CN113603309A - Treatment method of gas-making circulating wastewater - Google Patents
Treatment method of gas-making circulating wastewater Download PDFInfo
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- CN113603309A CN113603309A CN202111043933.5A CN202111043933A CN113603309A CN 113603309 A CN113603309 A CN 113603309A CN 202111043933 A CN202111043933 A CN 202111043933A CN 113603309 A CN113603309 A CN 113603309A
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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
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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
- C02F1/46104—Devices therefor; Their operating or servicing
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
Abstract
The invention discloses a method for treating gas-making circulating wastewater, which comprises the following steps: s1, standing and precipitating the circulating wastewater, adjusting the pH value of the wastewater to 4-6, and filtering the precipitate to obtain upper-layer turbid liquid; s2, feeding the upper layer turbid liquid into an iron-carbon micro-electrolysis reactor, introducing air for reacting for 2-3h, and then discharging the iron-carbon micro-electrolysis reactor to obtain primary wastewater; s3, adding a cyanogen breaking agent into the primary wastewater, wherein the cyanogen breaking agent accounts for 15-30% of the mass of the primary wastewater, then blowing air for aeration for 1-3h, and filtering to obtain secondary wastewater; s4, the secondary wastewater is sent into the anaerobic tank and the aerobic tank in turn, and can be directly discharged after biochemical treatment.
Description
Technical Field
The invention relates to the technical field of gas-making wastewater treatment, and particularly belongs to a gas-making circulating wastewater treatment method.
Background
At present, gas-making circulating wastewater is discharged from various production wastewater in a whole plant area, and is evaporated and concentrated for many years, so that the gas-making circulating wastewater is complex in components and contains various toxic and harmful substances. Such as a large number of cyanide, sulfide, etc. Meanwhile, the concentration of organic pollutants is high, the COD is as high as 50000mg/L, and the content of ammonia nitrogen is ultrahigh and is close to 30000 mg/L. Others such as high salt, high hardness, etc. Severely limiting its possibility to go directly into the biochemical system for processing.
At present, gas-making circulating water is mainly subjected to water quantity digestion by limited decrement means such as evaporation and the like. Is greatly influenced by weather, temperature and the like. The operation of the gas-making circulating water is seriously influenced by the reduction of a large amount of discharged gas-making circulating water and limited water amount. Therefore, in order to increase the treatment way of the gas-making circulating wastewater, aiming at the pollutant characteristics of the gas-making circulating wastewater and the water inlet requirement of a biochemical system, a new treatment scheme for the gas-making circulating wastewater is urgently developed. The invention provides a new treatment way for the gas-making circulating wastewater and a new solution basis for the gas-making circulating wastewater reduction.
Disclosure of Invention
The invention aims to provide a treatment method of gas-making circulating wastewater, which overcomes the defects of the prior art.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a treatment method of gas-making circulating wastewater comprises the following steps:
s1, standing and precipitating the circulating wastewater, adjusting the pH value of the wastewater to 4-6, and filtering the precipitate to obtain upper-layer turbid liquid;
s2, feeding the upper layer turbid liquid into an iron-carbon micro-electrolysis reactor, introducing air for reacting for 2-3h, and then discharging the iron-carbon micro-electrolysis reactor to obtain primary wastewater;
s3, adding a cyanogen breaking agent into the primary wastewater, wherein the cyanogen breaking agent accounts for 15-30% of the mass of the primary wastewater, then blowing air for aeration for 1-3h, and filtering to obtain secondary wastewater;
and S4, sequentially feeding the secondary wastewater into an anaerobic tank and an aerobic tank, and directly discharging the wastewater after biochemical treatment.
Preferably, the method for preparing the iron-carbon filler in the iron-carbon micro-electrolysis reactor in the step S2 is as follows:
a1, immersing activated carbon particles into a saturated ferric chloride solution until the activated carbon is saturated in adsorption, taking out the activated carbon, and heating to 80-120 ℃ for drying to obtain iron-containing activated carbon;
a2, heating the iron-containing activated carbon to 800-1000 ℃ in a humid inert gas atmosphere, and cooling to room temperature to obtain the iron-carbon composite material;
a3, mixing copper powder, aluminum powder and activated carbon powder, firing at 1100-;
a4, mixing copper aluminum microspheres, iron carbon composite materials, clay, pore-forming agent, vermiculite and water uniformly, pressing into a filler blank, heating the filler blank to 380-.
Preferably, the mass ratio of the copper powder, the aluminum powder and the activated carbon powder is 3-5:6-8: 20-30.
Preferably, the mass ratio of the copper-aluminum microspheres to the iron-carbon composite material to the clay to the pore-forming agent to the vermiculite to the water is 3-5:10-15:8-12:2-3:1-3: 5-8.
Preferably, the pore former is calcium bicarbonate.
Preferably, the moist inert gas is water containing 10-20g/m3Carbon dioxide (c).
Preferably, the preparation method of the cyanogen breaker comprises the following steps: soaking diatomite into saturated aqueous solution containing copper ions, nickel ions and aluminum ions, adsorbing until the diatomite is saturated, taking out, soaking in aqueous solution containing 5-10 wt% of chelating agent for 3-6h, taking out and drying to obtain the cyanogen breaking agent.
Preferably, the chelating agent is diethylenetriaminepentaacetic acid.
Compared with the prior art, the invention has the following implementation effects:
1. according to the invention, through precipitation, the gas-making circulating sewage is treated by using the iron-carbon filler and the cyanogen breaker, the COD value and ammonia nitrogen content of the sewage are greatly reduced, and the sewage can meet the water inlet requirement of biochemical treatment.
2. According to the invention, the activated carbon is used for reacting with steam, iron ions adsorbed by the activated carbon are reduced into elemental iron at high temperature, and simultaneously, in the process of reducing the elemental iron, carbon atoms around the elemental iron are consumed, so that a large number of elemental iron inlaying points and elemental iron containing spaces are formed in the activated carbon particles, and thus, when the iron carbon filler disclosed by the invention is used, the iron oxide refills the containing spaces in the activated carbon particles along with the oxidation of the elemental iron and the growth of the formed oxide, and simultaneously, the activated carbon prevents the aggregation growth of adjacent iron oxides, so that the problem that the iron carbon filler is easy to agglomerate is avoided. In addition, because the elemental iron in the iron-carbon filler is uniformly distributed in the active carbon particles, and the particles are smaller, the problem that the surface of the elemental iron is passivated to influence the water treatment effect is solved.
3. According to the invention, calcium bicarbonate is used as a pore-forming agent during the preparation of the iron-carbon filler, and is decomposed in the process of antipyresis of the filler blank, so that a large number of holes are formed in the filler blank, wastewater can be in full contact with effective components in the iron-carbon filler, and calcium carbonate formed by decomposition of calcium bicarbonate can neutralize wastewater and provide a calcium source. Improving the treatment effect.
4. According to the invention, the chelating agent is used for fixing the metal ions adsorbed by the diatomite, so that the metal ions are stably combined in the diatomite, and meanwhile, the chelating agent is an electron conjugation effect formed by carbon-carbon double bonds in the diethylenetriamine pentaacetic acid and amino and carboxyl, so that the activity of the metal ions is improved, and the cyanide decomposing capability of the cyanide breaking agent is promoted.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Firstly, the activated carbon is mixedSoaking the particles in a saturated ferric chloride solution until the activated carbon is saturated in adsorption, taking out the activated carbon, heating to 80 ℃ and drying to obtain iron-containing activated carbon; adding iron-containing activated carbon into water at the concentration of 10g/m3Heating to 800 ℃ in the carbon dioxide atmosphere, and cooling to room temperature to obtain the iron-carbon composite material; then, mixing 3kg of copper powder, 6kg of aluminum powder and 20kg of activated carbon powder, firing at 1100 ℃ for 0.2h in an inert gas atmosphere, and cooling to room temperature to prepare copper-aluminum microspheres; then, 3kg of copper-aluminum microspheres, 10kg of iron-carbon composite material, 8kg of clay, 2kg of pore-forming agent calcium bicarbonate, 1kg of vermiculite and 5kg of water are uniformly mixed and pressed into a filler blank, and then the filler blank is heated to 380 ℃, dried and cooled to obtain the iron-carbon filler.
Secondly, dissolving copper chloride, nickel chloride and aluminum chloride in water to prepare a saturated solution, then soaking diatomite into the saturated solution, taking out the diatomite, soaking the diatomite in an aqueous solution containing 5 wt% of chelating agent diethylene triamine pentaacetic acid for 3 hours, taking out the diatomite and drying the diatomite to obtain the cyanogen breaking agent.
Circulating wastewater COD 49862mg/L and ammonia nitrogen content 28791mg/L, when treating circulating wastewater, standing and precipitating the circulating wastewater, adjusting the pH of the wastewater to 4, and then filtering the precipitate to obtain upper-layer turbid liquid; then sending the upper layer turbid liquid into an iron-carbon micro-electrolysis reactor, filling iron-carbon filler in the iron-carbon micro-electrolysis reactor, introducing air for reaction for 2 hours, and then discharging the iron-carbon micro-electrolysis reactor to obtain primary wastewater; adding a cyanogen breaking agent into the primary wastewater, wherein the cyanogen breaking agent accounts for 30% of the mass of the primary wastewater, then blowing air for aeration for 1h, and filtering to obtain secondary wastewater; and (3) sequentially feeding the secondary wastewater into an anaerobic tank and an aerobic tank, and directly discharging the secondary wastewater after biochemical treatment. The treatment method runs for a week, the iron-carbon filler is not hardened, and the monitoring result is as follows: the treated water amount was 142m3And d, the COD concentration of the inlet water of the anaerobic tank is 193mg/L, the COD concentration of the outlet water of the aerobic tank is maintained at 29mg/L, the ammonia nitrogen concentration of the inlet water of the anaerobic tank is 27mg/L, and the ammonia nitrogen concentration of the outlet water of the aerobic tank is 1.1 mg/L.
Example 2
Firstly, immersing activated carbon particles into a saturated ferric chloride solution until activated carbon is saturated in adsorption, and thenTaking out the activated carbon, heating to 120 ℃, and drying to obtain iron-containing activated carbon; adding iron-containing activated carbon in water of 20g/m3Heating to 1000 ℃ in the atmosphere of carbon dioxide, and cooling to room temperature to obtain the iron-carbon composite material; then, mixing 5kg of copper powder, 8kg of aluminum powder and 30kg of activated carbon powder, firing for 1h at 1200 ℃ in an inert gas atmosphere, and cooling to room temperature to prepare copper-aluminum microspheres; then, 5kg of copper-aluminum microspheres, 15kg of iron-carbon composite material, 12kg of clay, 3kg of pore-forming agent calcium bicarbonate, 3kg of vermiculite and 8kg of water are uniformly mixed and pressed into a filler blank, and then the filler blank is heated to 450 ℃, dried and cooled to obtain the iron-carbon filler.
Secondly, dissolving copper chloride, nickel chloride and aluminum chloride in water to prepare a saturated solution, then soaking diatomite into the saturated solution, taking out the diatomite, soaking the diatomite in a 10 wt% aqueous solution containing chelating agent diethylenetriamine pentaacetic acid for 6 hours, taking out the diatomite and drying the diatomite to obtain the cyanogen breaking agent.
Circulating wastewater COD 49862mg/L and ammonia nitrogen content 28791mg/L, when treating circulating wastewater, standing and precipitating the circulating wastewater, adjusting the pH of the wastewater to 6, and then filtering the precipitate to obtain upper-layer turbid liquid; then sending the upper layer turbid liquid into an iron-carbon micro-electrolysis reactor, filling iron-carbon filler in the iron-carbon micro-electrolysis reactor, introducing air for reaction for 3 hours, and then discharging the iron-carbon micro-electrolysis reactor to obtain primary wastewater; adding a cyanogen breaking agent into the primary wastewater, wherein the cyanogen breaking agent accounts for 15% of the mass of the primary wastewater, then blowing air for aeration for 3h, and filtering to obtain secondary wastewater; and (3) sequentially feeding the secondary wastewater into an anaerobic tank and an aerobic tank, and directly discharging the secondary wastewater after biochemical treatment. The treatment method runs for a week, the iron-carbon filler is not hardened, and the monitoring result is as follows: the treated water amount is 134m3And d, the COD concentration of the inlet water of the anaerobic tank is 210mg/L, the COD concentration of the outlet water of the aerobic tank is maintained at 25mg/L, the ammonia nitrogen concentration of the inlet water of the anaerobic tank is 24mg/L, and the ammonia nitrogen concentration of the outlet water of the aerobic tank is 0.8 mg/L.
Example 3
Firstly, immersing activated carbon particles into a saturated ferric chloride solution until the activated carbon is saturated in adsorption, then taking out the activated carbon, and heating to 100 ℃ for drying to obtain iron-containing activated carbon; will be provided withIron-containing activated carbon in water of 13g/m3Heating to 900 ℃ in the carbon dioxide atmosphere, and cooling to room temperature to obtain the iron-carbon composite material; then, 4kg of copper powder, 7kg of aluminum powder and 26kg of activated carbon powder are mixed, fired for 0.5h at 1160 ℃ in the atmosphere of inert gas, and cooled to room temperature to prepare copper-aluminum microspheres; then, 3kg of copper-aluminum microspheres, 14kg of iron-carbon composite material, 9kg of clay, 2kg of pore-forming agent calcium bicarbonate, 2kg of vermiculite and 7kg of water are uniformly mixed and pressed into a filler blank, and then the filler blank is heated to 420 ℃, dried and cooled to obtain the iron-carbon filler.
Secondly, dissolving copper chloride, nickel chloride and aluminum chloride in water to prepare a saturated solution, then soaking diatomite into the saturated solution, taking out the diatomite, soaking the diatomite in a water solution containing 7 wt% of chelating agent diethylene triamine pentaacetic acid for 4 hours, taking out the diatomite and drying the diatomite to obtain the cyanogen breaking agent.
Circulating wastewater COD 49862mg/L and ammonia nitrogen content 28791mg/L, when treating circulating wastewater, standing and precipitating the circulating wastewater, adjusting the pH of the wastewater to 5, and then filtering the precipitate to obtain upper-layer turbid liquid; then sending the upper layer turbid liquid into an iron-carbon micro-electrolysis reactor, filling iron-carbon filler in the iron-carbon micro-electrolysis reactor, introducing air for reaction for 2 hours, and then discharging the iron-carbon micro-electrolysis reactor to obtain primary wastewater; adding a cyanogen breaking agent into the primary wastewater, wherein the cyanogen breaking agent accounts for 25% of the mass of the primary wastewater, then blowing air for aeration for 1.5h, and filtering to obtain secondary wastewater; and (3) sequentially feeding the secondary wastewater into an anaerobic tank and an aerobic tank, and directly discharging the secondary wastewater after biochemical treatment. The treatment method runs for a week, the iron-carbon filler is not hardened, and the monitoring result is as follows: the treated water amount is 150m3And d, the COD concentration of the inlet water of the anaerobic tank is between 162mg/L, the COD concentration of the outlet water of the aerobic tank is maintained at 23mg/L, the ammonia nitrogen concentration of the inlet water of the anaerobic tank is 22mg/L, and the ammonia nitrogen concentration of the outlet water of the aerobic tank is 0.4 mg/L.
Comparative example 1
The difference from example 3 is that the diatomaceous earth is not soaked with an aqueous solution of 7% by weight of the chelating agent diethylenetriaminepentaacetic acid. The circulating wastewater treatment process runs for one week, and the monitoring result is as follows: the amount of treated water was 100m3The COD concentration of the inlet water of the anaerobic tank is 562mgAnd the COD concentration of the effluent of the aerobic tank is maintained at 134mg/L, the ammonia nitrogen concentration of the influent of the anaerobic tank is 127mg/L, and the ammonia nitrogen concentration of the effluent of the aerobic tank is 62 mg/L.
Comparative example 2
The difference from example 3 is that the iron-containing activated carbon was heated to 900 ℃ in a dry inert gas atmosphere. The circulating wastewater treatment process runs for a week, the iron-carbon filler is slightly hardened, and the monitoring result is as follows: the amount of treated water was 100m3And d, the COD concentration of the inlet water of the anaerobic tank is 830mg/L, the COD concentration of the outlet water of the aerobic tank is maintained at 164mg/L, the ammonia nitrogen concentration of the inlet water of the anaerobic tank is 103mg/L, and the ammonia nitrogen concentration of the outlet water of the aerobic tank is 79 mg/L.
Comparative example 3
The difference from example 3 is that calcium bicarbonate was replaced by sodium bicarbonate. The circulating wastewater treatment process runs for a week, the iron-carbon filler is not hardened, and the monitoring result is as follows: the amount of treated water was 100m3And d, the COD concentration of the inlet water of the anaerobic tank is 1280mg/L, the COD concentration of the outlet water of the aerobic tank is maintained 849mg/L, the ammonia nitrogen concentration of the inlet water of the anaerobic tank is 974mg/L, and the ammonia nitrogen concentration of the outlet water of the aerobic tank is 831 mg/L.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A treatment method of gas-making circulating wastewater is characterized by comprising the following steps:
s1, standing and precipitating the circulating wastewater, adjusting the pH value of the wastewater to 4-6, and filtering the precipitate to obtain upper-layer turbid liquid;
s2, feeding the upper layer turbid liquid into an iron-carbon micro-electrolysis reactor, introducing air for reacting for 2-3h, and then discharging the iron-carbon micro-electrolysis reactor to obtain primary wastewater;
s3, adding a cyanogen breaking agent into the primary wastewater, wherein the cyanogen breaking agent accounts for 15-30% of the mass of the primary wastewater, then blowing air for aeration for 1-3h, and filtering to obtain secondary wastewater;
and S4, sequentially feeding the secondary wastewater into an anaerobic tank and an aerobic tank, and directly discharging the wastewater after biochemical treatment.
2. The method for treating the gas-making circulating wastewater according to claim 1, wherein the method for preparing the iron-carbon filler in the iron-carbon micro-electrolysis reactor in the step S2 comprises the following steps:
a1, immersing activated carbon particles into a saturated ferric chloride solution until the activated carbon is saturated in adsorption, taking out the activated carbon, and heating to 80-120 ℃ for drying to obtain iron-containing activated carbon;
a2, heating the iron-containing activated carbon to 800-1000 ℃ in a humid inert gas atmosphere, and cooling to room temperature to obtain the iron-carbon composite material;
a3, mixing copper powder, aluminum powder and activated carbon powder, firing at 1100-;
a4, mixing copper aluminum microspheres, iron carbon composite materials, clay, pore-forming agent, vermiculite and water uniformly, pressing into a filler blank, heating the filler blank to 380-.
3. The method for treating gas-making circulating wastewater according to claim 2, wherein the mass ratio of the copper powder, the aluminum powder and the activated carbon powder is 3-5:6-8: 20-30.
4. The method for treating gas-making circulating wastewater according to claim 2, wherein the mass ratio of the copper-aluminum microspheres, the iron-carbon composite material, the clay, the pore-forming agent, the vermiculite and the water is 3-5:10-15:8-12:2-3:1-3: 5-8.
5. The method for treating gas-making circulating wastewater according to claim 2, wherein the pore-forming agent is calcium bicarbonate.
6. A method as claimed in claim 2The method for treating the gas-making circulating wastewater is characterized in that the humid inert gas contains 10-20g/m of water3Carbon dioxide (c).
7. The method for treating gas-making circulating wastewater according to claim 1, wherein the cyanogen-breaking agent is prepared by the following steps: soaking diatomite into saturated aqueous solution containing copper ions, nickel ions and aluminum ions, adsorbing until the diatomite is saturated, taking out, soaking in aqueous solution containing 5-10 wt% of chelating agent for 3-6h, taking out and drying to obtain the cyanogen breaking agent.
8. The method for treating gas-making circulating wastewater according to claim 7, wherein the chelating agent is diethylenetriaminepentaacetic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115583749A (en) * | 2022-10-09 | 2023-01-10 | 本钢板材股份有限公司 | Process for removing cyanide in blast furnace gas washing turbid circulating wastewater |
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| CN101723499A (en) * | 2009-11-03 | 2010-06-09 | 燕山大学 | Preparation technology of diethylenetriaminepentaacetic acid modified diatomite |
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