CN112358097A - Method and device for strengthening high-electrolyte wastewater treatment by multiple physical fields - Google Patents
Method and device for strengthening high-electrolyte wastewater treatment by multiple physical fields 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for strengthening high electrolyte wastewater treatment by multiple physical fields, which is characterized by comprising the following steps of: introducing high-electrolyte wastewater into a reactor provided with more than one anion filtering component and more than one cation filtering component, wherein the anion filtering component and the cation filtering component are alternately arranged at intervals in the reactor, and because the membrane has an interception effect on electrolyte anions and cations and insoluble matters, the two ends of the filtering component keep certain water head pressure, and meanwhile, an electric field is applied to the anion filtering component and the cation filtering component, so that the wastewater passes through the anion filtering component and the cation filtering component to complete the purification treatment of the high-electrolyte wastewater, and when the number of attachments on the filtering component is large, the membrane is cleaned by ultrasonic; the method has the advantages of high desalting effect, low cost, simple technical operation and easy realization, and is favorable for the regeneration, the cyclic utilization, the market popularization and the application of high electrolyte wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method and a device for high-electrolyte wastewater treatment through multi-physical-field enhanced regulation and control.
Background
The high-salinity wastewater refers to concentrated waste liquid which is difficult to biochemically treat and has mass fraction of Total Dissolved Solids (TDS) of more than 8 percent and is obtained by evaporating or treating generated strong brine through other desalination technologies after most of 'fresh water' is recovered from standard discharged water through a reverse osmosis technology; or the wastewater which is directly generated in the chemical production process, has high COD content, has the Total Dissolved Solids (TDS) mass fraction of more than 15 percent and can not be biochemically treated. In order to thoroughly and radically treat the pollution of the high-salinity wastewater, the COD content of the high-salinity wastewater is reduced, and more importantly, the soluble salt substances are completely separated from the wastewater. Only then, the treatment target of the high-salinity wastewater can be really achieved. The pharmaceutical manufacturing process also produces large amounts of high salinity wastewater. According to statistics, pesticide production plants in China reach about 1600 families, and the annual output of pesticides reaches 47.6 ten thousand tons. Wherein, the production of the organophosphorus pesticide accounts for more than 50 percent of the pesticide industry. The pesticide wastewater is characterized in that: high concentration of organic matter, complex pollution components, high toxicity, difficult degradation, unstable water quality and the like. For example, in the production process of herbicide glyphosate, phosphate and sodium chloride wastewater with high concentration can be generated in the process of concentrating the mother liquor, the COD of the wastewater is about 50000mg/L, and the content of salts can reach 150 g/L. For the high COD and high salinity pesticide wastewater, effective treatment measures are required to be taken for treatment. Otherwise, serious environmental pollution is caused.
Because the synthetic pharmaceutical wastewater contains a large amount of salt, such as: sulfate, carbonate, nitrate, phosphate, organic salt and the like, wherein the desalting technology becomes the highest stage of the whole process cost in the treatment process of pharmaceutical wastewater, the common treatment technologies of the high-salinity wastewater at present comprise a membrane distillation technology, an incineration technology, an evaporation concentration-cooling crystallization technology and an evaporation-thermal crystallization technology, the technologies are used for treating the high-salinity wastewater to obtain part of high-salinity wastewater besides part of fresh water, and further treatment is needed to realize the complete separation of soluble salt substances, the salt content in the wastewater can influence the microbial activity and has obvious influence on organic degradation, and the degradation rate of organic substances is reduced along with the increase of salinity; the prior salt-containing wastewater treatment method comprises the traditional physical and chemical treatment methods such as distillation, fractional precipitation and the like, the biological treatment methods such as aerobic granular sludge, a biological filter and the like, and the physical and chemical combined treatment method. With the gradual improvement of membrane process technology, membrane separation treatment methods for salt-containing wastewater are receiving more and more attention. The membrane separation method comprises the process types of electrodialysis membranes, microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes and the like, and due to the particularity of membrane equipment, incoming water generally needs to be pretreated so as to prevent the occurrence of faults affecting the normal operation of the membrane system, such as membrane surface damage, membrane hole blockage and the like. The pharmaceutical wastewater desalination technology is a key technology for pharmaceutical wastewater treatment, pharmaceutical wastewater components are complex, if a membrane separation technology is applied, serious membrane pollution can be caused, and the problem of treatment of a subsequent polluted membrane is difficult to solve. Therefore, the removal of salt in pharmaceutical wastewater becomes a key technical problem in the current pharmaceutical wastewater treatment.
Patent CN201610316243.5 discloses a method for separating salt from coal chemical wastewater by electrodialysis technology, which uses the characteristics of electrodialysis to separate and concentrate salt to separate salt, and the application range of the desalination technology is not wide, especially not suitable for high-concentration organic wastewater with complex components; the patent CN201710440084.4 discloses a salt separation, concentration and solidification treatment system and method for high-salt and easily-scaling wastewater, and the method adopts multiple filtration and multiple electrodialysis coupling to remove salt, so that the process is complex and tedious, and the cost is high.
Disclosure of Invention
Aiming at the problems of low desalting efficiency, incomplete desalting, high cost, easy secondary pollution in the desalting process and the like in the existing high-salinity wastewater treatment technology, in particular to synthetic pharmaceutical wastewater with complex components, the method mainly adopts membrane separation, electrochemical technology and ultrasonic cleaning coupled desalination, high electrolyte wastewater passes through a cation and anion selective permeation membrane with a certain distance, the membrane is fixed by two conductive screens to form a filtering component, certain water head pressure is kept, an electric field is applied to the conductive screens, the voltage is 1-36V, under the action of the membrane, the voltage and a certain hydraulic pressure head, anions, cations and insoluble substances in the flowing high electrolyte wastewater are quickly isolated on the wastewater side of the membrane and are attached to the membrane, the substances attached to the membrane are sunk by an ultrasonic means, so that high electrolyte wastewater treatment is achieved to achieve a good effect; the technology has the advantages of high desalting effect, low cost, simple technical operation and easy realization, is favorable for recycling the synthesized pharmaceutical wastewater, belongs to integrated equipment, and is convenient to be applied as a movable component.
The method comprises introducing high electrolyte wastewater into a reactor provided with more than one anion filter assembly and more than one cation filter assembly at a flow rate of 0.5-1.5 m/s, wherein the anion filter assembly or the cation filter assembly is composed of two conductive screens sandwiching an anion selective permeable membrane or a cation selective permeable membrane, the anion filter assembly and the cation filter assembly are alternately arranged at intervals in the reactor, because the membrane has the interception function to electrolyte anions and cations and indissolvable substances, the two ends of the filtering component keep a certain water head pressure, and meanwhile, electric fields are applied to the anion filtering assembly and the cation filtering assembly, so that the wastewater passes through the anion filtering assembly and the cation filtering assembly to complete the purification treatment of high-electrolyte wastewater treatment, and when more attachments are attached to the filtering assembly, membrane cleaning is carried out by ultrasonic.
The membrane separation mainly adopts an anion selective permeable membrane and a cation selective permeable membrane to isolate anions and cations in the high-salinity wastewater and improve the treatment effect of the high-salinity wastewater, the anion selective permeable membrane or the cation selective permeable membrane used in the invention is a conventional commercially available product, the cation exchange membrane is one of CMX, CIMS and CMB, and the anion exchange membrane is one of AMX, AHA, ACS, AFN, AFX and ACM.
The electrochemical treatment technology is mainly used for enhancing the isolation effect of anions and cations in the high-salinity wastewater by using an electric field, and the voltage of the electric field is 1-36V.
The ultrasonic cleaning technology mainly applies an ultrasonic method to make substances attached to the membrane fall off, so that membrane pollution is prevented, the service life and the treatment efficiency of the membrane are enhanced, and the replacement frequency of the membrane is reduced.
The flow speed of the wastewater is 0.5-1.5 m/s, and the wastewater passes through the filtering component under the action of the water head pressure, so that the membrane is prevented from being broken due to overlarge pressure.
The membrane on one side of the wastewater in the reactor is an anion selective permeable membrane, the membrane on the clean water side is a cation selective permeable membrane, and the distance between an anion filtering component and a cation filtering component is 5 cm-150 cm.
The anion filtering component and the cation filtering component are respectively connected with a power supply, the water inlet side is connected with a positive electrode, and the water outlet side is connected with a negative electrode.
The grid size of the conductive mesh screen is 100-500 meshes.
The temperature of the treated wastewater is 0-100 ℃, and the pH = 2-11.
The invention also provides a multi-physical field reinforced high electrolyte wastewater treatment device, which comprises an anion filter assembly, a cation filter assembly, a water outlet II, a water outlet I, a clapboard, a salt discharge port, an ultrasonic generator, a water inlet tank, a water inlet, a shell and a water outlet tank, wherein the anion filter assembly or the cation filter assembly is composed of two conductive screens clamping an anion selective permeable membrane or a cation selective permeable membrane, the shell is divided into the water inlet tank and the water outlet tank by the clapboard, the water outlet II is arranged at the upper part of the clapboard and communicated with the water inlet tank and the water outlet tank, the cation filter assembly is arranged at the water outlet II and tightly matched with the water outlet II, the anion filter assembly is arranged at the left side of the cation filter assembly and tightly matched with the side wall of the water inlet tank, the water inlet is arranged at one side of the upper part of the water inlet tank, a flow control valve is arranged on the water inlet tank, the bottom of the, the bottom of the water outlet pool is provided with a water outlet I, and the anion filtering component and the cation filtering component are respectively connected with a power supply.
Clamping grooves are formed in the installation positions of the anion filtering component and the cation filtering component, and the anion filtering component and the cation filtering component are tightly matched with the clamping grooves through adhesive tapes; when a plurality of filtering components are arranged, a mode of alternately arranging yin and yang is adopted.
The use method of the device comprises the following steps:
(1) the filter assembly is installed, so that the filter assembly is tightly combined with the side wall of the reactor, and the wastewater is prevented from leaking;
(2) the flow of the waste water is adjusted to reduce the impact load of the membrane, so as to prevent the membrane from being damaged and ensure the quality of the effluent;
(3) applying a voltage to the filter assembly; separating salt anions and cations;
(4) the membrane is cleaned by ultrasonic, so that the membrane is prevented from being polluted and blocked, and the treatment effect is prevented from being influenced;
(5) and (5) immediately discharging salt.
The method and the device for the multi-physical-field enhanced regulation and control of the high-electrolyte wastewater treatment have the working principle that: the high electrolyte wastewater flows into the reactor at low speed, the reactor is separated by a filter assembly, the filter assembly is the treatment core of the high electrolyte wastewater, the component is composed of two pieces of conductive screen screens clamping an ion selective permeable membrane, the filtering component in the reactor is composed of two components, wherein the membrane on one side of the wastewater is an anion selective permeable membrane, the cation selective permeable membrane is on the water purification side, a certain distance of 5 cm-150 cm is kept between the two components, the positive and negative electricity of a power supply is respectively connected on two conductive screens of the anion and cation selective permeable membrane, when the wastewater passes through the anion selective permeable membrane, cations and other difficultly-compatible substances are isolated in a wastewater area, and under the action of an electric field, due to the acting force of the electric field, positively charged substances are repelled in the wastewater area and cannot approach the assembly, and anions quickly pass through the anion selective permeation membrane to enter the middle area under the combined action of the electric field and the hydraulic pressure head; when the positive ions selectively permeate the membrane assembly, the negatively charged substances are adsorbed on the surface of the membrane, and in the whole process, as the electric fields are respectively applied, the electro-deposition principle and the redox effect are generated, so that the charge of the whole system is conserved; the substances attached to the membrane fall off by intermittent ultrasound, and the substances difficult to dissolve in the wastewater are easy to settle and collect due to the inclined structure at the bottom of the wastewater area of the reactor, so that the high-efficiency treatment of the high-salinity wastewater is achieved.
The method has the advantages and the technical effects that:
(1) the recovery of salt in the wastewater with high salt content is promoted, and the treatment cost of the wastewater is reduced;
(2) the effluent quality has less salt content, which is beneficial to further advanced treatment of water;
(3) the recovery rate of salt is high;
(4) the required conditions are simple and easy to reach;
(5) the operation is simple, and the further treatment of the wastewater is convenient;
(6) the device is an integrated device and is convenient to move.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention;
FIG. 2 is a schematic view of a filter assembly;
in the figure: 1-an anion filter assembly; 2-a cation filtration module; 3-water outlet II; 4-water outlet I; 5-a separator; 6-salt discharge port; 7-an ultrasonic generator; 8-a water inlet pool; 9-a water inlet; 10-a flow control valve; 11-a housing; 12-a water outlet pool; 13-cation (anion) permselective membranes; 14-conductive screen.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples, but the scope of the present invention is not limited to the description.
Example 1: the salt content of certain synthetic pharmaceutical wastewater is 35% of TDS content, and the synthetic pharmaceutical wastewater is purified by adopting a multi-physical field enhanced high-electrolyte wastewater treatment device shown in figure 1, wherein the device comprises an anion filter assembly 1, a cation filter assembly 2, a water outlet II 3, a water outlet I4, a partition plate 5, a salt discharge port 6, an ultrasonic generator 7, a water inlet tank 8, a water inlet 9, a shell 11 and a water outlet tank 12, the anion filter assembly is formed by clamping an anion selective permeable membrane by two conductive screens, the conductive screen on the water inlet side of the anion filter assembly is connected with a positive electrode of a power supply, and the conductive screen on the water outlet side of the anion filter assembly is connected with a negative electrode of the power supply; the cation filtering component is composed of two conductive screens 14 which sandwich a cation selective permeable membrane 13, the conductive screen at the water inlet side of the cation filtering component is connected with the positive electrode of a power supply, and the conductive screen at the water outlet side of the cation filtering component is connected with the negative electrode of the power supply; the distance between the anion filtering component and the cation filtering component is 10 cm; the mesh size of the conductive mesh screen is 200 meshes; wherein the cation selective permeation membrane is a CIMS membrane, and the anion membrane is an AFN membrane; the interior of the shell 11 is divided into a water inlet pool 8 and a water outlet pool 2 by a partition plate 5, the upper part of the partition plate is provided with a water outlet II 3 and communicates the water inlet pool 8 and the water outlet pool 12, the cation filtering component 12 is arranged at the water outlet II 13, the anion filtering component 1 is arranged at the left side of the cation filtering component 12, the mounting positions of the anion filtering component 1 and the cation filtering component 12 are both provided with clamping grooves, and the anion filtering component 1 and the cation filtering component 12 are tightly matched with the clamping grooves through adhesive tapes; a water inlet 9 is formed in one side of the upper portion of the water inlet pool 8, a flow control valve 10 is arranged on the water inlet 9, the bottom of the water inlet pool 8 is obliquely arranged towards the direction of the water outlet pool 12 and is provided with a salt discharging port 6, a water outlet I4 is formed in the bottom of the water outlet pool 12, the anion filtering component 1 and the cation filtering component 2 are respectively connected with a power supply, and valves are arranged on the water outlet I4 and the salt discharging port 6;
the specific method for separating the salt in the synthetic pharmaceutical wastewater comprises the following steps:
(1) installing a filtering component, and checking whether the combination tightness of the filtering component and the side wall of the reactor is good or not;
(2) introducing the high electrolyte wastewater into a water inlet pool at the flow rate of 0.8m/s, and simultaneously applying 12V voltage to an anion filtering component and a cation filtering component respectively;
(3) removing attachments on the filter assembly by intermittent ultrasonic treatment in the treatment process; the attachments cleaned from the filtering component fall to the bottom of the water inlet pool under the action of gravity, and are collected and dried through the salt discharge port 6;
the TDS content in the treated water is 0.7%, and the desalting rate can reach 98%, which shows that the method and the device can realize the purification of high electrolyte wastewater.
Example 2: the salt content of a certain high-salt-content wastewater is 45% of TDS, a multi-physical field enhanced high-electrolyte wastewater treatment device shown in figure 1 is adopted to complete the purification treatment of the high-salt-content wastewater, the structure of the device is the same as that of example 1, and the device is different in that 2 anion filter assemblies and 2 cation filter assemblies are arranged, the anion filter assemblies and the cation filter assemblies are alternately arranged at intervals, the interval distance is 5cm, and the mesh size of a conductive mesh screen is 300 meshes; wherein the cation selective permeable membrane is a CMX membrane and the anion membrane is an ACM membrane.
The specific method for separating the salt in the synthetic pharmaceutical wastewater comprises the following steps:
(1) installing a filtering component, and checking whether the combination tightness of the filtering component and the side wall of the reactor is good or not;
(2) introducing the high electrolyte wastewater into a water inlet pool at the flow rate of 1.2m/s, and simultaneously applying 36V voltage to an anion filtering assembly and a cation filtering assembly respectively;
(3) removing attachments on the filter assembly by intermittent ultrasonic treatment in the treatment process; the attachments cleaned from the filtering component fall to the bottom of the water inlet pool under the action of gravity, and are collected and dried through the salt discharge port 6;
the TDS content in the treated water is 0.3%, and the desalting rate can reach 99.3%, which shows that the method and the device can realize the purification of high electrolyte wastewater.
Claims (6)
1. A method for strengthening high electrolyte wastewater treatment by multiple physical fields is characterized by comprising the following steps: the method comprises the steps of introducing high-electrolyte wastewater into a reactor provided with more than one anion filtering component and more than one cation filtering component at a flow speed of 0.5-1.5 m/s, wherein the anion filtering component or the cation filtering component is formed by clamping an anion selective permeable membrane or a cation selective permeable membrane by two conductive screen meshes, and the anion filtering component and the cation filtering component are alternately arranged at intervals in the reactor.
2. The method of multiphysics enhanced high electrolyte wastewater treatment according to claim 1, wherein: the distance between the anion filtering component and the cation filtering component is 5 cm-150 cm.
3. The method of multiphysics enhanced high electrolyte wastewater treatment according to claim 1, wherein: the conducting screen on the wastewater side is positively charged, the conducting screen on the water purification side is negatively charged, the voltage of an electric field is 1-36V, and each component is charged.
4. The method of multiphysics enhanced high electrolyte wastewater treatment according to claim 1, wherein: the grid size of the conductive mesh screen is 100-500 meshes.
5. Apparatus for performing the method of multiphysics enhanced high electrolyte wastewater treatment of any of claims 1-4, wherein: comprises an anion filtering component (1), a cation filtering component (2), a water outlet II (3), a water outlet I (4), a clapboard (5), a salt discharge port (6), an ultrasonic generator (7), a water inlet pool (8), a water inlet (9), a shell (11) and a water outlet pool (12), wherein the anion filtering component or the cation filtering component is composed of two conductive screens (14) which sandwich an anion selective permeable membrane or a cation selective permeable membrane, the shell (11) is internally divided into the water inlet pool (8) and the water outlet pool (2) through the clapboard (5), the upper part of the clapboard is provided with the water outlet II (3) and communicates the water inlet pool (8) and the water outlet pool (12), the cation filtering component (2) is arranged at the water outlet II (3) and is tightly matched with the water outlet II (3), the anion filtering component (1) is arranged at the left side of the cation filtering component (2) and is tightly matched with the side wall of the, a water inlet (9) is formed in one side of the upper portion of the water inlet pool (8), a flow control valve (10) is arranged on the water inlet (9), the bottom of the water inlet pool (8) is obliquely arranged towards the direction of the water outlet pool (12) and is provided with a salt discharging port (6), a water outlet I (4) is formed in the bottom of the water outlet pool (12), and the anion filtering component (1) and the cation filtering component (2) are respectively connected with a power supply.
6. The apparatus of claim 5, wherein: the installation positions of the anion filtering component (1) and the cation filtering component (2) are provided with clamping grooves, and the anion filtering component (1) and the cation filtering component (2) are tightly matched with the clamping grooves through adhesive tapes.
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