CN111995087A - Cold rolling leveling waste liquid treatment method based on forward osmosis theory - Google Patents
Cold rolling leveling waste liquid treatment method based on forward osmosis theory Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention discloses a cold rolling leveling liquid treatment method based on forward osmosis theory, which comprises the following steps: 1. filtering the flat waste liquid by a paper tape, wherein the filtering precision is 15-30 microns; 2. then 20-30m3The flow velocity of the flow/h enters a tubular microfiltration membrane, and the aperture of the filtration membrane is 0.1 mu m; filtering until more than 95% of solid impurities in the waste liquid are removed, and SS is less than 10 mg/L; 3. introducing the waste liquid treated in the step 2 into a coalescence oil-water separator, wherein the coalescence oil-water separator is sequentially provided with a rectifying area for fully and uniformly mixing the liquid, a coalescence area filled with a coalescence medium and an oil-phase water-phase outlet separation area according to the sequence of the waste liquid flowing; the base material of the coalescence medium is a composite fiber formed by weaving polytetrafluoroethylene fibers and stainless steel wires in a mixed mode; the contact angle between the polytetrafluoroethylene fiber and the surface of water is 120-130 degrees, and the contact angle between the polytetrafluoroethylene fiber and oil is 45 degrees; 4. and (4) concentrating the liquid separated from the water phase outlet in the step (3) by a forward osmosis membrane and recycling the liquid in the production link.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a cold rolling leveling waste liquid treatment method based on a forward osmosis theory.
Background
The essence of the leveling is cold rolling with small pressing rate (0.3-3%), the effect is to eliminate a yield platform, and a stamping 'slip line' does not appear in a long period of time after the strip steel is leveled; meanwhile, the yield limit of the plate strip is minimized, so that the forming performance of the plate shape is improved; the plate shape is improved, and the straightness of the plate strip is improved; the strip steel has certain roughness. The working procedure determines the surface state, plate shape, mechanical property and technological property of the product strip steel to a great extent.
Leveling is divided into a dry leveling mode and a wet leveling mode. The dry flattening is free from adding lubricant, and is characterized in that the surface of the rolled strip can be kept free from being stained; preparing for next processing (galvanizing); large friction is generated between the roller and a rolled piece; ensuring that only limited extension and reduction are provided for the rolled piece; the reduction rate is generally 0.5 to 6 percent. Wet leveling can be divided into two types, namely medicament wet leveling and pure water leveling. The pure water is smooth, as the name suggests, the pure water is used for operation, the lubricant which has stronger cleaning effect and can prevent repair is adopted for agent flattening, and the cost is higher. Compared with the wet chemical flattening, the method is more beneficial to the control of constant elongation and surface quality, the existing cold rolling process mostly adopts the wet chemical flattening process, flattening liquid is needed, and flattening waste liquid, namely high-concentration special organic wastewater, is correspondingly generated.
The leveling liquid is an important medium used in the chemical leveling process and is divided into an inorganic leveling liquid (nitrite type) and an organic leveling liquid (organic amine salt type). Currently, organic flattening liquid is mostly used and generally comprises the following parts: rust remover, surfactant, lubricant, defoaming agent, deionized water and the like. The chemical leveling is to dilute a leveling chemical stock solution by using pure water to prepare a use concentration of 1% -5%, namely, the leveling solution is used and then used in industrial production, a special wastewater generated after use is leveling waste liquid, the water quality condition is mainly characterized in that the molecular weight of pollutants is less than 650, the biodegradability is poor, and the water quality is characterized in that: the oil content is 1500mg/L, COD to 7000-40000 mg/L, the waste liquid discharge temperature is 50 ℃, and the pH value is about 9.0-10.0. For the wastewater, no mature treatment process exists at home and abroad, and most of the wastewater is diluted and then mixed with other wastewater for treatment.
Chinese patent application No. 201010022778.4 provides a method for treating a flat waste liquid, comprising the steps of: (1) adding iron salt into the leveling waste liquid, adding the iron salt at 6000-8000 mg/L, quickly mixing for 0.5-2 min to fully mix, reacting for 10-30 min, and then precipitating for 0.5-2 h to perform solid-liquid separation; (2) diluting COD of the effluent obtained in the step (1) to 1000-2000 mg/L, and allowing the effluent to enter a hydrolysis acidification reactor, wherein the hydraulic retention time is 12-24 h; (3) and (3) enabling the effluent obtained in the step (2) to enter an aerobic membrane bioreactor, and enabling the hydraulic retention time to be 24-48 h. The method for treating the leveling waste liquid can ensure that the treated effluent reaches the national discharge standard, effectively solves the problem of leveling waste liquid treatment, develops a new process for treating the leveling waste liquid, and has good environmental benefit and social benefit.
The Chinese patent document with the application number of 2013101103930.3 provides a stainless steel leveling waste liquid recycling treatment method and a system thereof, and the method sequentially comprises the steps of pH adjustment, advanced oxidation, coagulation flocculation precipitation, filtration and reverse osmosis; the system comprises a pH adjusting tank, an advanced oxidation device and a sludge sedimentation tank which are connected in sequence, wherein a coagulation flocculation mixing device and a coagulation sedimentation tank are also connected between the advanced oxidation device and the sludge sedimentation tank in sequence; a filtering device and a reverse osmosis device are sequentially connected behind the coagulating sedimentation tank. The invention aims at the recycling process of the stainless steel leveling waste liquid, effectively removes heavy metals in the stainless steel leveling waste liquid, and effectively reduces the consumption of a large amount of new water in the leveling process.
With the continuous development of high-concentration organic wastewater treatment technology, a treatment technology for carrying out standard treatment on the leveling liquid and the mixed wastewater thereof by using a high-efficiency anaerobic-aerobic biological process appears. The anaerobic biological treatment of wastewater refers to a process of decomposing and converting various complex organic matters in wastewater into substances such as methane, carbon dioxide and the like under the action of anaerobic microorganisms (including facultative microorganisms) under the condition of no molecular oxygen. However, the traditional anaerobic biological treatment has the problems of long culture and acclimation time, sludge loss, further improvement of treatment efficiency and the like, and the application of the anaerobic biological treatment reactor is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cold rolling leveling waste liquid treatment method which is simple in process and can be recycled and is based on a forward osmosis theory.
The technical problem to be solved can be implemented by the following technical scheme.
A cold rolling flattening fluid treatment method based on forward osmosis theory is characterized by comprising the following steps:
(1) carrying out paper tape filtration on the flat waste liquid, wherein the filtration precision is 15-30 microns;
(2) the flat waste liquid after the primary treatment of the paper tape filtration is 20-30m3The flow rate of the solution/h enters a tubular microfiltration membrane for tubular microfiltration, and the aperture of the membrane is 0.1-0.3 mu m; filtering until solid impurities in the flat waste liquid are removed by more than 95 percent, and SS is less than 10 mg/L;
(3) introducing the flat waste liquid treated in the step (2) into a coalescence oil-water separator, wherein the coalescence oil-water separator is sequentially provided with a rectifying area for fully and uniformly mixing the liquid, at least one primary coalescence area filled with coalescence media and an oil-phase and water-phase outlet separation area according to the flow sequence of the flat waste liquid; the base material of the coalescence medium is a composite fiber formed by weaving polytetrafluoroethylene fibers and stainless steel wires in a mixed mode; the contact angle of the polytetrafluoroethylene fiber and the surface of water is 120-130 degrees, and the contact angle of the polytetrafluoroethylene fiber and oil is 40-45 degrees;
(4) and (4) concentrating the liquid separated from the water phase outlet in the step (3) by a forward osmosis membrane and recycling the liquid in the production link.
As a further improvement of the technical scheme, the step (2) also comprises a backwashing step, wherein the backwashing frequency is once every 45-60min, the single backwashing time is not less than 30s, and normal-temperature industrial water is selected for backwashing.
As a further improvement of the technical scheme, the step (2) also comprises the step of irregularly cleaning the filter membrane by adopting an alkaline mixed solution of NaClO with the mass percent concentration of 5-10% and NaOH with the mass percent concentration of 1-2% as a cleaning agent.
And (3) leading the leveled waste liquid into a coalescent oil-water separator, wherein the hydraulic retention time is 45-60 min.
As a further improvement of the technical scheme, the polytetrafluoroethylene fibers in the step (3) are modified by high temperature and sulfuric acid.
In a preferred embodiment of the present invention, in the step (3), the stainless steel wires and the polytetrafluoroethylene fibers with a diameter of 80-90 μm are twisted and combined into a single-strand composite fiber at a ratio of 1:1, and the resultant single-strand composite fiber is filled in the polymerization zone with a porosity (i.e., standard porosity) of 0.977.
Also as one of the preferred embodiments of the present invention, the forward osmosis membrane in step (4) has a 3-layer structure, which is sequentially a dense skin layer and a porous support layer that are hydrophilic and electrically neutral, and a grid support structure layer.
Also as a further improvement of the technical proposal, the water body in the step (4) is 15-25m3The flow velocity of the flow velocity/h flows on the low osmotic pressure side of the forward osmosis membrane, and the high osmotic pressure side of the forward osmosis membrane circulates by taking the flattening medicament stock solution as an extraction solution.
As another preferred embodiment of the present invention, the pore size of the filter membrane in step (2) is 0.1 μm; in the step (3), the contact angle between the polytetrafluoroethylene fiber and oil is 45 degrees; the mixed weaving condition of the polytetrafluoroethylene fibers and the stainless steel wires is that the stainless steel wires with the diameter of 90 mu m and the polytetrafluoroethylene fibers are twisted into single-strand composite fibers according to the ratio of 1: 1.
The invention provides a cold rolling leveling waste liquid treatment method which is simple in process and capable of recycling. The main pollutants in the leveling waste liquid are removed by using a filtering and coalescence separation method, pure water in the waste liquid is recovered by using a forward osmosis process, and meanwhile, the effective components in the waste liquid are concentrated, so that the whole treatment process is safe and stable, the leveling waste liquid can be recycled, and the method has good economic benefits and environmental benefits.
The method applies the forward osmosis process to the treatment flow of the leveling waste liquid with high organic concentration generated by the cold rolling unit, simplifies the treatment flow and realizes the resource recovery of the leveling waste liquid.
Drawings
FIG. 1 is a schematic process flow diagram of the process of the present invention;
FIG. 2 is a schematic view of a coalescer oil water separator;
fig. 3 is a schematic diagram of the forward osmosis principle.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
The invention provides a cold rolling leveling waste liquid treatment method based on forward osmosis theory, which comprises the process steps of filtering, oil-water two-phase separation and forward osmosis. The system comprises a paper tape filter, a tubular microfiltration device, a coalescence oil-water separator and a forward osmosis device which are sequentially connected, wherein the forward osmosis device is connected with an absorption liquid circulating device and a recovery device of the treated waste leveling liquid. The method effectively removes two main pollutants, namely particles and oil, in the leveling waste liquid, effectively reduces the consumption of a large amount of new water for diluting the leveling agent stock solution in the leveling process, and provides possibility for recycling the leveling liquid.
Referring to the related processes and structures of fig. 1 to 2, the specific processing steps and conditions are as follows:
(1) and paper tape filtration:
the filtering process comprises two system links of paper tape filtering and tubular microfiltration, and the tubular microfiltration is arranged at the rear end of the paper tape filtering. The invention uses a gravity plate type paper tape filter, the filtering precision is 15-30 microns, solid impurities in the leveling waste liquid are filtered by non-woven fabrics to form filter cakes, the thicker the filter cakes are (the thickness can reach more than 15 mm), so that the liquid level of the dirty liquid rises, a floating ball of a liquid level relay floats, a speed reducer is started and dragged to replace the non-woven fabrics, filter residues fall into a filter residue box, and waste non-woven fabrics are rolled up by the speed reducer; after the non-woven fabric is updated, the liquid level of the dirty liquid drops, the speed reducer stops rotating, and the equipment enters the next purification cycle. The liquid filtered by the paper tape filter enters tubular microfiltration.
(2) And tubular microfiltration:
the flat waste liquid after the primary treatment of the paper tape filtration is 20-30m3The flow rate of the water enters a tubular microfiltration membrane at a flow rate of/h, the aperture of the filtration membrane is 0.1 mu m, the backwashing is carried out once every 45 to 60min, the backwashing time is 30s, and normal-temperature industrial water is used for the backwashing. And (3) cleaning the membrane by using an alkaline mixed solution of 5-10% of NaClO and 1-2% of NaOH in percentage by mass as a cleaning agent every month to remove organic pollutants. The effluent after tubular microfiltration enters a coalescent oil-water separator to remove oil.
(3) And a coalescent oil-water separator:
the solid impurities of the flat waste liquid treated by the filtering process can be removed by more than 95 percent, SS is less than 10mg/L, the flat waste liquid meets the water inlet requirement of a coalescence oil-water separator, and the hydraulic retention time is 45-60min after the flat waste liquid enters the oil-water separator. The coalescence oil-water separator is a self-processing non-standard device, and is a non-commercial circulation device for scientific research results, the internal structure of the coalescence oil-water separator consists of a rectifying area and a coalescence area, and the rectifying area aims to perfect fluid distribution and fully mix liquid so as to improve the oil-water separation efficiency; the coalescence area is an oil-water separation core part, the interior of the coalescence area is filled with modified polytetrafluoroethylene +304 mixed-woven composite filler (namely coalescence medium), and the structure can adopt the arrangement form of one or more coalescence areas. Wherein, the polytetrafluoroethylene fiber is modified by sulfuric acid and high temperature, so that the contact angle of the polytetrafluoroethylene fiber and the surface of water is 120-130 degrees, the hydrophobicity is enhanced, and the contact angle of the polytetrafluoroethylene fiber and oil is 45 degrees, thus being oleophilic and hydrophobic; 304 stainless steel wire, having a diameter of 90 μm, was used in a ratio of 1: the fiber was twisted into a single strand composite fiber at a ratio of 1, and the fiber was uniformly filled in a separation chamber of an oil-water separator at a void ratio of 0.977. The filler is super-oleophylic and hydrophobic, oil-containing wastewater flows through the surface of the filler, oil drops are adsorbed on the surface of the filler, a water phase passes through the filler, and the oil drops are accumulated and gathered on the surface of the filler continuously and fall off and float up from the surface of the material after being gathered into large oil drops, so that two-phase separation is realized. After the inflow water is rectified and coalesced, the oil phase as a light phase is discharged from the upper end of the equipment, and the water phase as a heavy phase is discharged from the bottom of the equipment, thereby realizing the oil-water separation of the waste liquid. The structure of the coalesced oil-water separator is shown in figure 2 of the accompanying drawings. After the liquid enters from the feed inlet and is treated by the rectifying area and the coalescence area, the oil phase and the water phase are separated and are respectively discharged from an oil phase outlet at the upper part and a water phase outlet at the lower part.
(4) And forward osmosis:
forward Osmosis (FO) is a concentration-driven membrane separation technology, and is a membrane separation process that does not require external pressure as a driving force and only relies on osmotic pressure for driving. In the forward osmosis process, water flows from a region on the low osmotic pressure side to a region on the higher osmotic pressure side through the permselective membrane. Unlike reverse osmosis, the driving force of forward osmosis is osmotic pressure rather than external pressure, manual pressurization is not required, and scaling is greatly reduced compared with other membrane treatment methods. The coalesced oil water separator effluent entered a forward osmosis unit using a forward osmosis membrane purchased from HTI corporation of america, with a 3-layer structure: a dense skin layer, a porous support layer and a lattice support structure. The membrane skin and porous support layers are hydrophilic, electrically neutral and approximately 50 μm thick. The water body is 15-25m3The flow velocity of/h flows on one side of the forward osmosis membrane (low osmotic pressure side), the other side of the forward osmosis membrane uses the flat medicament stock solution as a drawing solution to circulate (namely, high osmotic pressure side area), water in the flat waste liquid enters the flat medicament stock solution through the selective permeation membrane, so that the flat medicament stock solution is diluted to a certain extent, and meanwhile, the medicament active ingredients in the flat waste liquid are concentrated. The leveling agent stock solution can become the use solution only by diluting to 1% -5%, and pure water for dilution can be reduced through the dilution effect of forward osmosis; the leveling waste liquid is pretreated to remove two main pollutants of solid particles and oil, and after forward osmosis, the residual effective components are concentrated and can be returned to the production link for recycling.
As shown in fig. 3, which is a schematic diagram of the forward osmosis principle, the movement of pure water with respect to a forward osmosis membrane is illustrated.
Claims (9)
1. A cold rolling flattening solution treatment method based on forward osmosis theory is characterized by comprising the following steps:
(1) carrying out paper tape filtration on the flat waste liquid, wherein the filtration precision is 15-30 microns;
(2) the flat waste liquid after the primary treatment of the paper tape filtration is 20-30m3The flow rate of the solution/h enters a tubular microfiltration membrane for tubular microfiltration, and the aperture of the membrane is 0.1-0.3 mu m; filtering until solid impurities in the flat waste liquid are removed by more than 95 percent, and SS is less than 10 mg/L;
(3) introducing the flat waste liquid treated in the step (2) into a coalescence oil-water separator, wherein the coalescence oil-water separator is sequentially provided with a rectifying area for fully and uniformly mixing the liquid, at least one primary coalescence area filled with coalescence media and an oil-phase and water-phase outlet separation area according to the flow sequence of the flat waste liquid; the base material of the coalescence medium is a composite fiber formed by weaving polytetrafluoroethylene fibers and stainless steel wires in a mixed mode; the contact angle of the polytetrafluoroethylene fiber and the surface of water is 120-130 degrees, and the contact angle of the polytetrafluoroethylene fiber and oil is 40-45 degrees;
(4) and (4) concentrating the liquid separated from the water phase outlet in the step (3) by a forward osmosis membrane and recycling the liquid in the production link.
2. The cold rolling temper rolling process based on the forward osmosis theory as claimed in claim 1, wherein the step (2) further comprises a step of backwashing, the frequency of backwashing is once every 45-60min, the time of single backwashing is not less than 30s, and normal-temperature industrial water is selected for backwashing.
3. The cold rolling temper rolling liquid processing method based on the forward osmosis theory as claimed in claim 2, wherein the step (2) further comprises the step of irregularly cleaning the filter membrane by using an alkaline mixed solution of NaClO with the mass percentage concentration of 5-10% and NaOH with the mass percentage concentration of 1-2% as a cleaning agent.
4. The cold rolling temper rolling process based on forward osmosis theory according to claim 1, wherein the hydraulic retention time of the temper rolling waste liquid in the step (3) after being introduced into the coalesced oil-water separator is 45-60 min.
5. The cold rolling temper rolling process based on the forward osmosis theory according to claim 1 or 4, wherein the polytetrafluoroethylene fibers in the step (3) are modified by high temperature and sulfuric acid.
6. The cold-rolling temper mill fluid treatment method based on forward osmosis theory according to claim 1 or 4, wherein the condition of the mixture weaving of the polytetrafluoroethylene fibers and the stainless steel wires in the step (3) is that the stainless steel wires with the diameter of 80-90 μm and the polytetrafluoroethylene fibers are twisted into single-strand composite fibers in a ratio of 1:1 and then filled in the condensation zone with the void ratio of 0.977.
7. The cold rolling temper rolling liquid treatment method based on forward osmosis theory as claimed in claim 1, wherein the forward osmosis membrane in the step (4) has a 3-layer structure, and sequentially comprises a compact skin layer and a porous support layer which are hydrophilic and neutral, and a grid support structure layer.
8. The cold rolling temper rolling process based on forward osmosis theory according to claim 1, wherein the water body in the step (4) is 15-25m3The flow velocity of the flow velocity/h flows on the low osmotic pressure side of the forward osmosis membrane, and the high osmotic pressure side of the forward osmosis membrane circulates by taking the flattening medicament stock solution as an extraction solution.
9. The cold rolling temper rolling process based on the forward osmosis theory according to claim 6, wherein the pore size of the filter membrane in the step (2) is 0.1 μm; in the step (3), the contact angle between the polytetrafluoroethylene fiber and oil is 45 degrees; the mixed weaving condition of the polytetrafluoroethylene fibers and the stainless steel wires is that the stainless steel wires with the diameter of 90 mu m and the polytetrafluoroethylene fibers are twisted into single-strand composite fibers according to the ratio of 1: 1.
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