obtained3The comprehensive utilization rate of fresh water and ammonia distillation waste clear liquid is 65 percent.
In the embodiment, the pretreatment unit 4, the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16 and the third-stage nanofiltration unit 21 are provided with the water production tanks, so that the system is stable in operation and high in fault tolerance rate, and after one unit is stopped, the operation of other units cannot be influenced in a short time.
Example 2
Referring to fig. 1, compared with example 1, in this embodiment, the pretreatment unit 4, the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16, and the third-stage nanofiltration unit 21 are not provided with a water production tank, a hydrochloric acid adding inlet is located on a pretreatment water production line, a pipeline mixer is arranged at the downstream of the hydrochloric acid adding inlet, and reverse osmosis water production does not flow back; the pretreatment unit 4 adopts a hollow fiber ultrafiltration membrane; the secondary nanofiltration unit 16 adopts a two-section type, and a booster pump is arranged between the sections; the concentrated water pipelines of the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16 and the reverse osmosis unit 26 are all provided with a turbine type energy recovery device.
The working process is as follows:
(1) pre-precipitating the ammonia distillation wastewater, and taking supernatant 186m3Feeding the ammonia distillation wastewater into a raw water tank 1 for h, feeding the ammonia distillation wastewater into a pretreatment unit 4 through a pretreatment water inlet pump 3 through a pretreatment water inlet pipeline 2 to remove large solid particles and insoluble substances, wherein the pretreatment in the embodiment adopts a hollow fiber ultrafiltration membrane, the ammonia distillation wastewater after impurity removal is not diluted, adding hydrochloric acid through a hydrochloric acid adding inlet arranged on a pretreatment water production pipeline, adjusting the pH value to 6.0 to obtain ammonia distillation wastewater clear liquid with the turbidity of 1.5NTU, and a pipeline mixer is arranged at the downstream of the hydrochloric acid adding inlet;
(2) the ammonia distillation waste clear liquid obtained in the step (1) passes through a primary nanofiltration water inlet pipeline 7, is pressurized by a primary nanofiltration water inlet pump 8 and enters a primary nanofiltration unit 9 to obtain primary nanofiltration product water and primary nanofiltration concentrated water, the primary nanofiltration concentrated water enters a concentrated water tank 11, and the primary nanofiltration unit 9 carries out SO treatment4 2-A retention rate of 88% for Ca2+The retention rate of (1) to Na was 20%+The interception rate is 8 percent, the operation pressure is 4.9 MPa, the recovery rate is 62 percent, the first-stage nanofiltration 9 is not added with scale inhibitor, and the concentrated water side has no scaling phenomenon;
(3) the first-stage nanofiltration water product obtained in the step (2) is pressurized by a second-stage nanofiltration water inlet pump 13 through a second-stage nanofiltration water inlet pipeline 14 to enter a second-stage nanofiltration unit 16, a third-stage nanofiltration concentrated water backflow inlet is arranged on the second-stage nanofiltration water inlet pipeline 14, a pipeline mixer 15 is arranged at the downstream of the inlet to obtain second-stage nanofiltration water product and second-stage nanofiltration concentrated water, the second-stage nanofiltration concentrated water is the calcium chloride concentrated solution which is the product, and is sent into a concentrated solution tank 18, the second-stage nanofiltration unit 16 is divided into two sections, a booster pump is arranged between the two sections to pump Ca2+A retention rate of 79% for Na+The retention rate is-11%, the operation pressure is 7.2 MPa, and the recovery rate is 71%;
(4) pressurizing the second-stage nanofiltration product water obtained in the step (3) by a third-stage nanofiltration water inlet pump 20 to enter a third-stage nanofiltration unitAnd 21, obtaining three-stage nanofiltration water production and three-stage nanofiltration concentrated water, wherein the three-stage nanofiltration concentrated water is pressurized by a booster pump 22, is connected into a second-stage nanofiltration water inlet pipeline 14 through a third-stage nanofiltration concentrated water return pipeline 23 and enters a second-stage nanofiltration unit 16 again, and the third-stage nanofiltration unit 21 is used for Ca treatment2+The retention rate of (1) to Na is 88%+The retention rate is 23 percent, the operation pressure is 3.6MPa, and the recovery rate is 64 percent;
(5) and (3) pressurizing the three-stage nanofiltration product water obtained in the step (4) by a reverse osmosis water inlet pump 25 to enter a reverse osmosis unit 26 to obtain reverse osmosis product water and reverse osmosis concentrated water, wherein the reverse osmosis product water is totally used as product fresh water to enter a fresh water tank 30, the reverse osmosis concentrated water is used as product sodium chloride concentrated solution to enter a brine tank 28, the desalination rate of the reverse osmosis unit 26 is 95%, the recovery rate is 45%, and the operating pressure is 5.2 MPa.
In this embodiment, a security filter is disposed in front of the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16, the third-stage nanofiltration unit 21, and the reverse osmosis unit 26, and the concentrated water pipelines of the first-stage nanofiltration unit 9, the second-stage nanofiltration unit 16, and the reverse osmosis unit 21 are all provided with a turbine type energy recovery device, and the pipelines are all provided with an online flowmeter, an online water quality analyzer, and an automatic control valve to realize automatic control.
Finally obtain 42m3A concentrate of calcium chloride at a concentration of 208.9g/L (18 wt.%), in which Na is present+At a concentration of 17g/L, 37m were obtained3H a concentrate of 87.2g/L (8.3 wt%) sodium chloride, wherein Ca is present2+The concentration was 0.9g/L, and 30m was obtained3The comprehensive utilization rate of fresh water and ammonia distillation waste clear liquid is 59 percent.
Claims (9)
1. A device for preparing calcium chloride concentrated solution by ammonia distillation wastewater is characterized by comprising a pretreatment unit, a first-stage nanofiltration unit, a second-stage nanofiltration unit, a third-stage nanofiltration unit and a reverse osmosis unit which are sequentially connected by pipelines, wherein a water production pipeline of the previous unit is used as a water inlet pipeline of the next unit; the pretreatment unit and the primary nanofiltration unit are both provided with concentrated water outlets and are respectively connected to a concentrated water tank through pipelines; the second-stage nanofiltration unit is provided with a concentrated water outlet and is connected to a concentrated liquid tank through a concentrated water pipeline; the third-stage nanofiltration unit is provided with a concentrated water reflux pipeline which is communicated with a second-stage nanofiltration water inlet pipeline; the water production pipeline of the reverse osmosis unit is connected to the fresh water tank, a branch line is further arranged on the reverse osmosis water production pipeline and serves as a fresh water backflow pipeline to be communicated with the primary nanofiltration water inlet pipeline, and the reverse osmosis concentrated water pipeline is connected to the brine tank.
2. The apparatus for preparing concentrated calcium chloride solution from ammonia distillation wastewater according to claim 1, wherein the pretreatment, primary nanofiltration, secondary nanofiltration and tertiary nanofiltration water production pipelines are respectively provided with a clear liquid tank, a primary nanofiltration water production tank, a secondary nanofiltration water production tank and a tertiary nanofiltration water production tank.
3. The device for preparing the calcium chloride concentrated solution from the ammonia distillation wastewater according to claim 1, wherein the pretreatment unit adopts microfiltration and/or ultrafiltration and comprises one or a combination of a ceramic membrane, a hollow fiber ultrafiltration membrane and an organic tubular membrane.
4. The apparatus for preparing calcium chloride concentrate from ammonia distillation wastewater as claimed in claim 1, wherein the first-stage nanofiltration unit adopts SO4 2-A retention rate of 81-92%, Ca2+The rejection rate is 8-46%, and Na+A nanofiltration membrane with the rejection rate of-12-8%, the operating pressure of 2.0-5.5 MPa and the recovery rate of 45-85%; a hydrochloric acid adding port is arranged on the primary nanofiltration water production pipeline; the second-stage nanofiltration unit adopts Ca2+Rejection rate is 63-91%, Na+A nanofiltration membrane with the retention rate of-21 to-5 percent, the operating pressure of 5.5 to 8.8 MPa and the recovery rate of 55 to 85 percent; the second-stage nanofiltration adopts a sectional design, and a booster pump is arranged between sections; the third-stage nanofiltration unit adopts Ca2+The rejection rate is 72-89%, and Na+A nanofiltration membrane with the rejection rate of 15-32%, the operating pressure of 2.0-5.8 MPa and the recovery rate of 55-85%; the reverse osmosis unit adopts a reverse osmosis membrane with the desalination rate of 92-98%, the operating pressure is 4.5-7.9 MPa, and the recovery rate is 32-65%.
5. The apparatus for preparing concentrated calcium chloride solution from ammonia distillation wastewater as claimed in claim 1, wherein the inlet lines of the pretreatment, primary nanofiltration, secondary nanofiltration, tertiary nanofiltration and reverse osmosis units are all provided with inlet pumps, the inlet lines of the primary nanofiltration, secondary nanofiltration, tertiary nanofiltration and reverse osmosis units are simultaneously provided with security filters, the return line of the tertiary nanofiltration concentrated water is provided with a booster pump, and the return line of the reverse osmosis fresh water is provided with a return pump.
6. The device for preparing the calcium chloride concentrated solution by distilling the ammonia wastewater according to the claim 2, wherein the clear solution tank is provided with a pretreatment water production inlet, a hydrochloric acid adding inlet and a reverse osmosis water production backflow inlet, and the clear solution tank is provided with stirring or aeration.
7. The apparatus for preparing calcium chloride concentrate from ammonia distillation wastewater as claimed in claim 1, wherein the interface position of the three-stage nanofiltration concentrate reflux pipeline merged into the two-stage nanofiltration water inlet pipeline after pressurization is arranged on the water outlet side of the two-stage nanofiltration water inlet pump, and the downstream of the interface position is provided with a pipeline mixer.
8. The apparatus for preparing concentrated calcium chloride solution by ammonia distillation wastewater according to claim 1, wherein the first-stage nanofiltration, the second-stage nanofiltration and the reverse osmosis concentrated water pipelines are all provided with energy recovery devices, including a turbine type energy recovery device or a PX energy recovery device.
9. The apparatus for preparing calcium chloride concentrated solution from ammonia distillation wastewater as claimed in claim 1, wherein the water inlet pipeline, the water production pipeline, the concentrated water pipeline and the return pipeline are all provided with an online flowmeter, the online water quality analyzer is also provided with an automatic control valve, and the hydrochloric acid feeding pipeline is provided with an online flowmeter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202122985968.2U CN216336747U (en) | 2021-12-01 | 2021-12-01 | Device for preparing calcium chloride concentrated solution by ammonia distillation wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202122985968.2U CN216336747U (en) | 2021-12-01 | 2021-12-01 | Device for preparing calcium chloride concentrated solution by ammonia distillation wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN216336747U true CN216336747U (en) | 2022-04-19 |
Family
ID=81156858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202122985968.2U Active CN216336747U (en) | 2021-12-01 | 2021-12-01 | Device for preparing calcium chloride concentrated solution by ammonia distillation wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN216336747U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116040672A (en) * | 2023-01-28 | 2023-05-02 | 山东海化集团有限公司 | Method for preparing basic calcium chloride eutectic by ammonia distillation wastewater |
-
2021
- 2021-12-01 CN CN202122985968.2U patent/CN216336747U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116040672A (en) * | 2023-01-28 | 2023-05-02 | 山东海化集团有限公司 | Method for preparing basic calcium chloride eutectic by ammonia distillation wastewater |
| CN116040672B (en) * | 2023-01-28 | 2023-06-20 | 山东海化集团有限公司 | Method for preparing basic calcium chloride eutectic by ammonia distillation wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114133065B (en) | Method for preparing calcium chloride concentrate from ammonia distillation wastewater | |
| CN201634539U (en) | Treatment system for reclaiming incision waste water into ultrapure water in semiconductor industry | |
| CN210206461U (en) | Concentration device for low-hardness sodium chloride solution | |
| CN109081488A (en) | A kind of method and system of industry strong brine resource utilization | |
| CN216336747U (en) | Device for preparing calcium chloride concentrated solution by ammonia distillation wastewater | |
| CN112607926A (en) | Sodium nitrate wastewater recycling treatment system and method | |
| CN209081494U (en) | A kind of reverse osmosis concentrated water recovery device | |
| CN202358930U (en) | Production plant for original brine denitration | |
| CN112679020B (en) | Low-cost shale gas fracturing flowback fluid treatment system and treatment method | |
| CN101602560A (en) | The concentrated recovery method and the device of low-concentration industrial waste acid water | |
| CN113562917A (en) | High-recovery-rate seawater desalination process | |
| CN211620231U (en) | Device for efficient desalination and comprehensive utilization of seawater | |
| CN106800351A (en) | Full Membrane seawater desalination and strong brine utilization system | |
| CN202193629U (en) | Filter device for brine denitration and purification | |
| CN215439958U (en) | Softening system suitable for landfill leachate concentrated solution | |
| CN211283959U (en) | Strong brine deep purification device | |
| CN205974092U (en) | Preliminary treatment dephosphorization of hydrogen peroxide solution waste water and organic matter device | |
| CN209081466U (en) | A kind of system carrying out sea water desalination using waste heat | |
| CN210419557U (en) | Continuous operation's concentrated processing apparatus of multiunit modularization membrane | |
| RU77097U1 (en) | LIQUID WASTE PROCESSING PLANT | |
| CN112370971A (en) | Separation and concentration method and separation and concentration device for food materials | |
| CN201596467U (en) | Concentrated water reuse system for reverse osmosis unit | |
| CN221085216U (en) | High-salt wastewater super-concentration and recycling system | |
| CN111204843A (en) | Energy-saving water filtering system combining reverse osmosis membrane and nanofiltration membrane | |
| CN218893496U (en) | Reverse osmosis chemical cleaning permeate collection device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |