CN111875094B - Comprehensive treatment process for beryllium-containing wastewater - Google Patents
Comprehensive treatment process for beryllium-containing wastewater Download PDFInfo
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Abstract
The invention discloses a beryllium-containing wastewater comprehensive treatment process, which comprises the steps of a, classifying wastewater into recovered BeO washing wastewater, raffinate wastewater and mixed wastewater, respectively collecting the wastewater in a collecting tank, and b, respectively carrying out front-end wastewater treatment on the recovered BeO washing wastewater and the raffinate wastewater; c. and (3) classifying and recycling the front-end clear liquid of the recycled BeO washing wastewater, the front-end clear liquid of the raffinate wastewater and the front-end clear liquid of the mixed wastewater, and carrying out rear-end comprehensive wastewater treatment on the comprehensive wastewater formed by converging the front-end concentrated solution of the recycled BeO washing wastewater, the front-end concentrated solution of the raffinate wastewater and the front-end concentrated solution of the mixed wastewater. According to the invention, according to the characteristics of wastewater from beryllium smelting and beryllium product production, wastewater with high acid concentration is treated independently, so that a large amount of alkali consumption can be avoided, and the technical problem that the treatment cost of subsequent high-salinity wastewater in the traditional water treatment process is greatly increased can be solved; the high-concentration wastewater in each process is formed into comprehensive wastewater for centralized treatment, and the low-concentration fresh water after the comprehensive wastewater treatment is formed into internal circulation treatment, so that the process load and the operation cost of the whole wastewater treatment system are reduced.
Description
Technical Field
The invention relates to the technical field of non-ferrous metal production, in particular to a comprehensive treatment process for beryllium-containing wastewater.
Background
In industrial production, particularly comprehensive beryllium-containing sewage generated in non-ferrous metal production and production from smelting, mining, special materials, radio equipment and instrument parts, a large amount of beryllium-containing wastewater is discharged, even beryllium element is contained in clothes cleaning wastewater of non-ferrous metal production staff, alkaline cleaning wastewater, oxalic acid cleaning wastewater and the like in production. This portion of the wastewater contains a large amount of acid, alkali and beryllium salts. Beryllium is a highly toxic substance, and the environmental-protection discharge requirement is extremely strict, but the beryllium concentration in a lot of beryllium-containing wastewater is very low, and the recycling value is not high, so the treatment technology is very difficult, and a great discharge pressure is formed.
For the treatment of beryllium-containing wastewater, the traditional physical and chemical methods, such as chemical precipitation, ion exchange, adsorption, electrolysis, coagulation, redox and ferrite methods, require lime milk to precipitate the wastewater to remove most of the beryllium salt, and then separate and remove the beryllium salt by settling separation and flocculation methods and physical filtration. Because the waste water is huge in volume and the beryllium salt concentration is very low, a large amount of lime milk is consumed, and even the sedimentation effect is improved by a method of a flocculating agent so as to stabilize the subsequent physical filtration operation process. The traditional physical chemical method can not achieve a good separation effect, is long in process and high in operating cost, and meanwhile, a large amount of precipitator and flocculating agent are added to the traditional physical chemical method, so that new environmental protection pressure is increased.
In recent years, biological methods are gradually taken as a main development direction in the field of treatment of waste water in non-ferrous metal production. However, the bacterial activity has high requirements on the environment, so that the field of producing beryllium-containing sewage is quite wide, and the components are complex. Therefore, huge and harsh pretreatment is needed as a precondition for final biological treatment of beryllium-containing wastewater, and even different strains are adopted for biological treatment according to different sewage, so that the method is difficult to adapt to various complex beryllium-containing wastewater systems discharged in different fields. In addition, the biological method has low mechanical strength, low density, fine particles, and difficulty in solid-liquid separation after adsorption of metals. For beryllium-containing wastewater with complex working conditions or low content, the bacteria are volatile to deactivate or are not easy to reach the optimal biological activity condition, so that the whole beryllium-containing wastewater treatment process becomes extremely unstable.
Therefore, a comprehensive treatment system and process for beryllium-containing wastewater are needed.
Disclosure of Invention
The invention mainly aims to provide a beryllium-containing wastewater comprehensive treatment system to solve the problem of poor comprehensive treatment effect of beryllium-containing wastewater in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a beryllium-containing wastewater comprehensive treatment system, comprising a classification treatment front end and a comprehensive treatment rear end;
the classification treatment front end comprises a BeO washing wastewater recovery treatment front end, a raffinate wastewater treatment front end and a mixed wastewater treatment front end;
the front end of the treatment of the recycled BeO washing wastewater comprises a recycled BeO washing wastewater collecting tank, a recycled BeO washing wastewater primary filtering device, a recycled BeO washing wastewater film clarifying device and a recycled BeO washing wastewater film purifying device which are sequentially connected;
the extraction waste water treatment front end comprises an extraction waste water collecting pool, an extraction waste water primary filtering device, an extraction waste water membrane clarifying device and an extraction waste water membrane purifying device which are sequentially connected;
the mixed wastewater treatment front end comprises a mixed wastewater collecting tank, a pH adjusting tank, a mixed wastewater primary filtering device, a mixed wastewater membrane clarifying device and a fine filtering membrane separating device which are connected in sequence;
the integrated processing back-end comprises: the device comprises a rear-end pH adjusting tank, a rear-end pre-filtering device, a rear-end membrane clarifying device and a membrane concentration system, wherein the rear-end pre-filtering device is connected with a supernatant outlet of the rear-end pH adjusting tank;
and the concentrated solution outlet of the recovered BeO washing wastewater membrane purification device, the concentrated solution outlet of the raffinate wastewater membrane purification device and the concentrated solution outlet of the fine filtration membrane separation device are communicated with a rear-end pH adjusting tank.
Furthermore, the membrane clarification device for the recycled BeO washing wastewater is a cross-flow filtration device, and a concentrated solution outlet of the membrane clarification device for the recycled BeO washing wastewater is communicated with a recycled BeO washing wastewater collection tank.
Further, the raffinate wastewater membrane clarification device is a cross-flow filtration device, and a concentrated solution outlet of the raffinate wastewater membrane clarification device is communicated with the raffinate wastewater collection tank.
Further, the mixed wastewater film clarification device is a cross-flow filtration device, and a concentrated solution outlet of the mixed wastewater film clarification device is connected with a rear-end pH adjusting tank.
Further, a concentrated solution outlet of the pH adjusting tank is connected with a plate-and-frame filter press, and a filtrate outlet of the plate-and-frame filter press is connected with the mixed wastewater collecting tank.
Further, a concentrated solution outlet of the rear-end pH adjusting tank is connected with a rear end plate frame filter press, and a filtrate outlet of the rear end plate frame filter press is communicated with a liquid inlet of the mixed wastewater membrane clarifying device.
Further, a concentrated solution outlet of the rear-end membrane clarification device is connected with a rear-end pH adjusting tank.
Further, the primary filter device for the recovered BeO washing wastewater, the primary filter device for the raffinate wastewater, the primary filter device for the mixed wastewater and the rear-end pre-filter device all comprise plate-frame filter devices or cloth-bag filter devices.
Further, when the wastewater is low-concentration wastewater, the rear-end membrane concentration system comprises a membrane separation device for removing part of divalent inorganic salts, a concentration desalting device for intercepting most of inorganic salts and a fine desalting device for further intercepting inorganic salts, which are sequentially connected; when the wastewater is high-concentration wastewater, the rear-end membrane concentration system comprises a membrane separation device, a fine filtration device and an electrodialysis device.
Further, the reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device are all one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral-wound membrane filtration device, a disc-type membrane filtration device, a plate-type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cutoff of the reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device is one of 5000Da, 8000Da, 10000Da, 30000Da, 50000Da, 80000Da, 100000Da, 150000Da, 200000Da and 250000 Da;
the purification membrane adopted for membrane purification of the recovered BeO washing wastewater is one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral membrane filtration device, a disc membrane filtration device, a plate membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cut-off of the purification membrane is 5000 Da;
the purification membrane adopted by the extraction waste water membrane purification is one of an inorganic membrane filtration device, an organic membrane filtration device, a roll type membrane filtration device, a disc type membrane filtration device, a plate type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the interception molecular weight of the purification membrane is one of 5000Da,3000Da,2500Da,1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da and 20 Da;
the mixed wastewater is separated by a filter membrane, and one of an inorganic membrane filter device, an organic membrane filter device, a spiral membrane filter device, a disc type membrane filter device, a plate type membrane filter device, a hollow fiber membrane filter device and a tubular membrane filter device is adopted.
In order to achieve the above object, according to another aspect of the present invention, there is provided a beryllium-containing wastewater comprehensive treatment process, including the following steps:
a. classifying the wastewater into recycled BeO washing wastewater, raffinate wastewater and mixed wastewater, and respectively collecting the wastewater in a collecting tank, wherein the mixed wastewater comprises domestic and bathing wastewater, poor organic alkali washing wastewater and poor organic acid washing wastewater;
b. sequentially carrying out primary filtration, membrane clarification and membrane purification on the recovered BeO washing wastewater to obtain a front-end clear solution of the recovered BeO washing wastewater and a front-end concentrated solution of the recovered BeO washing wastewater; sequentially carrying out primary filtration, membrane clarification and membrane purification on the raffinate wastewater to obtain a raffinate wastewater front end clear liquid and a raffinate wastewater front end concentrated liquid; sequentially carrying out pH adjustment, preliminary filtration, membrane clarification and fine filtration membrane separation on the mixed wastewater to obtain a mixed wastewater front end clear solution and a mixed wastewater front end concentrated solution;
c. and classifying and recycling the front-end clear liquid of the recycled BeO washing wastewater, the front-end clear liquid of the raffinate wastewater and the front-end clear liquid of the mixed wastewater, regulating the pH of the comprehensive wastewater formed by converging the front-end concentrated liquid of the recycled BeO washing wastewater, the front-end concentrated liquid of the raffinate wastewater and the front-end concentrated liquid of the mixed wastewater, and sequentially carrying out rear-end pre-filtration, rear-end membrane clarification and rear-end membrane concentration on the clear liquid obtained by regulating the pH to obtain the recyclable fresh water and the concentrated water discharged out of the system.
And further, the concentrated solution obtained after the recovered BeO washing wastewater in the step b is clarified by a membrane flows back to a collection pool of the BeO washing wastewater.
And further, the concentrated solution obtained after the raffinate wastewater in the step b is clarified by the membrane flows back to a collecting tank of the raffinate wastewater.
And further, the concentrated solution obtained by clarifying the mixed wastewater in the step b by using a membrane is also converged with the concentrated solution at the front end of the recovered BeO washing wastewater, the concentrated solution at the front end of the raffinate wastewater and the concentrated solution at the front end of the mixed wastewater, and the pH value is adjusted.
And further, carrying out filter pressing on the concentrated solution obtained after the mixed wastewater in the step b is subjected to pH adjustment, and returning filtrate obtained by filter pressing to the mixed wastewater collection pool.
And further, after the concentrated solution at the front end of the BeO washing wastewater, the concentrated solution at the front end of the raffinate wastewater and the concentrated solution at the front end of the mixed wastewater are recovered in the step c and are converged, the pH value of the converged concentrated solution is adjusted to obtain a concentrated solution, the concentrated solution is subjected to pressure filtration, and the filtrate obtained by the pressure filtration and the clear solution obtained by the rear-end pretreatment are converged and enter a rear-end membrane clarification section.
Further, the concentrated solution obtained by the back-end membrane clarification is returned to a back-end pH adjusting section to repeat the step c.
Further, the primary filtration of the recovered BeO washing wastewater, the primary filtration of raffinate wastewater, the primary filtration of mixed wastewater and the rear-end pre-filtration are plate-frame filtration or cloth-bag filtration.
Further, the back-end membrane concentration includes membrane separation to remove a portion of the divalent inorganic salts, concentration desalination to intercept most of the inorganic salts, and further fine desalination to intercept inorganic salts.
Further, when the wastewater is low-concentration wastewater, the rear-end membrane concentration comprises membrane separation, concentration desalination and fine desalination; when the wastewater is high-concentration wastewater, the back-end membrane concentration comprises membrane separation, fine filtration and electrodialysis.
Further, the reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device are all one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral-wound membrane filtration device, a disc-type membrane filtration device, a plate-type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cutoff of the reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device is one of 5000Da, 8000Da, 10000Da, 30000Da, 50000Da, 80000Da, 100000Da, 150000Da, 200000Da and 250000 Da;
the purification membrane adopted for membrane purification of the recovered BeO washing wastewater is one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral membrane filtration device, a disc membrane filtration device, a plate membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cut-off of the purification membrane is 5000 Da;
the purification membrane adopted by the extraction waste water membrane purification is one of an inorganic membrane filtration device, an organic membrane filtration device, a roll type membrane filtration device, a disc type membrane filtration device, a plate type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the interception molecular weight of the purification membrane is one of 5000Da,3000Da,2500Da,1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da and 20 Da;
the mixed wastewater is separated by a filter membrane, and one of an inorganic membrane filter device, an organic membrane filter device, a spiral membrane filter device, a disc type membrane filter device, a plate type membrane filter device, a hollow fiber membrane filter device and a tubular membrane filter device is adopted.
Therefore, according to the characteristics of beryllium smelting and beryllium product production sewage, the wastewater with high acid concentration is treated independently, so that a large amount of alkali consumption can be avoided, and the technical problem that the treatment cost of subsequent high-salinity wastewater of the traditional water treatment process is greatly increased is solved;
the high-concentration wastewater in each process is formed into comprehensive wastewater for centralized treatment, and the low-concentration fresh water after the comprehensive wastewater treatment is formed into internal circulation treatment, so that the process load and the operation cost of the whole wastewater treatment system are reduced. The whole technical scheme has good economical efficiency and scientific and reasonable process route design.
The invention is further described with reference to the following figures and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
FIG. 1 is a schematic diagram of the process flow of the integrated beryllium-containing wastewater treatment equipment of the invention.
FIG. 2 is a schematic diagram of a back-end membrane concentration system according to the present invention.
FIG. 3 is a second schematic diagram of a back-end membrane concentration system according to the present invention.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only examples of a part of the present invention, and not all examples. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions. As shown in fig. 1:
the comprehensive treatment system for the beryllium-containing wastewater comprises a classification treatment front end and a comprehensive treatment rear end;
the classification treatment front end comprises a BeO washing wastewater recovery treatment front end, a raffinate wastewater treatment front end and a mixed wastewater treatment front end;
the front end of the treatment of the recycled BeO washing wastewater comprises a recycled BeO washing wastewater collection tank 11, a recycled BeO washing wastewater primary filtering device 12, a recycled BeO washing wastewater film clarifying device 13 and a recycled BeO washing wastewater film purifying device 14 which are sequentially connected;
the extraction waste water treatment front end comprises an extraction waste water collecting tank 21, an extraction waste water primary filtering device 22, an extraction waste water membrane clarifying device 23 and an extraction waste water membrane purifying device 24 which are connected in sequence;
the front end of the mixed wastewater treatment comprises a mixed wastewater collecting tank 31, a pH adjusting tank 32, a mixed wastewater primary filtering device 33, a mixed wastewater membrane clarifying device 34 and a fine filtering membrane separating device 35 which are connected in sequence;
the integrated processing back-end comprises: a rear end pH adjusting tank 41, a rear end pre-filtering device 42 connected with a supernatant outlet of the rear end pH adjusting tank 41, a rear end membrane clarifying device 43 and a membrane concentration system 44;
and a concentrated solution outlet of the recovered BeO washing wastewater membrane purification device 14, a concentrated solution outlet of the raffinate wastewater membrane purification device 24 and a concentrated solution outlet of the fine filtration membrane separation device 35 are communicated with a rear-end pH adjusting tank 41.
The membrane clarification device 13 for the recycled BeO washing wastewater is a cross-flow filtration device, and a concentrated solution outlet of the membrane clarification device 13 for the recycled BeO washing wastewater is communicated with the collection tank 11 for the recycled BeO washing wastewater.
The raffinate wastewater membrane clarification device 23 is a cross-flow filtration device, and a concentrated solution outlet of the raffinate wastewater membrane clarification device 23 is communicated with the raffinate wastewater collection tank 21.
The mixed wastewater film clarification device 34 is a cross-flow filtration device, and a concentrated solution outlet of the mixed wastewater film clarification device 34 is connected with a rear end pH adjusting tank 41.
And a concentrated solution outlet of the pH adjusting tank 32 is connected with a plate-and-frame filter press 36, and a filtrate outlet of the plate-and-frame filter press 36 is connected with the mixed wastewater collecting tank 31.
The concentrated solution outlet of the rear end pH adjusting tank 41 is connected with a rear end plate frame filter press 45, and the filtrate outlet of the rear end plate frame filter press 45 is communicated with the liquid inlet of the mixed wastewater membrane clarifying device 34.
And a concentrated solution outlet of the rear-end membrane clarification device 43 is connected with the rear-end pH adjusting tank 41.
The primary filter device 12 for the recovered BeO washing wastewater, the primary filter device 22 for the raffinate wastewater, the primary filter device 33 for the mixed wastewater and the rear end pre-filter device 42 all comprise plate-frame filter devices or cloth-bag filter devices.
As shown in fig. 2 and 3, when the wastewater is low-concentration wastewater, the back-end membrane concentration includes membrane separation, concentration desalination and fine desalination; when the wastewater is high-concentration wastewater, the back-end membrane concentration comprises membrane separation, fine filtration and electrodialysis.
The reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device are all one of an inorganic membrane filtration device, an organic membrane filtration device, a roll-type membrane filtration device, a disc-type membrane filtration device, a plate-type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cutoff of the reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device is one of 5000Da, 8000Da, 10000Da, 30000Da, 50000Da, 80000Da, 100000Da, 150000Da, 200000Da and 250000 Da;
the purification membrane adopted for membrane purification of the recovered BeO washing wastewater is one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral membrane filtration device, a disc membrane filtration device, a plate membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cut-off of the purification membrane is 5000 Da;
the purification membrane adopted by the extraction waste water membrane purification is one of an inorganic membrane filtration device, an organic membrane filtration device, a roll type membrane filtration device, a disc type membrane filtration device, a plate type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the interception molecular weight of the purification membrane is one of 5000Da,3000Da,2500Da,1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da and 20 Da;
the mixed wastewater is separated by a filter membrane, and one of an inorganic membrane filter device, an organic membrane filter device, a spiral membrane filter device, a disc type membrane filter device, a plate type membrane filter device, a hollow fiber membrane filter device and a tubular membrane filter device is adopted.
The comprehensive treatment process of the beryllium-containing wastewater comprises the following steps:
a. classifying the wastewater into recycled BeO washing wastewater, raffinate wastewater and mixed wastewater, and respectively collecting the wastewater in a collecting tank, wherein the mixed wastewater comprises domestic and bathing wastewater, poor organic alkali washing wastewater and poor organic acid washing wastewater;
b. sequentially carrying out primary filtration, membrane clarification and membrane purification on the recovered BeO washing wastewater to obtain a front-end clear solution of the recovered BeO washing wastewater and a front-end concentrated solution of the recovered BeO washing wastewater; sequentially carrying out primary filtration, membrane clarification and membrane purification on the raffinate wastewater to obtain a raffinate wastewater front end clear liquid and a raffinate wastewater front end concentrated liquid; sequentially carrying out pH adjustment, preliminary filtration, membrane clarification and fine filtration membrane separation on the mixed wastewater to obtain a mixed wastewater front end clear solution and a mixed wastewater front end concentrated solution;
c. and classifying and recycling the front-end clear liquid of the recycled BeO washing wastewater, the front-end clear liquid of the raffinate wastewater and the front-end clear liquid of the mixed wastewater, regulating the pH of the comprehensive wastewater formed by converging the front-end concentrated liquid of the recycled BeO washing wastewater, the front-end concentrated liquid of the raffinate wastewater and the front-end concentrated liquid of the mixed wastewater, and sequentially carrying out rear-end pre-filtration, rear-end membrane clarification and rear-end membrane concentration on the clear liquid obtained by regulating the pH to obtain the recyclable fresh water and the concentrated water discharged out of the system.
And c, refluxing the concentrated solution obtained after the recovered BeO washing wastewater in the step b is clarified by the membrane to a collection pool of the BeO washing wastewater.
And c, performing membrane clarification on the raffinate wastewater in the step b to obtain a concentrated solution, and refluxing the concentrated solution to a raffinate wastewater collection tank.
And c, the concentrated solution obtained by clarifying the mixed wastewater in the step b by using a membrane is also converged with the concentrated solution at the front end of the recycled BeO washing wastewater, the concentrated solution at the front end of the raffinate wastewater and the concentrated solution at the front end of the mixed wastewater, and the pH value is adjusted.
And c, carrying out filter pressing on the concentrated solution obtained after the mixed wastewater in the step b is subjected to pH adjustment, and returning the filtrate obtained by filter pressing to the mixed wastewater collection tank.
And c, recovering the concentrated solution at the front end of the BeO washing wastewater, the concentrated solution at the front end of the raffinate wastewater and the concentrated solution at the front end of the mixed wastewater in the step c, converging the concentrated solution, performing pH adjustment to obtain a concentrated solution, performing filter pressing, converging the filtrate obtained by filter pressing and the clear solution obtained by rear-end pretreatment, and then entering a rear-end membrane clarification section.
And c, returning the concentrated solution obtained by clarifying the rear-end membrane to a rear-end pH adjusting section, and repeating the step c.
The primary filtration of the recovered BeO washing wastewater, the primary filtration of the raffinate wastewater, the primary filtration of the mixed wastewater and the back-end pre-filtration are plate-frame filtration or cloth-bag filtration.
The back-end membrane concentration includes membrane separation to remove a portion of divalent inorganic salts, concentration desalination to intercept most of the inorganic salts, and further fine desalination to intercept inorganic salts.
The reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device are inorganic membrane filtration devices, organic membrane filtration devices, roll-up membrane filtration devices, disc-type membrane filtration devices, plate-type membrane filtration devices, hollow fiber membrane filtration devices and tubular membrane filtration devices, and the molecular weight cutoff of the reclaimed BeO washing wastewater membrane clarification device is one of 5000Da, 8000Da, 10000Da, 30000Da, 50000Da, 80000Da, 100000Da, 150000Da, 200000Da and 250000 Da.
The following details of the various process stages and the equipment employed:
preliminary filtration stage
The primary filtration aims at intercepting large particles and most hard fine particles in sewage and avoiding damaging an impeller and a clarifying membrane under the high-speed operation of a circulating pump; and selecting the filtration mode of the primary filtration section according to solid contents in different waste water and whether the pH value needs to be adjusted.
For wastewater containing a small amount of solid suspended matters, the sewage containing a small amount of solid suspended matters is directly pretreated by adopting a bag type filtration or multi-medium filtration method;
for sewage or slurry-like materials with solid content of more than 2%, for example, the mixed wastewater can be directly treated by primary filtration by a plate-and-frame filter press, a sludge centrifuge or other separation equipment;
for fine particles which are difficult to filter and have the content of less than 1 percent or are difficult to separate and are formed by regulating the pH value of the sewage in advance, plate-and-frame filter pressing or other solid-liquid separation equipment can be adopted for the pre-settled concentrated solution so as to improve the solid-liquid separation efficiency; the clear liquid after sedimentation can be subjected to primary filtration treatment by adopting a plate-frame or bag filtration method;
the mesh number of the plate frame filtration is 500-2500 meshes; the filtering precision of the cloth bag filtering is 1-10 mu m.
The mesh number of plate frame filter pressing is 500 meshes and 2500 meshes.
Membrane clarification section
The main purpose of membrane clarification is to utilize the characteristics of membrane separation 'cross flow filtration' to solve the technical problem that the traditional 'dead end' filtration is easy to block, and simultaneously, to provide qualified inlet water for the subsequent fine filtration.
The membrane clarification device is selected according to different materials entering the system: for the material with strong corrosivity, PP, PVDF and a clarifying film made of inorganic materials with strong corrosion resistance can be adopted; for the solid content from low to high, an internal pressure type hollow fiber membrane, an external pressure type hollow fiber membrane and a tubular membrane can be adopted so as to overcome the technical problem of traditional 'dead-end' filtration.
Membrane purification
The purification membrane adopted by the membrane purification of the recovered BeO washing wastewater is one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral membrane filtration device, a disc type membrane filtration device, a plate type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cut-off of the purification membrane is 5000 Da;
the purification membrane adopted by the extraction waste water membrane purification is one of an inorganic membrane filtration device, an organic membrane filtration device, a roll type membrane filtration device, a disc type membrane filtration device, a plate type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the interception molecular weight of the purification membrane is one of 5000Da,3000Da,2500Da,1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da and 20 Da;
the mixed wastewater is separated by a filter membrane, and one of an inorganic membrane filter device, an organic membrane filter device, a spiral membrane filter device, a disc type membrane filter device, a plate type membrane filter device, a hollow fiber membrane filter device and a tubular membrane filter device is adopted.
Fine filtration membrane separation
The purpose of fine filtration membrane separation is to make the clear liquid reach the requirements of recycling production or standard discharge treatment.
According to the different materials entering the system: for materials with strong corrosivity, a corrosion-resistant material film can be adopted; the common materials can meet the requirements by adopting films made of common materials.
According to the processing requirements of different precisions: a structure that a clear liquid outlet of a first-stage membrane purification device is connected with a multi-stage membrane in series can be adopted, so that the clear liquid separated by a fine filtration membrane meets the recycling or standard discharge requirements; the concentrated solution outlet of the first-stage membrane purification device can be connected with a multi-stage membrane purification structure in series to improve the concentrated solution concentration of the outlet system and meet the liquid inlet requirement of the subsequent process in consideration of the single index requirement from the economical aspect; two primary membrane purification devices can also be used in parallel.
The clear liquid obtained by the fine filtering membrane separation device is directly discharged or recycled and produced, and the concentrated liquid with greatly reduced volume after the concentrated liquid enters the next procedure, so that the treatment efficiency of the next procedure is improved.
Membrane concentration system
The membrane concentration system aims at achieving the best economic benefit of the concentrated solution in recycling and production or subsequent concentrated solution treatment without considering the concentration of clear solution or fresh water.
A nanofiltration device is adopted as a membrane separation device in the membrane concentration system, and the nanofiltration device is one of a roll type, butterfly type or plate type membrane nanofiltration device.
The concentration desalting device in the membrane concentration system adopts a reverse osmosis device, and the cut-off molecular weight of the concentration desalting device is one of 300Da,150Da, 100Da, 50Da, 30Da and 10 Da.
The fine desalting device in the membrane concentration system adopts a reverse osmosis device, and the filtering precision of the fine desalting device is one of 300Da,150Da, 100Da, 50Da, 30Da and 10 Da.
The fine filtration is one of an inorganic membrane filtration device, an organic membrane filtration device, a roll-up membrane filtration device, a disc type membrane filtration device, a plate type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cutoff of the fine filtration is 5000Da,3000Da,2500Da,1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da, 20Da and 10 Da. The electrodialysis is one of inorganic ion exchange membrane electrodialysis, organic polymer ion exchange membrane electrodialysis, homogeneous ion exchange membrane electrodialysis, semi-homogeneous ion exchange membrane electrodialysis, heterogeneous ion exchange membrane electrodialysis, gel ion exchange membrane electrodialysis, porous ion exchange membrane electrodialysis, macroporous ion exchange membrane electrodialysis, cation exchange membrane electrodialysis, anion exchange membrane electrodialysis, special functional ion exchange membrane electrodialysis, general water treatment ion exchange membrane electrodialysis, special purpose ion exchange membrane electrodialysis, omeless electrodialysis, omentum electrodialysis, substrate membrane electrodialysis, and various devices which have different combinations and have the desalting function and are used for carrying out the dialysis under the action of an electric field and have the same principle with the electrodialysis.
Examples
In the smelting, production or purification process of beryllium, beryllium oxide or beryllium salt, very much strongly acidic waste water, strongly alkaline waste water and other waste water are often generated. The beryllium-containing wastewater is divided into various types, including recovered BeO washing wastewater, raffinate wastewater, and mixed wastewater consisting of acid pickling wastewater, alkali washing wastewater and bathing and domestic wastewater. The technical scheme of the invention is specifically described by taking the comprehensive wastewater generated by recovering the beryllium and the beryllium oxide as an example.
The components of the mixed wastewater consisting of the recovered BeO washing wastewater, the raffinate wastewater, the acid washing wastewater, the alkali washing wastewater and the bath and domestic wastewater are shown in the following table:
based on the above beryllium-containing wastewater feeding conditions, the following analysis is carried out,
1) recovering BeO washing waste liquid: the waste water contains oxalic acid with relatively high value, so the method has high recycling value. The treatment method for recovering the BeO washing wastewater is the same as that for the raffinate wastewater, and a special film made of an acid-resistant material is adopted for treatment, so that a large amount of neutralization alkali is saved, oxalic acid with higher value can be recovered, and the aims of saving energy and reducing consumption are fulfilled.
2) Extraction of the residual water phase: the raffinate waste water is extremely acidic, and although the recovery value of the sulfuric acid is not very high, the treatment of the waste water needs much alkali to neutralize the sulfuric acid in the waste water. The waste water after the neutralization of the raffinate waste water contains a large amount of salt, so the method for treating the raffinate waste water is limited, and the treatment cost is very high.
When the waste water is treated, the special membrane made of patent acid-resistant materials is very suitable for treating the raffinate waste water. Not only does not need a large amount of alkali to neutralize the sulfuric acid, but also the purified sulfuric acid after membrane purification can be recycled and produced, thereby forming circular economy and realizing zero emission in production in a real sense.
3) Poor organic acid pickling wastewater: the sulfuric acid content of the poor organic acid washing waste water is relatively low, the volume is large, and the economical efficiency is not very outstanding if a special membrane made of patent acid-resistant materials is adopted for treatment. Therefore, pretreatment and neutralization are preferably adopted, and then treatment by using an economical common membrane is more suitable for the wastewater.
4) Poor organic alkaline washing wastewater: the properties of the poor organic alkaline washing wastewater are the same as those of the poor organic acid washing wastewater, and the poor organic alkaline washing wastewater and the poor organic acid washing wastewater are both suitable for being treated by a method of neutralization after pretreatment and a common membrane with good economical efficiency.
5) Bath and sanitary wastewater: the bath and domestic wastewater is mainly still beryllium and cannot be discharged outside. Is suitable for directly adopting a common membrane to intercept beryllium after pretreatment.
Classifying the following three classes:
1) extraction of the residual water phase: after pretreatment, a special membrane made of patent acid-resistant materials is used for intercepting impurities in the wastewater, so that the sulfuric acid is purified and reused for production. And the concentrated solution for intercepting impurities such as beryllium salt is conveyed to a concentrated solution treatment process for centralized treatment. The treated clear liquid returns to the mixed wastewater for centralized treatment.
2) Recovering BeO washing waste liquid: after pretreatment, a special membrane made of patent acid-resistant materials is used for intercepting impurities in the wastewater, so that the oxalic acid can be purified and reused for production. And the concentrated solution for intercepting impurities such as beryllium salt is conveyed to a concentrated solution treatment process for centralized treatment. The treated clear liquid returns to the mixed wastewater for centralized treatment.
3) The mixed wastewater after the poor organic acid-washing wastewater, the poor organic alkali-washing wastewater, the bathing and sanitary wastewater and the internal blowdown (containing concentrated solution) of the whole system are mixed and then are comprehensively treated.
The scheme is adopted to classify the wastewater, and the method has the following advantages:
1) the high-concentration acidic wastewater is recycled for production after being subjected to membrane separation and purification, so that a large amount of alkali for neutralization is saved compared with the traditional treatment mode of acid-base neutralization in advance, and the consumption of acid in production is reduced. The treatment method has great economic advantages;
2) in the production process, the volume of the beryllium-containing wastewater is greatly reduced after membrane concentration, the chemical reaction effect in the sewage treatment process is greatly improved, the investment of additives is reduced, the environment-friendly treatment pressure is reduced, and the environment is quite friendly;
3) the membrane technology is adopted for treating the beryllium-containing wastewater, the separation efficiency is high, and a long and complicated process is not needed.
4) According to the raw water condition and treatment requirements of different working conditions, the invention adopts a mode of combining the membrane separation technology and electrodialysis, can improve the content of inorganic salt in the raw water to more than 20%, is not favorable for purifying useful substances in the wastewater in production, recycling or environmental protection treatment of high-concentration solution, thoroughly realizes 'circular economy', and achieves 'zero emission'.
Recovering BeO washing waste liquid:
the recovered BeO washing waste liquid is collected to a waste water collecting tank by each process point to be mixed, then large particles and hard particles are preliminarily filtered by a plate frame or a cloth bag and then enter a membrane clarifying device, and residues or materials are collected and transported outwards. The membrane clarification device adopts cross-flow type circulating filtration, fine particles which cannot be filtered by a plate frame or a cloth bag and a part of macromolecular impurities are intercepted to form concentrated solution, and the concentrated solution is returned to a collection pool for recovering BeO washing waste liquid; pure permeate formed by the clear liquid permeate film is conveyed to a nanofiltration device with higher filtration precision for desalination and purification; the nanofiltration device intercepts most inorganic salt by utilizing molecular weight and charge property in the solution through membrane purification, concentrated solution formed by the membrane purification enters the next rear-end comprehensive wastewater treatment stage for comprehensive treatment, clear solution which permeates the purity of the nanofiltration membrane, namely oxalic acid solution, needs to enter a recovery process for fine desalination due to higher purity requirement, and the oxalic acid solution after the fine desalination returns to production for use after acid supplementation and qualified detection.
Extraction of the residual water phase: and the recovered extraction water phase wastewater is collected to an extraction water phase wastewater collecting tank for mixing by each process point, then large particles and hard particles are preliminarily filtered by a plate frame or a cloth bag and enter a membrane clarifying device, and slag or materials are collected and transported outwards. The membrane clarification device adopts cross-flow type circulating filtration, fine particles which cannot be filtered by a plate frame or a cloth bag and a part of macromolecular impurities are intercepted to form concentrated solution which is returned to the collection tank; the sulfuric acid clear solution permeate film forms pure sulfuric acid permeate liquid which is conveyed to a nanofiltration system with higher filtration precision for desalination and purification; the membrane purification system utilizes the molecular weight and the charge property in the solution to intercept most inorganic salts to form concentrated solution, the concentrated solution enters the next rear-end comprehensive wastewater treatment stage for comprehensive treatment, and the sulfuric acid which permeates through the membrane is returned to production for use after acid supplementation and qualified detection.
Pretreatment of mixed wastewater: the pickling waste water, the bath and sanitary waste water and the pickling waste water are collectively referred to as mixed waste water. The mixed wastewater is collected to a wastewater collection pool by each process point to be mixed, then a raw water pump and a metering dosing pump are mixed and react in a pipeline mixer according to a certain proportion until the pH value is neutral, and the solution is precipitated due to the change of the pH value to form turbid liquid which is settled and layered in a pH adjusting pool: the clear liquid part in the layering overflows to a clear liquid tank and is sent to a plate frame or cloth bag filtering device by a clear liquid pump, clear liquid obtained by the plate frame or cloth bag filtering device enters a membrane clarifying device, and obtained solid substances are transported outside; the precipitate in the pool is enriched at the lower part of the pH adjusting pool and is sent into a plate-and-frame filter press by a slurry, namely a concentrated solution pump, the solid obtained by the plate-and-frame filter press is transported outwards, and the obtained filtrate is returned to the raw water collecting pool.
The mixed wastewater is pretreated and enters a membrane clarification device according to the membrane clarification feeding requirement, and the membrane clarification device uses fine particles and a part of macromolecular impurities which are filtered and intercepted by a high-precision filtering plate frame or a cloth bag filter in the pretreatment to form a concentrated solution and then enters a pH adjusting tank; the part penetrating through the membrane clarification device is the clear liquid and enters a fine filtration membrane separation system. The fine filtering membrane separation system adopts different processes and equipment structures to meet different treatment requirements of mixed wastewater. The clear liquid permeating the membrane is directly reused for production or discharged after reaching the standard; the concentrated solution enters a rear end pH adjusting tank of the comprehensive wastewater treatment stage for further treatment.
The recovered BeO washing waste liquid concentrated solution, the extracted water phase concentrated solution, the mixed wastewater membrane clarified concentrated solution, the mixed wastewater fine filtration membrane separation concentrated solution and the comprehensive wastewater membrane clarified concentrated solution are collectively called as comprehensive wastewater. The comprehensive wastewater is collected to the rear-end pH adjusting tank from each process point and mixed, fresh raw water continuously enters the rear-end pH adjusting tank to cause the pH value in the rear-end pH adjusting tank to change, and the dosing system feeds back and adjusts the dosing amount according to the pH value signal of the adjusting tank so as to meet the process requirements. The solution is precipitated due to the change of pH to form turbid liquid, and the turbid liquid is settled and layered in a pH adjusting tank: the clear liquid part overflows to a clear liquid tank and is sent to a clear liquid plate-and-frame filter press by a clear liquid pump, the filtrate enters a membrane clarification device, and solid substances are transported out for treatment; the precipitate in the pH adjusting tank is enriched at the lower part of the pH adjusting tank and is sent into a concentrated solution plate-and-frame filter press by a slurry pump, the solid is transported outside, and the filtrate returns to the pH adjusting tank.
After the clear liquid from the clear liquid plate-and-frame filter press enters a membrane clarification device, fine suspended matters and macromolecular substances are removed by the membrane clarification device, the obtained clear liquid enters a membrane separation device 441, and the concentrated liquid obtained by membrane clarification returns to a pH adjusting tank to continue to settle and separate solid suspended matters.
Clear liquid obtained by membrane separation of low-concentration stock solution passes through a concentration desalting device 442, clear liquid obtained by the concentration desalting device 442 enters a fine desalting device 443 for further desalting to obtain clear liquid, and concentrated liquid obtained by the fine desalting device 443 returns to the concentration desalting device 442 again;
and (3) filtering the clear liquid obtained by the membrane separation of the high-concentration stock solution by using a fine filtering device 446, continuously feeding the concentrated solution obtained by filtering by using the fine filtering device 446 into an electrodialysis device 447 for concentration, and returning the concentrated solution obtained by filtering by using the electrodialysis device 447 to the fine filtering device 446.
The following further explains the beneficial effects of the invention by comparing the experimental data of various wastewater treatments and the experimental data of the prior art which are classified firstly and then comprehensively treated in the technical scheme of the invention respectively:
the experimental data are shown in table 2:
data analysis
According to the characteristics of wastewater generated in beryllium smelting and beryllium product production, wastewater with high acid concentration is treated independently, so that a large amount of alkali consumption can be avoided, and the technical problem that the treatment cost of subsequent high-salinity wastewater in the traditional water treatment process is greatly increased is solved;
the high-concentration wastewater in each process is formed into comprehensive wastewater for centralized treatment, and the low-concentration fresh water after the comprehensive wastewater treatment is formed into internal circulation treatment, so that the process load and the operation cost of the whole wastewater treatment system are reduced. The whole technical scheme has good economical efficiency and scientific and reasonable process route design.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (9)
1. The comprehensive treatment process of the beryllium-containing wastewater is characterized by comprising the following steps of:
a. classifying the wastewater into recycled BeO washing wastewater, raffinate wastewater and mixed wastewater, and respectively collecting the wastewater in a collecting tank, wherein the mixed wastewater comprises domestic and bathing wastewater, poor organic alkali washing wastewater and poor organic acid washing wastewater;
b. sequentially carrying out primary filtration, membrane clarification and membrane purification on the recovered BeO washing wastewater to obtain a front-end clear solution of the recovered BeO washing wastewater and a front-end concentrated solution of the recovered BeO washing wastewater; sequentially carrying out primary filtration, membrane clarification and membrane purification on the raffinate wastewater to obtain a raffinate wastewater front end clear liquid and a raffinate wastewater front end concentrated liquid; sequentially carrying out pH adjustment, preliminary filtration, membrane clarification and fine filtration membrane separation on the mixed wastewater to obtain a mixed wastewater front end clear solution and a mixed wastewater front end concentrated solution;
c. classifying and recycling the front-end clear liquid of the recycled BeO washing wastewater, the front-end clear liquid of the raffinate wastewater and the front-end clear liquid of the mixed wastewater, regulating the pH of the comprehensive wastewater formed by converging the front-end concentrated liquid of the recycled BeO washing wastewater, the front-end concentrated liquid of the raffinate wastewater and the front-end concentrated liquid of the mixed wastewater, and sequentially performing rear-end pre-filtration, rear-end membrane clarification and rear-end membrane concentration on the clear liquid obtained by regulating the pH to obtain the recyclable fresh water and the concentrated water discharged out of the system;
the reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device are one of an inorganic membrane filtration device, an organic membrane filtration device, a roll-type membrane filtration device, a disc-type membrane filtration device, a plate-type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cutoff of the reclaimed BeO washing wastewater membrane clarification device, the raffinate wastewater membrane clarification device, the mixed wastewater membrane clarification device and the rear-end membrane clarification device is one of 5000Da, 8000Da, 10000Da, 30000Da, 50000Da, 80000Da, 100000Da, 150000Da, 200000Da and 250000 Da;
the purification membrane adopted for membrane purification of the recovered BeO washing wastewater is one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral membrane filtration device, a disc membrane filtration device, a plate membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cut-off of the purification membrane is 5000 Da;
the purification membrane adopted for membrane purification of the raffinate wastewater is one of an inorganic membrane filtration device, an organic membrane filtration device, a roll-type membrane filtration device, a disc-type membrane filtration device, a plate-type membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the interception molecular weight of the purification membrane is 5000Da,3000Da,2500Da,1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da and 20 Da;
the mixed wastewater fine filtration membrane separation adopts one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral membrane filtration device, a disc membrane filtration device, a plate membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device.
2. The integrated beryllium-containing wastewater treatment process as claimed in claim 1, wherein the concentrated solution obtained after membrane clarification of the recovered BeO washing wastewater in the step b flows back to a collection tank of the BeO washing wastewater.
3. The integrated beryllium-containing wastewater treatment process of claim 1, wherein the concentrated solution obtained after the raffinate wastewater in the step b is clarified by a membrane is returned to a raffinate wastewater collection tank.
4. The process of claim 1, wherein the concentrated solution obtained by membrane clarification of the mixed wastewater in step b is also merged with the concentrated solution at the front end of the recovered BeO washing wastewater, the concentrated solution at the front end of the raffinate wastewater and the concentrated solution at the front end of the mixed wastewater, and the pH value of the merged concentrated solution is adjusted.
5. The comprehensive treatment process of beryllium-containing wastewater as claimed in claim 1, wherein the concentrated solution obtained after the pH adjustment of the mixed wastewater in the step b is subjected to pressure filtration, and the filtrate obtained by the pressure filtration is returned to the mixed wastewater collection tank.
6. The comprehensive treatment process of beryllium-containing wastewater as claimed in claim 1, wherein the concentrated solution obtained by recovering the concentrated solution at the front end of the BeO washing wastewater, the concentrated solution at the front end of the raffinate wastewater and the concentrated solution at the front end of the mixed wastewater in the step c are converged and then subjected to pH adjustment to be subjected to pressure filtration, and the filtrate obtained by the pressure filtration and the clear solution obtained by the rear-end pretreatment are converged and then enter the rear-end membrane clarification section.
7. The integrated beryllium-containing wastewater treatment process of claim 1, wherein the concentrated solution obtained by clarifying the rear-end membrane is returned to the pH adjusting section of the step c, and then the step c is repeated.
8. The comprehensive treatment process of beryllium-containing wastewater as claimed in claim 1, wherein the preliminary filtration of the recovered BeO washing wastewater, the preliminary filtration of the raffinate wastewater, the preliminary filtration of the mixed wastewater and the preliminary filtration of the rear end are plate-frame filtration or cloth-bag filtration.
9. The integrated beryllium-containing wastewater treatment process of claim 1, wherein when the wastewater is low-concentration wastewater, the back-end membrane concentration comprises membrane separation, concentration desalination and fine desalination; when the wastewater is high-concentration wastewater, the back-end membrane concentration comprises membrane separation, fine filtration and electrodialysis.
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Effective date of registration: 20221206 Address after: Team 6, Group 3, Hejiayan Village, Jinniu Township, Jinniu District, Chengdu, Sichuan 610000 Patentee after: Lu Xianhua Address before: No.1, 3 / F, building 1, No.8 Dayuan Beizhong street, high tech Zone, Chengdu, Sichuan 610000 Patentee before: CHENGDU HONGRUN TECHNOLOGY Co.,Ltd. |