CN211921101U - Titanium dioxide acid waste water reuse of reclaimed water device - Google Patents
Titanium dioxide acid waste water reuse of reclaimed water device Download PDFInfo
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- CN211921101U CN211921101U CN201922235799.3U CN201922235799U CN211921101U CN 211921101 U CN211921101 U CN 211921101U CN 201922235799 U CN201922235799 U CN 201922235799U CN 211921101 U CN211921101 U CN 211921101U
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Abstract
The utility model relates to a titanium dioxide acid waste water recycle device. The neutralization reaction tank is used for carrying out neutralization reaction treatment on the wastewater; the lime milk dosing device is connected with the neutralization reaction tank; a primary sedimentation tank is connected with the neutralization reaction to remove the precipitate; the coagulating sedimentation tank is connected with the primary sedimentation tank; the coarse filter is connected to the coagulation sedimentation tank; the solid-liquid separation membrane is connected to the filtrate side of the coarse filter and is used for carrying out solid-liquid separation treatment on the filtrate obtained by the coarse filter; the nanofiltration membrane is connected to the filtrate side of the solid-liquid separation membrane; the reverse osmosis membrane is connected to the filtrate side of the nanofiltration membrane; the concentrated water treatment system is connected to the concentrated sides of the nanofiltration membrane and the reverse osmosis membrane and is used for carrying out dephosphorization and oxidation treatment on the concentrated solution; and the phosphorus removing agent feeding device and the oxidant feeding device are connected with the concentrated water treatment system.
Description
Technical Field
The utility model relates to an acid waste water recycle device, specifically speaking relate to a titanium white trade acid waste water treatment recycle device, belong to the water treatment field.
Background
Titanium dioxide is a white inorganic pigment, has the advantages of no toxicity, optimal opacity, optimal whiteness and brightness, is considered to be a white pigment with the best performance in the world nowadays, and is widely applied to the industries of coatings, plastics, papermaking, printing ink, chemical fibers, rubber, cosmetics and the like.
At present, the production process of titanium dioxide mainly comprises two processes, namely a sulfuric acid process and a chlorination process. The production process of titanium dioxide is mainly based on sulfuric acid process at home, and mainly based on chlorination process at abroad. In the production process of titanium dioxide by a sulfuric acid method, a large amount of sulfuric acid is required to be consumed, so that the discharge amount of waste gas, waste residue and waste water, three wastes and serious pollution are large. The dilute acid generated by each 1 ton of finished titanium dioxide in the existing titanium dioxide industry can reach60 tons. The acid wastewater of the sulfuric acid process contains a large amount of free sulfuric acid and F2+、Ti3+、Ca2+、Mg2+And a small amount of metal ions, etc.
The traditional titanium dioxide acid wastewater treatment process adopts neutralization treatment, quicklime is firstly digested into lime milk, then the lime milk is neutralized to be neutral with acid wastewater, after sufficient aeration and oxidation, gypsum slag and water are separated out through precipitation and filter pressing, and the filter-pressed water is discharged after passing through a sewage station. The process is low in cost, simple and reliable, but has large sewage discharge, and the sulfuric acid process titanium dioxide production enterprises at home and abroad basically adopt the method to treat the acidic wastewater. With the increase of domestic environmental protection pressure, the requirement on reuse water is higher and higher, and the process defect of simple neutralization and discharge by lime is more obvious.
SUMMERY OF THE UTILITY MODEL
The utility model aims at: solves the problem that the prior art does not have a better method for carrying out advanced treatment on titanium dioxide wastewater, and provides a process and a device for recycling titanium dioxide acid wastewater.
The technical scheme is as follows:
a process for recycling reclaimed water of titanium dioxide acid wastewater comprises the following steps:
step 1, neutralizing the titanium dioxide acidic wastewater to ensure that the pH value reaches more than 7.5;
3, settling the wastewater after coagulation treatment, and filtering the wastewater through a coarse filter and a solid-liquid separation membrane in sequence;
and 5, adding a phosphorus removing agent and an oxidant into the concentrated solution of the nanofiltration membrane and the reverse osmosis membrane for reaction.
In one embodiment, the coagulant is selected from polyaluminium chloride, polyferric sulfate, etc., and the addition amount of the coagulant is 50-200 mg/L.
In one embodiment, a flocculating agent is added in the coagulation process; the addition amount of the flocculating agent is 50-200 mg/L.
In one embodiment, the flocculant is polyacrylamide.
In one embodiment, a coagulation nucleating agent is also added in the coagulation process; the addition amount of the coagulation nucleating agent is 100-500 mg/L.
In one embodiment, the coagulating nucleating agent is an anionized microsphere.
In one embodiment, the anionized microspheres are surface cross-linked phosphorylated starch microspheres.
In one embodiment, after the sedimentation treatment in the steps 2 and 3, the sludge is subjected to filter pressing dehydration to obtain solid waste.
In one embodiment, the solid-liquid separation membrane is an ultrafiltration membrane or a microfiltration membrane; the filtering pressure is 0.1-0.5 MPa.
In one embodiment, the filtration pressure of the nanofiltration membrane is 1.0-1.5 MPa; the filtering pressure of the reverse osmosis membrane is 2.0-3.0 MPa.
In one embodiment, the phosphorus removal agent is an aluminum, calcium, or iron salt phosphorus removal agent; the oxidant is sodium hypochlorite, ozone or hydrogen peroxide.
A titanium dioxide acid waste water reclaimed water recycling device comprises:
the neutralization reaction tank is used for carrying out neutralization reaction treatment on the wastewater;
the lime milk dosing device is connected with the neutralization reaction tank and is used for adding lime milk into the neutralization reaction tank;
the primary sedimentation tank is connected with the neutralization reaction tank and is used for carrying out sedimentation treatment on the wastewater obtained in the neutralization reaction tank to remove sediments;
the coagulating sedimentation tank is connected with the primary sedimentation tank and is used for coagulating the clear liquid obtained in the primary sedimentation tank;
the coarse filter is connected with the coagulating sedimentation tank and is used for filtering the clear liquid obtained in the coagulating sedimentation tank;
the solid-liquid separation membrane is connected to the filtrate side of the coarse filter and is used for carrying out solid-liquid separation treatment on the filtrate obtained by the coarse filter;
the nanofiltration membrane is connected to the filtrate side of the solid-liquid separation membrane and is used for performing nanofiltration treatment on the filtrate obtained by the solid-liquid separation membrane;
the reverse osmosis membrane is connected to the filtrate side of the nanofiltration membrane and is used for performing reverse osmosis treatment on the filtrate obtained by the nanofiltration membrane;
the concentrated water treatment system is connected to the concentrated sides of the nanofiltration membrane and the reverse osmosis membrane and is used for carrying out dephosphorization and oxidation treatment on the concentrated solution;
and the phosphorus removing agent adding device and the oxidant adding device are connected to the concentrated water treatment system and are respectively used for adding a phosphorus removing agent and an oxidant into the concentrated water treatment system.
In one embodiment, the device further comprises a first stirring device for stirring the wastewater in the neutralization reaction tank.
In one embodiment, the pH on-line monitor is used for detecting the pH value of the wastewater in the neutralization reaction tank.
In one embodiment, the system further comprises a second stirring device for stirring the wastewater in the coagulation sedimentation tank.
In one embodiment, the system further comprises a coagulant adding device for adding a coagulant into the coagulation sedimentation tank.
In one embodiment, the device further comprises a coagulation nucleating agent adding device for adding the coagulation nucleating agent into the coagulation sedimentation tank.
In one embodiment, the coagulation sedimentation tank is a high-density sedimentation tank or a magnetic coagulation sedimentation tank.
In one embodiment, the coarse filter is a carbon filter, a sand filter or a multi-media filter.
In one embodiment, the device further comprises a final water production tank connected to the reverse osmosis membrane and used for collecting filtrate obtained in the reverse osmosis membrane; and the final water production tank is also connected with a clean water pump for supplying produced water.
In one embodiment, further comprising: and the first sludge delivery pump and the second sludge delivery pump are respectively connected to the primary sedimentation tank and the coagulating sedimentation tank and are respectively used for delivering the sludge obtained in the primary sedimentation tank and the coagulating sedimentation tank into a filter press for dehydration treatment.
In one embodiment, the coarse filter is connected to the solid-liquid separation membrane through a heat exchanger for reducing the temperature of the wastewater.
The application of the water reuse device in the titanium dioxide acid wastewater in treating the titanium dioxide acid wastewater.
Advantageous effects
Compared with the prior art, the utility model has the advantages of it is following:
1. the utility model discloses a to the advanced treatment of titanium dioxide acid waste water, through the neutralization, subside, receive and strain, reverse osmosis's processing back, filtrating can direct retrieval and utilization, and the conductivity is low.
2. The concentrated solution of reverse osmosis and nanofiltration can be further chemically treated, so that the content of total phosphorus, ammonia nitrogen and COD of the concentrated solution reaches the discharge standard.
3. In the wastewater coagulation process after neutralization, the microspheres with anionic property are introduced as nucleating agents, so that electropositive colloidal particles generated in the neutralization process can be adsorbed, and the coagulation sedimentation effect is improved.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a diagram of the apparatus of the present invention;
fig. 3 is a diagram of the device of the present invention.
FIG. 4 is a graph showing the steady flux for the ultrafiltration membrane run in the examples.
FIG. 5 is a graph showing flux attenuation of an ultrafiltration membrane in the examples.
1. A neutralization reaction tank; 11. a lime milk dosing device; 12. a first stirring device; 13. a pH on-line monitor; 14. a wastewater delivery pump; 2. a primary sedimentation tank; 21. a first sludge transfer pump; 22. a filter press; 3. a coagulating sedimentation tank; 31. a coagulant adding device; 32. a coagulation nucleating agent adding device; 33. a second stirring device; 34. a second sludge transfer pump; 35. a sewage delivery pump; 4. a coarse filter; 5. a heat exchanger; 6. a solid-liquid separation membrane; 7. a nanofiltration membrane; 8. a reverse osmosis membrane; 9. a concentrated water treatment system; 91. a phosphorus removing agent adding device; 92. an oxidant adding device; 93. a third stirring device; 10. a final water production tank; 101. a clean water pump;
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The recitation of values by ranges is to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range.
Reference throughout this specification to "one embodiment," "another embodiment," "an implementation," or the like, means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment described generally throughout this application. The appearances of the same phrase in various places in the specification are not necessarily all referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with any embodiment, it is submitted that it is within the purview of this application to effect such feature, structure, or characteristic in connection with other ones of the embodiments.
The utility model relates to a titanium dioxide acid wastewater recycling process and a device, belonging to the field of titanium dioxide industry acid wastewater recycling process and water treatment. The process and the device mainly comprise: the titanium dioxide acid wastewater enters a neutralization system, and lime milk is added to neutralize the titanium dioxide acid wastewater; the neutralized wastewater enters a primary sedimentation tank for pre-sedimentation, the supernatant after sedimentation enters a coagulating sedimentation tank, and a flocculating agent is added for flocculating sedimentation to remove most suspended particles; the sludge in the primary sedimentation tank and the sludge in the coagulating sedimentation tank enter a plate-and-frame filter press for filter pressing, the filter pressing clear liquid and the supernatant liquid in the coagulating sedimentation tank are mixed and then enter a coarse filter, and the red gypsum after filter pressing is treated as solid waste; the coarse filter mainly removes larger suspended particles in the wastewater, filtered water is cooled by a heat exchanger and then enters an ultrafiltration membrane filtration system to remove fine suspended matters, concentrated liquid of an ultrafiltration membrane system returns to a coagulating sedimentation tank, clear liquid of the ultrafiltration membrane system enters a nanofiltration membrane system to be filtered to remove multivalent salt in the wastewater, clear liquid of the nanofiltration membrane system enters a reverse osmosis membrane system to be filtered to remove monovalent salt in the water, and the obtained clear liquid can be recycled in production; and (3) mixing the concentrated solution of the nanofiltration membrane system and the concentrated solution of the reverse osmosis membrane system, then feeding the mixed solution into a concentrated water treatment system, adding a phosphorus removal agent, an oxidant and the like to reduce COD (chemical oxygen demand), ammonia nitrogen and total phosphorus in the concentrated water, and discharging the concentrated solution after reaching the standard.
The utility model adopts the technical proposal that: a titanium dioxide acid wastewater recycling process and a device thereof mainly comprise: step 1: the titanium dioxide acid wastewater enters a neutralization system, lime milk is added to neutralize the titanium dioxide acid wastewater, and the pH of the wastewater is adjusted to be more than 8.5; in this process, the acid in the wastewater can be neutralized, and Ti in the wastewater can be neutralized due to the alkali process3+、Ca2 +、Mg2+And a small amount of metal ions are converted into precipitates or other colloidal substances, and are separated through subsequent sedimentation and filtration processes, such as magnesium hydroxide colloid, calcium hydroxide colloid and the like can be generated.
Step 2: the neutralized wastewater enters a primary sedimentation tank for pre-sedimentation; the function here is to separate a part of the sediment by natural sedimentation;
and step 3: the supernatant of the primary sedimentation tank enters a coagulating sedimentation tank, and most suspended particles are removed by coagulating sedimentation by adding a coagulant; because the colloid generated in the neutralization reaction is small and is in a dispersed state in water, the reaction can generate larger particles by adding a coagulant, and the larger particles can be better separated; in order to make the coagulation effect better, a flocculating agent can be added for strengthening; the coagulant used herein may be polyaluminium chloride, polyferric sulfate, etc.; the flocculant used may be polyacrylamide or the like. In addition, because most of titanium hydroxide, calcium hydroxide and magnesium hydroxide colloids generated in the neutralization process are positively charged, in order to improve the coagulation effect, microspheres with anions on the surfaces can be added in the coagulation process to serve as nucleating agents, the colloids in the wastewater can grow better, the coagulation effect is improved, and fine colloids are prevented from entering a subsequent solid-liquid separation membrane to block membrane pores and cause too fast attenuation of membrane flux. The nucleating agent used in the method can be cross-linked by acrylamide, epichlorohydrin and starch under the condition of reverse suspension to obtain starch-based microspheres, and then the starch-based microspheres are reacted by sodium trimetaphosphate to obtain anionized microspheres; because the negative charges on the surface of the nucleating agent can adsorb the colloid around the nucleating agent through electrostatic action during coagulation nucleation, more coagulants can be produced, and the coagulation effect is improved.
And 4, step 4: the sludge precipitated in the primary sedimentation tank and the coagulating sedimentation tank enters a filter press for filter pressing; mixing the clear filter-pressing liquid and the supernatant liquid of the coagulating sedimentation tank, and then feeding the mixture into a coarse filter, wherein the red gypsum after filter-pressing is treated as solid waste and can be used for building materials such as bricks and the like after subsequent roasting; the coagulating sedimentation tank can be a high-density sedimentation tank, a magnetic coagulating sedimentation tank and other sedimentation tanks.
And 5: the coarse filter mainly removes larger suspended particles in the wastewater, and filtered water enters an ultrafiltration membrane filtering system after being cooled to below 40 ℃ by a heat exchanger;
step 6: filtering by an ultrafiltration membrane system to further remove fine suspended particulate matters in the wastewater, and returning the concentrated solution of the ultrafiltration membrane system to a coagulating sedimentation tank;
as the solid-liquid separation membrane used herein, an ultrafiltration membrane or a microfiltration membrane can be used.
The microfiltration membrane used for the utility model is a membrane with the average pore diameter of 0.01 mu m-5 mm, such as a microfiltration membrane, an MF membrane and the like for short. In addition, be used for the utility model discloses an ultrafiltration membrane is 1000~200000 membranes, is ultrafiltration membrane, UF membrane etc. for short for the molecular weight cut-off. Here, since the pore diameter of the ultrafiltration membrane is too small to measure the pore diameter on the membrane surface with an electron microscope or the like, a value called a molecular weight cut-off is used as an index of the pore diameter size instead of the average pore diameter. Regarding molecular weight cut-off, as described in textbooks in the art: "A curve obtained by plotting the solute molecular weight on the horizontal axis and the rejection on the vertical axis is referred to as a molecular weight cut-off curve. The molecular weight having a rejection of 90% is also referred to as a molecular weight cut-off of the membrane, which is an index representing the membrane performance of the ultrafiltration membrane and is well known to those skilled in the art. The material of the microfiltration membrane or ultrafiltration membrane is not particularly limited as long as the object of the present invention can be achieved by removing the water-soluble polymer and the colloidal component, and examples thereof include: cellulose, cellulose ester, polysulfone, polyethersulfone, polyvinyl chloride, chloropropylene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene, or other organic materials, or stainless steel or other metals, or ceramics or other inorganic materials. The material of the microfiltration membrane or ultrafiltration membrane may be appropriately selected in consideration of the properties of the hydrolysate or the running cost, and is preferably an organic material, preferably polyvinyl chloride, polypropylene, polyvinylidene fluoride, polysulfone, or polyether sulfone, in view of ease of handling. The material of the porous membrane constituting the ceramic separation membrane can be appropriately selected from conventionally known ceramic materials. For example, oxide-based materials such as alumina, zirconia, magnesia, silica, titania, ceria, yttria, and barium titanate; composite oxide materials such as cordierite, mullite, forsterite, steatite, sialon, zircon, ferrite and the like; nitride materials such as silicon nitride and aluminum nitride; carbide-based materials such as silicon carbide; hydroxide materials such as hydroxyapatite; elemental materials such as carbon and silicon; or an inorganic composite material containing two or more of them. Natural minerals (clay, clay minerals, earthenware slag, silica sand, pottery stone, feldspar, white sand) or blast furnace slag, fly ash, etc. may also be used. Among them, 1 or 2 or more kinds selected from alumina, zirconia, titania, magnesia and silica are preferable, and ceramic powder mainly composed of alumina, zirconia or titania is more preferable. The term "mainly" as used herein means that 50 mass% or more (preferably 75 mass% or more, and more preferably 80 to 100 mass%) of the entire ceramic powder is alumina or silica. For example, among porous materials, alumina is inexpensive and excellent in handling properties. Further, since a porous structure having pore diameters suitable for liquid separation can be easily formed, a ceramic separation membrane having excellent liquid permeability can be easily produced. Among the above aluminas, alpha-alumina is particularly preferably used. Alpha-alumina has the characteristics of being chemically stable and having high melting point and mechanical strength. Therefore, by using α -alumina, a ceramic separation membrane that can be utilized in a wide range of applications (e.g., industrial fields) can be manufactured.
And 7: the clear liquid of the ultrafiltration membrane system enters a nanofiltration membrane system to be filtered to remove multivalent salt in the wastewater;
nanofiltration membranes, as used herein, are defined as "pressure driven membranes that block particles smaller than 2nm and dissolved macromolecules". Suitable for the utility model discloses an effective nanofiltration membrane is preferred to be such membrane: there is an electric charge on the membrane surface, and thus improved separation efficiency is exhibited by a combination of fine pore separation (particle size separation) and electrostatic separation benefiting from the electric charge on the membrane surface. Therefore, it is necessary to use a nanofiltration membrane capable of removing a high molecular substance by particle size separation while separating an alkali metal ion to be recovered from another ion having a different charge characteristic by means of charge. As the material of the nanofiltration membrane used in the utility model, high polymer materials such as cellulose acetate polymer, polyamide, sulfonated polysulfone, polyacrylonitrile, polyester, polyimide, vinyl polymer and the like can be used. The film is not limited to one composed of only one material, and may be a film containing a plurality of the materials. With respect to the membrane structure, the membrane may be an asymmetric membrane having a dense layer on at least one side of the membrane and having micropores with pore diameters gradually increasing from the dense layer toward the inside of the membrane or the other side; or a composite membrane having a very thin functional layer of another material on the dense layer of the asymmetric membrane.
And 8: filtering the clear liquid of the nanofiltration membrane system by using a reverse osmosis membrane system to remove monovalent salt in the wastewater, wherein the obtained clear liquid can be recycled in production;
the liquid to be treated supplied to the reverse osmosis membrane apparatus is usually supplied to the apparatus after being subjected to pretreatment such as coagulation, precipitation, sand filtration, activated carbon filtration, microfiltration, ultrafiltration, permeation through a safety filter, etc., by adding chemical agents such as a bactericide, a coagulant, a reducing agent, a pH adjuster, etc. For example, in the case of seawater desalination, seawater is taken, particles and the like are separated in a sedimentation tank, and a bactericide such as ammonia is added to the sedimentation tank to sterilize the seawater. Next, a coagulant such as ferric chloride or polyaluminum chloride is added to the mixture, followed by sand filtration. The filtrate is stored in a storage tank, the pH is adjusted with sulfuric acid or the like, and then the liquid is transferred, and in the process of transferring the liquid, a reducing agent such as sodium hydrogen sulfite is added to reduce and remove the bactericide, and after passing through a safety filter, the pressure of the permeate is raised by a high-pressure pump to supply the permeate to a reverse osmosis membrane module. The reverse osmosis membrane is a semipermeable membrane that allows a part of components in a liquid, for example, a solvent to permeate therethrough and does not allow other components to permeate therethrough. Further, as the structure thereof, there are an asymmetric membrane having a dense layer on at least one side of the membrane and having fine pores with gradually increasing pore diameters from the dense layer to the inside of the membrane or the other side surface, a composite membrane having a very thin active layer made of another material on the dense layer of the asymmetric membrane, and the like. Examples of the reverse osmosis membrane include a hollow fiber and a flat membrane. In general, it is preferable that the film thickness of the hollow fiber and the flat film is 10 μm to 1mm, and the outer diameter of the hollow fiber is 50 μm to 4 mm. In addition, the flat membrane is preferably an asymmetric membrane, and the composite membrane is preferably a membrane supported on a base material such as a woven fabric, a knitted fabric, or a nonwoven fabric. However, the method of the present invention can be used independently of the material, membrane structure, or form of the reverse osmosis membrane, and is effective in any case. Typical examples of the reverse osmosis membrane include cellulose acetate-based or polyamide-based asymmetric membranes, and composite membranes having a polyamide-based or polyurea-based active layer. The reverse osmosis membrane module is a substance formed into a shape for actually using the reverse osmosis membrane. When the form of the reverse osmosis membrane is a flat membrane, it can be used by being incorporated into a module of a spiral, a tube or a plate and a frame, and when the membrane is a hollow wire, it can be used by being incorporated into a module after being bundled. The present invention can be applied independently of the configuration of these reverse osmosis membrane modules.
And step 9: and after the concentrated solution of the nanofiltration membrane system and the concentrated solution of the reverse osmosis membrane system are mixed, the mixed solution enters a concentrated water treatment system, and a phosphorus removing agent, an oxidant and the like are added to reduce COD, ammonia nitrogen and total phosphorus in the concentrated water to reach the discharge standard.
Based on the above method, the device provided by the present invention is shown in fig. 2 and fig. 3, and includes:
the neutralization reaction tank 1 is used for carrying out neutralization reaction treatment on the wastewater;
the lime milk dosing device 11 is connected to the neutralization reaction tank 1 and is used for adding lime milk into the neutralization reaction tank 1;
the primary sedimentation tank 2 is connected with the neutralization reaction tank 1 and is used for carrying out sedimentation treatment on the wastewater obtained in the neutralization reaction tank 1 and removing sediments;
the coagulating sedimentation tank 3 is connected to the primary sedimentation tank 2 and is used for coagulating the clear liquid obtained in the primary sedimentation tank 2;
the coarse filter 4 is connected to the coagulating sedimentation tank 3 and is used for filtering the clear liquid obtained in the coagulating sedimentation tank 3;
a solid-liquid separation membrane 6 connected to the filtrate side of the coarse filter 4 for performing solid-liquid separation treatment on the filtrate obtained by the coarse filter 4;
a nanofiltration membrane 7 connected to the filtrate side of the solid-liquid separation membrane 6 and used for performing nanofiltration treatment on the filtrate obtained by the solid-liquid separation membrane 6;
the reverse osmosis membrane 8 is connected to the filtrate side of the nanofiltration membrane 7 and is used for performing reverse osmosis treatment on the filtrate obtained by the nanofiltration membrane 7;
the concentrated water treatment system 9 is connected to the concentration sides of the nanofiltration membrane 7 and the reverse osmosis membrane 8 and is used for carrying out dephosphorization and oxidation treatment on the concentrated solution;
and the phosphorus removing agent adding device 91 and the oxidant adding device 92 are connected to the concentrated water treatment system 9 and are respectively used for adding a phosphorus removing agent and an oxidant into the concentrated water treatment system 9.
In one embodiment, a first stirring device 12 is further included for stirring the wastewater in the neutralization reaction tank 1.
In one embodiment, an online pH monitor 13 is used to detect the pH of the wastewater in the neutralization reaction tank 1.
In one embodiment, a second stirring device 33 is further included for stirring the wastewater in the coagulation sedimentation tank 3.
In one embodiment, the system further comprises a coagulant adding device 31 for adding a coagulant into the coagulation sedimentation tank 3.
In one embodiment, the device further comprises a coagulation nucleating agent adding device 32, which is used for adding the coagulation nucleating agent into the coagulation sedimentation tank 3.
In one embodiment, the coagulation sedimentation tank 3 is a high-density sedimentation tank or a magnetic coagulation sedimentation tank.
In one embodiment, the coarse filter 4 is a carbon filter, a sand filter or a multi-media filter.
In one embodiment, the system further comprises a final water production tank 10 connected to the reverse osmosis membrane 8 and used for collecting the filtrate obtained in the reverse osmosis membrane 8; the final water producing tank 10 is also connected with a clean water pump 101 for supplying produced water.
In one embodiment, further comprising: the first sludge delivery pump 21 and the second sludge delivery pump 34 are respectively connected to the primary sedimentation tank 2 and the coagulating sedimentation tank 3, and are respectively used for delivering the sludge obtained in the primary sedimentation tank 2 and the coagulating sedimentation tank 3 to the filter press 22 for dehydration treatment.
In one embodiment, the coarse filter 4 is connected to the solid-liquid separation membrane 6 through a heat exchanger 5 for lowering the temperature of the wastewater.
Example 1
Pumping the titanium dioxide acid wastewater into a wastewater neutralization tank, automatically adding lime milk for neutralization reaction, adjusting the pH value to be more than 8.5, stirring for reaction for 30min, pumping into a primary sedimentation tank for pre-sedimentation through a pump, after the sedimentation retention time is 30min, overflowing into a coagulative sedimentation tank, adding 100mg/L polyferric chloride sulfate for coagulation reaction for 20min, adding 75mg/L polyacrylamide as a flocculating agent, stirring for reaction for 10-15min, after the sedimentation is 30min, cooling through a heat exchanger, and pumping into an ultrafiltration membrane system; the ultrafiltration membrane system adopts a hollow fiber membrane of 0.45um for filtration, the filtration pressure is 0.2MPa, the water recovery rate is 80%, concentrated water returns to a coagulating sedimentation tank to remove suspended particles, filtered water enters a nanofiltration membrane system for filtration to remove multivalent salt ions such as sulfate radicals, calcium, magnesium and the like, the filtration pressure of the nanofiltration membrane system is 1.5MPa, the water recovery rate is 60%, the filtered water enters a reverse osmosis membrane system for filtration to remove monovalent salt ions such as chloride ions, sodium ions and the like, the filtration pressure of the reverse osmosis membrane system is 3.0MPa, the water recovery rate is 90%, and finally clean water is obtained and reused in the production process; and (3) the filtered concentrated water of the nanofiltration membrane system and the filtered concentrated water of the reverse osmosis membrane system enter a concentrated water treatment system, and 84ppm of calcium salt phosphorus removing agent and 120ppm of ozone are respectively added to remove part of COD, ammonia nitrogen, total phosphorus and the like which reach the discharge standard.
Example 2
Pumping the titanium dioxide acid wastewater into a wastewater neutralization tank, automatically adding lime milk for neutralization reaction, adjusting the pH value to be more than 8.5, stirring for reaction for 30min, pumping the titanium dioxide acid wastewater into a primary sedimentation tank for pre-sedimentation, allowing the titanium dioxide acid wastewater to overflow into a coagulative sedimentation tank after the sedimentation retention time is 30min, adding 120mg/L polymerized ferric chloride sulfate for coagulation reaction for 30min, adding 100mg/L polyacrylamide as a flocculating agent, stirring for reaction for 10-15min, allowing the titanium dioxide acid wastewater to precipitate for 30min, pumping into a sand filter for filtering to remove large-particle impurities, cooling by a heat exchanger, and then feeding into an ultrafiltration membrane system; the ultrafiltration membrane system is filtered by a ceramic membrane with the average pore diameter of 50nm, the filtering pressure is 0.3MPa, the water recovery rate is 90%, concentrated water returns to the coagulating sedimentation tank to remove suspended particles, filtered water enters a nanofiltration membrane system to be filtered to remove sulfate radicals, calcium, magnesium and other multivalent salt ions, the filtering pressure of the nanofiltration membrane system is 1.0 MPa, the water recovery rate is 80%, the filtered water enters a reverse osmosis membrane system to be filtered to remove chloride ions, sodium ions and other monovalent salt ions, the filtering pressure of the reverse osmosis membrane system is 2.5MPa, the water recovery rate is 90%, and finally clean water is obtained and reused in the production process; and (3) enabling the filtered concentrated water of the nanofiltration membrane system and the reverse osmosis membrane system to enter a concentrated water treatment system, and respectively adding 95ppm of a phosphorus removal agent and 180ppm of an oxidant to remove part of COD, ammonia nitrogen, total phosphorus and the like which reach the discharge standard.
Example 3
Pumping the titanium dioxide acidic wastewater into a wastewater neutralization tank, automatically adding lime milk for neutralization reaction, adjusting the pH value to be more than 8.5, stirring for reaction for 30min, pumping the titanium dioxide acidic wastewater into a primary sedimentation tank for pre-sedimentation, allowing the titanium dioxide acidic wastewater to stay for 30min, then overflowing the titanium dioxide acidic wastewater into a coagulative sedimentation tank, adding 150mg/L polymerized ferric chloride sulfate for coagulation reaction for 30min, adding 120mg/L polyacrylamide as a flocculating agent, stirring for reaction for 10-15min, allowing the titanium dioxide acidic wastewater to settle for 30min, pumping the titanium dioxide acidic wastewater into a multi-media filter for filtering to remove large-particle impurities, cooling the titanium dioxide acidic wastewater by a heat exchanger, and; the ultrafiltration membrane system adopts a hollow fiber membrane for filtration, the filtration pressure is 0.3MPa, the water recovery rate is 95 percent, concentrated water returns to the coagulating sedimentation tank to remove suspended particles, filtered water enters a nanofiltration membrane system for filtration to remove sulfate radicals, calcium, magnesium and other multivalent salt ions, the filtration pressure of the nanofiltration membrane system is 2.0MPa, the water recovery rate is 85 percent, the filtered water enters a reverse osmosis membrane system for filtration to remove chloride ions, sodium ions and other monovalent salt ions, the filtration pressure of the reverse osmosis membrane system is 3.5MPa, the water recovery rate is 95 percent, and finally clean water is obtained and reused in the production process; and (3) enabling the filtered concentrated water of the nanofiltration membrane system and the reverse osmosis membrane system to enter a concentrated water treatment system, and respectively adding a phosphorus removal agent of 120ppm and an oxidant of 240ppm to remove part of COD, ammonia nitrogen, total phosphorus and the like which reach the discharge standard.
Example 4
The difference from example 1 is that: sodium trimetaphosphate modified starch-based microspheres are also added as nucleating agents in the coagulation process.
Pumping the titanium dioxide acidic wastewater into a wastewater neutralization tank, automatically adding lime milk for neutralization reaction, adjusting the pH value to be more than 8.5, stirring for reaction for 30min, pumping into a primary sedimentation tank for pre-sedimentation through a pump, after the sedimentation retention time is 30min, overflowing into a coagulative sedimentation tank, firstly adding 100mg/L polyferric chloride sulfate and 100mg/L sodium trimetaphosphate modified starch-based microsphere nucleating agent for coagulation reaction for 20min, then adding 75mg/L polyacrylamide as a flocculating agent, stirring for reaction for 10-15min, after sedimentation for 30min, cooling through a heat exchanger, and pumping into an ultrafiltration membrane system; the ultrafiltration membrane system adopts a hollow fiber membrane of 0.45um for filtration, the filtration pressure is 0.2MPa, the water recovery rate is 80%, concentrated water returns to a coagulating sedimentation tank to remove suspended particles, filtered water enters a nanofiltration membrane system for filtration to remove multivalent salt ions such as sulfate radicals, calcium, magnesium and the like, the filtration pressure of the nanofiltration membrane system is 1.5MPa, the water recovery rate is 60%, the filtered water enters a reverse osmosis membrane system for filtration to remove monovalent salt ions such as chloride ions, sodium ions and the like, the filtration pressure of the reverse osmosis membrane system is 3.0MPa, the water recovery rate is 90%, and finally clean water is obtained and reused in the production process; and (3) the filtered concentrated water of the nanofiltration membrane system and the filtered concentrated water of the reverse osmosis membrane system enter a concentrated water treatment system, and 84ppm of calcium salt phosphorus removing agent and 120ppm of ozone are respectively added to remove part of COD, ammonia nitrogen, total phosphorus and the like which reach the discharge standard.
Example 5
The difference from example 2 is that: sodium trimetaphosphate modified starch-based microspheres are also added as nucleating agents in the coagulation process.
Pumping the titanium dioxide acidic wastewater into a wastewater neutralization tank, automatically adding lime milk for neutralization reaction, adjusting the pH value to be more than 8.5, stirring for reaction for 30min, pumping the titanium dioxide acidic wastewater into a primary sedimentation tank for pre-sedimentation, allowing the titanium dioxide acidic wastewater to stay for 30min, then overflowing the titanium dioxide acidic wastewater into a coagulative sedimentation tank, firstly adding 120mg/L of polymeric ferric chloride sulfate and 120mg/L of sodium trimetaphosphate modified starch-based microsphere nucleating agent for coagulation reaction for 30min, then adding 100mg/L of polyacrylamide as a flocculating agent, stirring for reaction for 10-15min, precipitating for 30min, pumping into a sand filter for filtering to remove large-particle impurities, cooling by a heat exchanger, and then feeding into an ultrafiltration membrane system; the ultrafiltration membrane system is filtered by a ceramic membrane with the average pore diameter of 50nm, the filtering pressure is 0.3MPa, the water recovery rate is 90%, concentrated water returns to the coagulating sedimentation tank to remove suspended particles, filtered water enters a nanofiltration membrane system to be filtered to remove sulfate radicals, calcium, magnesium and other multivalent salt ions, the filtering pressure of the nanofiltration membrane system is 1.0 MPa, the water recovery rate is 80%, the filtered water enters a reverse osmosis membrane system to be filtered to remove chloride ions, sodium ions and other monovalent salt ions, the filtering pressure of the reverse osmosis membrane system is 2.5MPa, the water recovery rate is 90%, and finally clean water is obtained and reused in the production process; and (3) enabling the filtered concentrated water of the nanofiltration membrane system and the reverse osmosis membrane system to enter a concentrated water treatment system, and respectively adding 95ppm of a phosphorus removal agent and 180ppm of an oxidant to remove part of COD, ammonia nitrogen, total phosphorus and the like which reach the discharge standard.
Example 6
The difference from example 3 is that: sodium trimetaphosphate modified starch-based microspheres are also added as nucleating agents in the coagulation process.
Pumping the titanium dioxide acidic wastewater into a wastewater neutralization tank, automatically adding lime milk for neutralization reaction, adjusting the pH value to be more than 8.5, stirring for reaction for 30min, pumping the wastewater into a primary sedimentation tank for pre-sedimentation, allowing the wastewater to stay for 30min, then overflowing the wastewater into a coagulative sedimentation tank, firstly adding 150mg/L of polymeric ferric chloride sulfate and 130mg/L of sodium trimetaphosphate modified starch-based microsphere nucleating agent for coagulation reaction for 30min, then adding 120mg/L of polyacrylamide serving as a flocculating agent, stirring for reaction for 10-15min, precipitating for 30min, pumping into a multi-media filter for filtering to remove large-particle impurities, cooling by a heat exchanger, and then feeding into an ultrafiltration membrane system; the ultrafiltration membrane system adopts a hollow fiber membrane for filtration, the filtration pressure is 0.3MPa, the water recovery rate is 95 percent, concentrated water returns to the coagulating sedimentation tank to remove suspended particles, filtered water enters a nanofiltration membrane system for filtration to remove sulfate radicals, calcium, magnesium and other multivalent salt ions, the filtration pressure of the nanofiltration membrane system is 2.0MPa, the water recovery rate is 85 percent, the filtered water enters a reverse osmosis membrane system for filtration to remove chloride ions, sodium ions and other monovalent salt ions, the filtration pressure of the reverse osmosis membrane system is 3.5MPa, the water recovery rate is 95 percent, and finally clean water is obtained and reused in the production process; and (3) enabling the filtered concentrated water of the nanofiltration membrane system and the reverse osmosis membrane system to enter a concentrated water treatment system, and respectively adding a phosphorus removal agent of 120ppm and an oxidant of 240ppm to remove part of COD, ammonia nitrogen, total phosphorus and the like which reach the discharge standard.
Example 7
The difference from example 6 is that: the nucleating agent is not modified by sodium trimetaphosphate, and starch microspheres are directly used as the nucleating agent.
Pumping the titanium dioxide acid wastewater into a wastewater neutralization tank, automatically adding lime milk for neutralization reaction, adjusting the pH value to be more than 8.5, stirring for reaction for 30min, pumping the titanium dioxide acid wastewater into a primary sedimentation tank for pre-sedimentation, allowing the titanium dioxide acid wastewater to overflow into a coagulative sedimentation tank after the sedimentation retention time is 30min, firstly adding 150mg/L of polymeric ferric chloride sulfate and 130mg/L of starch microsphere nucleating agent for coagulation reaction for 30min, then adding 120mg/L of polyacrylamide serving as a flocculating agent, stirring for reaction for 10-15min, pumping into a multi-media filter for filtering to remove large-particle impurities after the sedimentation is 30min, cooling by a heat exchanger, and then feeding into an ultrafiltration membrane system; the ultrafiltration membrane system adopts a hollow fiber membrane for filtration, the filtration pressure is 0.3MPa, the water recovery rate is 95 percent, concentrated water returns to the coagulating sedimentation tank to remove suspended particles, filtered water enters a nanofiltration membrane system for filtration to remove sulfate radicals, calcium, magnesium and other multivalent salt ions, the filtration pressure of the nanofiltration membrane system is 2.0MPa, the water recovery rate is 85 percent, the filtered water enters a reverse osmosis membrane system for filtration to remove chloride ions, sodium ions and other monovalent salt ions, the filtration pressure of the reverse osmosis membrane system is 3.5MPa, the water recovery rate is 95 percent, and finally clean water is obtained and reused in the production process; and (3) enabling the filtered concentrated water of the nanofiltration membrane system and the reverse osmosis membrane system to enter a concentrated water treatment system, and respectively adding a phosphorus removal agent of 120ppm and an oxidant of 240ppm to remove part of COD, ammonia nitrogen, total phosphorus and the like which reach the discharge standard.
In the above processes, the wastewater treatment conditions are as follows:
it can be seen from the above table, through the utility model discloses titanium dioxide acid waste water after handling can reach the emission requirement, and finally the conductivity, COD, ammonia nitrogen and the total phosphorus content of producing water all obviously accord with emission standard. The COD value and the total phosphorus content in the wastewater are obviously reduced by adding a phosphorus removal agent and an oxidant into the nanofiltration and reverse osmosis concentrated solution; in addition, by comparing examples 4-6 with examples 1-3, when nucleating agent microspheres with anionic surfaces are added in the coagulation process, because the nucleating agent microspheres can generate electrostatic interaction with magnesium hydroxide and calcium hydroxide colloid with positive charges, the coagulation effect is improved, flocculating constituents can be effectively grown and settled, the turbidity of coarse filtration effluent is reduced, the running load of the ultrafiltration membrane is reduced, and the stable running flux of the ultrafiltration membrane is improved; however, as can be seen from examples 6 and 7, when the ordinary starch microspheres are directly used as the nucleating agent, more positive charge colloids cannot be adsorbed through electrostatic action, and the treatment effect is slightly poor; it can be seen from the comparison graph of the stable flux of the ultrafiltration membrane in fig. 4 and the flux decay graph of the ultrafiltration membrane in the example in fig. 5 that the flux decay curve of the ultrafiltration membrane is slower after the nucleation coagulation treatment.
Claims (10)
1. The utility model provides a titanium dioxide acid waste water reuse of reclaimed water device which characterized in that includes:
the neutralization reaction tank (1) is used for carrying out neutralization reaction treatment on the wastewater;
the lime milk dosing device (11) is connected to the neutralization reaction tank (1) and is used for adding lime milk into the neutralization reaction tank (1);
the primary sedimentation tank (2) is connected with the neutralization reaction tank (1) and is used for carrying out sedimentation treatment on the wastewater obtained in the neutralization reaction tank (1) and removing sediments;
the coagulating sedimentation tank (3) is connected to the primary sedimentation tank (2) and is used for coagulating the clear liquid obtained in the primary sedimentation tank (2);
the coarse filter (4) is connected to the coagulating sedimentation tank (3) and is used for filtering the clear liquid obtained in the coagulating sedimentation tank (3);
a solid-liquid separation membrane (6) connected to the filtrate side of the coarse filter (4) and used for performing solid-liquid separation treatment on the filtrate obtained by the coarse filter (4);
a nanofiltration membrane (7) connected to the filtrate side of the solid-liquid separation membrane (6) and used for performing nanofiltration treatment on the filtrate obtained by the solid-liquid separation membrane (6);
the reverse osmosis membrane (8) is connected to the filtrate side of the nanofiltration membrane (7) and is used for performing reverse osmosis treatment on the filtrate obtained by the nanofiltration membrane (7);
the concentrated water treatment system (9) is connected to the concentration sides of the nanofiltration membrane (7) and the reverse osmosis membrane (8) and is used for carrying out dephosphorization and oxidation treatment on concentrated solution;
and the phosphorus removing agent adding device (91) and the oxidant adding device (92) are connected to the concentrated water treatment system (9) and are respectively used for adding the phosphorus removing agent and the oxidant into the concentrated water treatment system (9).
2. The device for recycling the titanium dioxide acidic wastewater reclaimed water according to claim 1, further comprising a first stirring device (12) for stirring the wastewater in the neutralization reaction tank (1).
3. The device for recycling the reclaimed water from the titanium dioxide acidic wastewater according to claim 1, further comprising: and the pH on-line monitor (13) is used for detecting the pH value of the wastewater in the neutralization reaction tank (1).
4. The device for recycling the titanium dioxide acidic wastewater reclaimed water according to claim 1, further comprising a second stirring device (33) for stirring the wastewater in the coagulation sedimentation tank (3).
5. The device for recycling the water in the titanium dioxide acidic wastewater according to claim 1, further comprising a coagulant adding device (31) for adding a coagulant into the coagulation sedimentation tank (3).
6. The titanium dioxide acid wastewater reclaimed water recycling device according to claim 1, further comprising a coagulation nucleating agent adding device (32) for adding a coagulation nucleating agent into the coagulation sedimentation tank (3).
7. The device for recycling the reclaimed water in the titanium dioxide acid wastewater according to claim 1, wherein the coagulation sedimentation tank (3) is a high-density sedimentation tank or a magnetic coagulation sedimentation tank; in one embodiment, the coarse filter (4) is a carbon filter, a sand filter or a multi-media filter.
8. The titanium dioxide acid wastewater reclaimed water recycling device according to claim 1, further comprising a final water production tank (10) connected to the reverse osmosis membrane (8) for collecting filtrate obtained in the reverse osmosis membrane (8); the final water production tank (10) is also connected with a clean water pump (101) for supplying produced water.
9. The device for recycling the reclaimed water from the titanium dioxide acidic wastewater according to claim 1, further comprising: the first sludge delivery pump (21) and the second sludge delivery pump (34) are respectively connected to the primary sedimentation tank (2) and the coagulating sedimentation tank (3) and are respectively used for delivering sludge obtained in the primary sedimentation tank (2) and the coagulating sedimentation tank (3) into the filter press (22) for dehydration treatment.
10. The titanium dioxide acid wastewater reclaimed water reusing device according to claim 1, wherein the coarse filter (4) is connected to the solid-liquid separation membrane (6) through a heat exchanger (5) for reducing the temperature of the wastewater.
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