CN111732254A - Phenol ammonia semi-coke wastewater treatment device and treatment method - Google Patents
Phenol ammonia semi-coke wastewater treatment device and treatment method Download PDFInfo
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Abstract
A semi-coke wastewater treatment device and a semi-coke wastewater treatment method for phenol ammonia comprise an oil separator, a plurality of extraction towers, an acid removal tower, a water tower, a deamination tower, an extractant circulating tank and a phenol tower, wherein organic matters and impurities such as oil, dust, phenol and the like in the semi-coke wastewater are removed by adopting an oil remover and an extraction oil removal method, and the problems of device equipment blockage, unqualified recycled product index, substandard effluent and the like in the traditional semi-coke wastewater treatment process are solved.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a phenol ammonia semi-coke wastewater treatment device and a treatment method.
Background
The resource of China has the characteristics of rich coal, oil and gas shortage, coal is the main consumption energy of China, the reserve of low-rank coal accounts for more than 55% of the reserve of coal proven in China, the quality improvement and utilization of the low-rank coal is an important measure for promoting the clean and high-efficiency utilization of the coal in China and ensuring the national energy safety, the low-rank coal is taken as a raw material, a method of pyrolysis and dry distillation is adopted to produce clean fuel and basic chemical raw materials, the low-rank coal is used for producing semi-coke clean fuel and coal gasification under the condition of medium-low temperature dry distillation (about 600-800 ℃), the produced industrial wastewater with difficult degradation and high CODVS (phenol ammonia blue carbon wastewater is high, and the wastewater contains a large amount of pollutants with difficult degradation and high toxicity, such as organic pollutants and inorganic pollutants like phenols, polycyclic aromatic hydrocarbons, benzene series, nitrogen oxygen heterocycles, ammonia nitrogen, sulfides, cyanides, thiocyanides and the like, in addition, because the temperature of the low-rank coal in the dry distillation process is low, a large amount of macromolecular emulsified oil is contained in the phenol ammonia semi-coke wastewater; therefore, the phenol ammonia semi-coke wastewater is typical high-pollution and high-toxicity industrial wastewater, and the wastewater cannot be effectively treated, so that the wastewater not only has great harm to human beings, aquatic products, crops and the like, but also restricts the development of the coal chemical industry in China, and can be discharged or recycled only after being treated so as to relieve the shortage of water resources.
The method is characterized in that the phenol ammonia semi-coke wastewater is treated by only adopting physical and chemical methods and is difficult to reach the emission standard, the treatment is usually completed by combining chemical separation pretreatment, biochemical treatment and reuse water treatment, namely, the pretreatment method is firstly adopted to reduce harmful substances such as dust particles, phenol, ammonia nitrogen, oil and the like in the phenol ammonia semi-coke wastewater and recycle the harmful substances, and then biochemical treatment and reuse water treatment processes are further adopted to ensure that the wastewater reaches the emission standard and the reuse water standard. The prior sodium phenolate wastewater pretreatment mode is basically as follows: deacidifying-deammoniating-extracting dephenolizing or deacidifying-deammoniating-extracting dephenolizing route. At present, the existing phenol-ammonia wastewater treatment process routes are designed aiming at coking phenol-ammonia wastewater with low oil content, low dust content or no oil or dust, namely deacidification and deamination are carried out before extraction and dephenolization, but the problems of unqualified effluent indexes, easy blockage of treatment equipment, unqualified recovered products and the like exist in the phenol-ammonia semi-coke wastewater treatment with high oil, dust and phenol contents by the treatment process.
Disclosure of Invention
The invention provides a device and a method for treating semi-coke phenol-ammonia wastewater with high oil content, dust content and phenol content in a semi-coke production process by utilizing low-rank coal according to quality, which are used for removing organic matters and impurities such as oil, dust and phenol in phenol-ammonia raw material wastewater by adopting an oil remover and an extraction oil removal method, and solve the problems of device equipment blockage, unqualified recycled product index, unqualified effluent and the like in the traditional semi-coke phenol-ammonia wastewater treatment process.
The technical scheme adopted by the invention is as follows:
a phenol ammonia semi-coke wastewater treatment device comprises an oil separator, a plurality of extraction towers, a deacidification tower, a water tower, a deamination tower, an extractant circulating tank and a phenol tower, wherein the oil separator is communicated to the upper part of the extraction tower through a pipeline, the top of the extraction tower is connected with an extractant conveying pipeline, the extractant conveying pipeline is connected with a phenol tower heat exchanger, the phenol tower heat exchanger is connected with the phenol tower through a pipeline, the bottom of the phenol tower is connected with a phenol oil conveying pipeline, the extractant conveying pipeline connected with the top of the phenol tower is connected to the extractant circulating tank after the heat exchange of the phenol tower heat exchanger, the extractant conveying pipeline connected with the extractant circulating tank is connected to the lower part of the extraction tower, the bottom of the extraction tower is connected with a dephenolizing and deoiling wastewater conveying pipeline, the extraction towers are sequentially connected in series, the dephenolizing and deoiling wastewater conveying pipeline of the upper stage extraction tower is connected to the upper part of the next stage extraction, the top of the deacidification tower is connected with an acid gas discharge pipeline, the acid gas discharge pipeline is communicated with a sulfur production device, the bottom of the deacidification tower is connected with a deacidification wastewater conveying pipeline, the deacidification wastewater conveying pipeline is connected with a water tower, the top of the water tower is connected with a water tower condensation cooler through a pipeline, the water tower condensation cooler is connected with a water tower reflux tank through a pipeline, the bottom of the water tower reflux tank is connected with a water return pipe, the water return pipe is connected with the water tower, the top of the water tower reflux tank is connected with an extractant recycling conveying pipeline, the extractant recycling conveying pipeline is connected with an extractant circulating tank, a water tower kettle is connected with a deacidification wastewater conveying pipeline, the deacidification wastewater conveying pipeline is connected with the upper part of a deamination tower, a sodium hydroxide solution injection pipeline is connected onto the deamination tower, the top of the deamina, the ammonia gas that the separator separates is carried to the refined system of ammonia through top connecting line, and the condensate that the separator separates returns the deamination tower through the tube coupling, and deamination waste water conveying line is connected to the deamination tower bottom, and deamination waste water conveying line carries the purified water to biochemical treatment system.
The phenol and oil removing wastewater conveying pipeline connected with the extraction tower and the deacidification tower is divided into two feeding pipelines, one is a cold feeding pipeline connected to the top of the deacidification tower, the other is a hot feeding pipeline connected to the upper part of the deacidification tower.
The hot feeding pipeline is connected with a deacidification tower feeding preheater, and the deacidification tower feeding preheater is in heat exchange connection with a deacidification wastewater conveying pipeline output from the bottom of the deacidification tower.
The deamination tower is characterized in that a deamination tower feeding preheater is connected to the deamination agent wastewater conveying pipeline and is in heat exchange connection with a deamination wastewater conveying pipeline output from the bottom of the deamination tower.
The number of the extraction towers is 1-6, and the extraction towers are connected in series and are 1# -6 # extraction towers in sequence.
The extraction stages of the extraction tower are 1-5, and the stages of the extraction towers can be the same or different.
A phenol ammonia semi-coke wastewater treatment method comprises the following steps:
(a) oil removal and dust removal: allowing the phenol ammonia semi-coke raw material wastewater to enter an oil separator, adjusting the temperature to 25-50 ℃, and removing oil and dust impurities in the phenol ammonia semi-coke wastewater in the oil separator to obtain oil-separating and dust-removing wastewater;
(b) extracting, dephenolizing and deoiling: feeding the oil-separating and dust-removing wastewater obtained in the step (a) into a No. 1 extraction tower from the upper part of the extraction tower, and feeding an extracting agent into the No. 1 extraction tower from the bottom of the No. 1 extraction tower; in the No. 1 extraction tower, continuously performing countercurrent extraction on the oil-separating and dust-removing wastewater and an extracting agent to obtain a No. 1 extract at the top of the No. 1 extraction tower and obtain No. 1 dephenolizing and oil-removing wastewater at the bottom of the No. 1 extraction tower; the 1# dephenolizing and deoiling wastewater enters a 2# extraction tower from the upper part of the 2# extraction tower, and an extracting agent enters the 2# extraction tower from the bottom of the 2# extraction tower; in a No. 2 extraction tower, continuously performing countercurrent extraction on the No. 1 dephenolizing and dedusting wastewater and an extracting agent to obtain a No. 2 extract at the top of the No. 2 extraction tower and obtain No. 2 dephenolizing and deoiling wastewater at the tower kettle of the No. 2 extraction tower; sequentially and continuously feeding the No. 2 dephenolized oil-removing wastewater into a subsequent extraction tower and carrying out continuous countercurrent extraction with an extracting agent according to the same method to obtain dephenolized oil-removing wastewater and extracts, wherein a mixture obtained by mixing the extracts of the towers is called an extraction mixture, and wastewater produced by a tower kettle of the last-stage extraction tower is called dephenolized oil-removing wastewater;
(c) stripping and deacidifying: dividing the dephenolized and deoiled wastewater obtained in the step (b) into two feed streams, wherein one feed stream is cold feed and directly enters a deacidification tower; the other strand is hot feed, exchanges heat with deacidification wastewater extracted from the tower kettle of the deacidification tower and enters the deacidification tower; the temperature of cold feeding is 25-50 ℃, the temperature of hot feeding is 50-100 ℃, and the volume ratio of the cold feeding to the hot feeding is 1: 1-1: 10; the operating pressure of the deacidification tower is 0.1-0.7 MPa; carbon dioxide and hydrogen sulfide acid gas are discharged from the top of the deacidification tower, and the acid gas is sent to a sulfur production device; deacidifying wastewater is extracted from a tower kettle of the deacidifying tower, the deacidifying wastewater contains a small amount of an extracting agent and ammonia substances, and the deacidifying wastewater is conveyed to a water tower to recover the extracting agent;
(d) and (3) recovering an extracting agent: sending the deacidification wastewater produced in the step (c) to a water tower, recovering a trace amount of extractant dissolved in water by using the water tower, collecting a mixture of the extractant and water from the top of the water tower, passing the mixture through a water tower condensation cooler, then entering a water tower reflux tank, layering the extractant and water in the water tower reflux tank, collecting the extractant from the upper layer of the water tower reflux tank to an extractant circulating tank, and recycling the extractant; the produced water at the lower layer of the water tower reflux tank returns to the water tower as reflux liquid; and extracting the agent-removing wastewater from the tower kettle of the water tower. The operation pressure of the top of the water tower is 0.01-0.6 MPa, the operation temperature of the top of the water tower is 80-145 ℃, and the operation temperature of the bottom of the water tower is 120-165 ℃.
(e) Stripping and deamination: ammonia is removed from the dealcoholization wastewater in the step (d) by adopting a deamination tower, and the dealcoholization wastewater enters the deamination tower from the upper part of the deamination tower; injecting a sodium hydroxide solution with the mass fraction of 5-36% into a deamination tower below a feed layer of the deamination tower, and converting fixed ammonia into ammonia gas for removal; mixed gas containing water and ammonia is extracted from the top of the deamination tower, and is subjected to three-stage condensation through a condenser and a separator, and the ammonia gas is subjected to pressure reduction and temperature reduction step by step to obtain high-purity ammonia gas, the ammonia gas is sent to an ammonia refining system, and condensate liquid returns to the deamination tower; the operation pressure at the top of the deamination tower is 0.1-0.6 MPa, and the operation temperature at the top of the deamination tower is 85-150 ℃; deamination wastewater meeting the biochemical treatment requirement is extracted from the tower kettle of the deamination tower, and the deamination wastewater, namely purified water, is sent to a biochemical treatment system;
(f) regeneration of an extracting agent: feeding the extraction mixture obtained by the step (b) into a phenol tower; extracting a high-purity extractant from the top of the phenol tower, and returning the extractant to a circulating tank of the extraction tower for use; phenol oil is extracted from the tower bottom of the phenol tower and is taken as a byproduct to be sent to a storage tank; the top pressure of the extraction tower is-0.01-0.02 MPa, the operation temperature of the tower top is 70-110 ℃, and the operation temperature of the tower bottom is 150-.
The number of the extraction towers is 1-6, the extraction temperature of the extraction towers is 25-50 ℃, the operation pressure is normal pressure, the PH value of semi-coke phenol ammonia wastewater is 3-11, and phenol ammonia semi-coke wastewater flows through the extraction towers in series.
The extractant is one or the combination of methyl isobutyl ketone, diisopropyl ether, butyl acetate, dimethyl carbonate and petroleum ether
The extractant entering each extraction tower is fresh, the fresh extractant is in countercurrent contact with the phenol ammonia semi-coke wastewater, and cross-flow extraction is formed between the extraction towers. The fresh extractant is newly purchased extractant, recycled extractant or extractant mixed with the newly purchased extractant and the recycled extractant.
The proportion of the extracting agent entering each extraction tower to the phenol ammonia semi-coke wastewater is 1: 1-1: 10, the ratio may be the same or different for each extraction column.
The invention has the beneficial effects that: the oil separator is adopted firstly, so that oil substances, dust impurities and the like in the phenol ammonia semi-coke wastewater are effectively removed, the burden of blocking subsequent treatment equipment is reduced, the COD (chemical oxygen demand) of the wastewater is reduced, and the treatment effect is improved; the extraction tower is placed before the procedures of deacidification and deamination, so that not only phenol in the phenol ammonia semi-coke wastewater is effectively removed, but also 'emulsified oil' in the phenol ammonia semi-coke wastewater is extracted and removed, the quality index of product liquid ammonia or ammonia water is favorably improved, the stable operation of the deacidification and deamination tower or the deacidification tower and the deamination tower is favorably realized, the operation efficiency is favorably improved, and the operation cost is reduced; countercurrent extraction and series extraction are combined, respective advantages are exerted to realize dephenolization and oil removal, namely, the semi-coke wastewater passes through each extraction tower in series, and countercurrent contact is performed inside a single extraction tower; the extractant entering each extraction tower is fresh, so that the effects of extraction dephenolization and deoiling are improved, and the loss of the extractant is reduced; with deacidifying, deamination, extractant recovery (water tower), extractant regeneration (phenol tower) separately handle alone, improved the stability of device operation, improve the product: the quality indexes of ammonia water or liquid ammonia and phenol oil are improved, and the operation efficiency is improved; the reflux ratio of each tower operation is reduced, the energy consumption of water treatment per ton is reduced, and the index of water quality after biochemical treatment is better; the operation pressure of the extractant recovery regeneration (phenol tower) can be negative pressure or positive pressure, so that the applicability is more flexible and practical.
Drawings
FIG. 1 is a schematic view of a processing apparatus according to the present invention.
Wherein: 1-oil separator; 2-an extraction column; 3-dephenolizing and deoiling wastewater conveying pipeline; 4-a deacidification tower; 5-a deacidification tower feed preheater; 6-a water tower; 7-water tower condensation cooler; 8-a feed preheater of the deamination tower; 9-a deamination tower; 10-a condenser; 11-a separator; 12-a deamination waste water conveying pipeline; 13-cold feed line; 14-hot feed line; 15-sodium hydroxide solution injection line; a 16-phenol column; a 17-phenol column heat exchanger; 18-an extractant circulation tank; 19-water tower reflux drum; 20-an extract delivery line; 21-phenol oil conveying pipeline; 22-an extractant conveying pipeline; 23-an acid gas discharge line; 24-deacidifying waste water conveying pipeline; 25-a water return pipe; 26-an extractant recovery conveying pipeline; 27-a desiccant wastewater delivery line.
Detailed Description
A phenol ammonia semi-coke wastewater treatment device comprises an oil separator 1, a plurality of extraction towers 2, a deacidification tower 4, a water tower 6, a deamination tower 9, an extractant circulating tank 18 and a phenol tower 16, wherein the oil separator 1 is communicated to the upper part of the extraction towers 2 through a pipeline, the top of each extraction tower 2 is connected with an extractant conveying pipeline 20, the extractant conveying pipeline 20 is connected with a phenol tower heat exchanger 17, the phenol tower heat exchanger 17 is connected with the phenol tower 16 through a pipeline, the bottom of the phenol tower 16 is connected with a phenol oil conveying pipeline 21, an extractant conveying pipeline 22 connected to the top of the phenol tower 16 is connected to the extractant circulating tank 18 after the heat exchange of the phenol tower heat exchanger 17, the extractant conveying pipeline 22 connected with the extractant circulating tank 18 is connected to the lower part of each extraction tower 2, the bottom of each extraction tower 2 is connected with a dephenolizing and deoiling wastewater conveying pipeline 3, each extraction tower 2 is sequentially connected in series, the dephenolizing and deoiling wastewater conveying, a dephenolization and deoiling wastewater conveying pipeline 3 connected with the bottom of the last stage extraction tower 2 is connected with a deacidification tower 4, the top of the deacidification tower 4 is connected with an acid gas discharge pipeline 23, the acid gas discharge pipeline 23 is communicated with a sulfur production device, the bottom of the deacidification tower 4 is connected with a deacidification wastewater conveying pipeline 24, the deacidification wastewater conveying pipeline 24 is connected with a water tower 6, the top of the water tower 6 is connected with a water tower condensing cooler 7 through a pipeline, the water tower condensing cooler 7 is connected with a water tower reflux tank 19 through a pipeline, the bottom of the water tower reflux tank 19 is connected with a water reflux pipe 25, the water reflux pipe 25 is connected with the water tower 6, the top of the water tower reflux tank 19 is connected with an extractant recovery conveying pipeline 26, the extractant recovery conveying pipeline 26 is connected with an extractant circulating tank 18, the kettle of the water tower 6 is connected with a dephenolization wastewater conveying pipeline 27, the dephenolization, the top of the deammoniation tower 9 is connected with a mixed gas conveying pipeline, three groups of condensers 10 and separators 11 which are alternately connected are connected in series on the mixed gas conveying pipeline, ammonia gas separated out by the separators 11 is conveyed to an ammonia refining system through a top connecting pipeline, condensate separated out by the separators 11 is returned to the deammoniation tower 9 through pipeline connection, the bottom of the deammoniation tower 9 is connected with a deammoniation waste water conveying pipeline 12, and the deammoniation waste water conveying pipeline 12 conveys purified water to a biochemical treatment system.
The phenol and oil removing wastewater conveying pipeline 3 connected with the extraction tower 2 and the deacidification tower 4 is divided into two feeding pipelines, one is a cold feeding pipeline 13, the cold feeding pipeline 13 is connected to the top of the deacidification tower 4, the other is a hot feeding pipeline 14, and the hot feeding pipeline 14 is connected to the upper part of the deacidification tower 4.
The hot feed pipeline 14 is connected with a deacidification tower feed preheater 5, and the deacidification tower feed preheater 5 is in heat exchange connection with a deacidification wastewater conveying pipeline 24 output from the bottom of the deacidification tower 4.
And the deamination tower feeding preheater 8 is connected to the deamination agent wastewater conveying pipeline 27, and the deamination tower feeding preheater 8 is in heat exchange connection with a deamination wastewater conveying pipeline 12 output from the bottom of the deamination tower 9.
The number of the extraction towers 2 is 1-6, and the extraction towers 2 are connected in series and are 1# to 6# in sequence.
The extraction stages of the extraction towers 2 are 1-5, and the stages of the extraction towers 2 can be the same or different.
A phenol ammonia semi-coke wastewater treatment method comprises the following steps:
(a) oil removal and dust removal: and (3) allowing the phenol ammonia semi-coke raw material wastewater to enter an oil separator 1, adjusting the temperature to 25-50 ℃, extracting impurities such as oil, dust and the like from an oil outlet of the oil separator 1, and extracting oil-separating dedusting wastewater from a water outlet of the oil separator 1.
(b) Extracting, dephenolizing and deoiling: the oil removal and dust removal wastewater obtained in the step (a) enters a No. 1 extraction tower 2 from the upper part of the extraction tower 2, and an extractant in an extractant conveying pipeline 22 enters the No. 1 extraction tower from the bottom of the extraction tower 2; in the No. 1 extraction tower, the oil-separating and dust-removing wastewater is in countercurrent contact with an extracting agent; 1# extract and 1# dephenolizing and deoiling wastewater are respectively extracted from the top of a 1# extraction tower and the bottom of a 1# extraction tower, the 1# dephenolizing and dedusting wastewater enters a 2# extraction tower from the upper part of an extraction tower 2 along a dephenolizing and deoiling wastewater conveying pipeline 3, and an extractant enters the 2# extraction tower from the bottom of the extraction tower 2; in a No. 2 extraction tower, continuous countercurrent extraction is carried out on No. 1 dephenolized oil-removed wastewater and an extracting agent, a No. 2 extract and No. 2 dephenolized oil-removed wastewater are respectively obtained at the top and the bottom of the No. 2 extraction tower, the No. 2 dephenolized wastewater continuously enters a subsequent extraction tower 2 to be continuously subjected to continuous countercurrent extraction with the extracting agent according to the same method, and extracts extracted at the top of each extraction tower 2 are mixed and then are used as the feed of a phenol tower 16; the wastewater extracted from the tower bottom of the last stage extraction tower 2 is called dephenolizing and deoiling wastewater which is used as the feed of the water tower. The number of the extraction towers 2 is 1-6, and the proportion of the extracting agent entering each extraction tower 2 to the phenol ammonia semi-coke wastewater is 1: 1-1: 10.
(c) stripping and deacidifying: the dephenolizing and deoiling wastewater extracted from the tower bottom of the extraction tower 2 in the step (b) is divided into two feeds, wherein one feed is cold feed and directly enters the deacidification tower 4 along a cold feed pipeline 13; the other strand is hot feed, the hot feed is preheated in a hot feed pipeline 14 by a deacidification tower feed preheater 5, and the hot feed enters the deacidification tower 4 after exchanging heat with deacidification wastewater collected from the tower bottom of the deacidification tower 4 in the deacidification tower feed preheater 5 until the temperature of the hot feed is 50-100 ℃. The volume ratio of the cold feed to the hot feed is 1: 1-1: 10; the operation pressure of the deacidification tower 4 is 0.1-0.7 MPa. Acid gases such as carbon dioxide, hydrogen sulfide and the like are discharged from the top of the deacidification tower 4, and the acid gases are conveyed to a sulfur production device along an acid gas discharge pipeline 23; deacidifying wastewater is extracted from the tower kettle 4 of the deacidifying tower and is used as the feeding material of the water tower.
(d) And (3) recovering an extracting agent: conveying the deacidification wastewater produced in the step (c) to a water tower 6 along a deacidification wastewater conveying pipeline 24, recovering a trace amount of extractant dissolved in water by using the water tower 6, collecting a mixture of the extractant and water from the top of the water tower 6, condensing and cooling the mixture by a water tower condensing cooler 7, then feeding the mixture into a water tower reflux tank 19, layering the extractant and water in the water tower reflux tank 19, collecting the extractant from the upper layer of the water tower reflux tank 19 to an extractant circulating tank 18, and recycling the extractant; the lower layer produced water in the water tower reflux tank 19 is returned to the water tower 6 as reflux liquid; and extracting agent-removing wastewater from the tower 6 of the water tower. The operation pressure of the top of the water tower 6 is 0.01-0.6 MPa, the operation temperature of the top of the tower is 80-145 ℃, and the operation temperature of the bottom of the tower is 120-165 ℃.
(e) Stripping and deamination: and (d) removing ammonia from the wastewater subjected to agent removal in the step (d) by using a deamination tower 9, wherein the wastewater subjected to agent removal enters the deamination tower 9 from the upper part of the deamination tower 9. Injecting a sodium hydroxide solution with the mass fraction of 5-36% into a deamination tower 9 below a feed layer or a feed layer of the deamination tower 9, and converting fixed ammonia into ammonia gas for removal; mixed gas containing water and ammonia is extracted from the top of the deamination tower 9, and is subjected to three-stage condensation, three-stage flash evaporation, step-by-step pressure reduction, temperature reduction and flash evaporation through a condenser 10 and a separator 11 to finally obtain high-purity ammonia gas, the ammonia gas is sent to an ammonia refining system, and condensate of a flash evaporation tank returns to the deamination tower 9; the operation pressure at the top of the deamination tower 9 is 0.1-0.6 MPa, and the operation temperature at the top of the deamination tower is 85-150 ℃; deamination waste water meeting the biochemical treatment requirement is extracted from the tower 9 of the deamination tower, and the deamination waste water, namely purified water, is sent to a biochemical treatment system.
(f) Regeneration of an extracting agent: the extraction mixture obtained from the treatment in step (b) is used as feed to the phenol column 16 and preheated to 65 ℃ in the phenol column feed preheater 17 to enter the phenol column 16. Extracting a high-purity extractant from the top of the phenol tower 16, and returning the extractant to the extractant circulating tank 18 to be recycled by the extraction tower 2; and (3) extracting phenol oil from the bottom of the phenol tower 16, and conveying the phenol oil serving as a byproduct to a storage tank. The top pressure of the phenol tower 16 is-0.01-0.02 MPa, the top operating temperature is 70-120 ℃, and the bottom operating temperature is 150-.
The invention will be illustrated in detail below with reference to specific examples:
example 1
The treatment capacity of 100t/h of phenol ammonia blue carbon wastewater raw material is 41500mg/L, the oil content is 3800mg/L, the total phenol content is 11800mg/L, the ammonia nitrogen content is 8000mg/L, the sulfide content is 2500mg/L, the dust content is 1500mg/L, the PH value is 9.5, and the temperature is 25 ℃. The treatment device in the attached figure 1 is adopted for treatment according to the treatment process steps, and the main process parameters are as follows:
(a) oil removal and dust removal: the phenol ammonia semi-coke wastewater is primarily purified by an oil separator 1, the raw material of the phenol ammonia semi-coke wastewater directly enters the oil separator 1, light oil, heavy oil and impurities are extracted from an oil outlet, and oil-separating and dedusting wastewater with the oil content of 2000mg/L and the solid dust content of 150mg/L is extracted from a water outlet.
(b) Extracting, dephenolizing and deoiling: in the embodiment, 3 extraction towers 2 are adopted, the extraction stage number of each extraction tower 2 is 4, the extracting agent is a mixed extracting agent consisting of 60% of methyl isobutyl ketone and 40% of petroleum ether in volume ratio, the operating temperature of each extraction tower 2 is 40 ℃, the operating pressure of each extraction tower 2 is normal pressure, and the volume ratio of the extracting agent of each extraction tower 2 to the phenol ammonia semi-coke wastewater is 1: 3. the oil content in the dephenolized oil-removing wastewater extracted from the tower bottom of the 3# extraction tower is 100mg/L, and the total phenol content is 800 mg/L.
(c) Stripping and deacidifying: the operating pressure of the deacidification tower 4 is 0.5MPa, the operating temperature of the tower top is 50 ℃, the operating temperature of the tower kettle is 150 ℃, the dephenolizing and deoiling wastewater extracted from the tower kettle of the extraction tower 2 is divided into two feeds, one of the two feeds is a cold feed, and the two feeds directly enter the deacidification tower 4 along a cold feed pipeline 13; the other strand is hot feed, and the hot feed exchanges heat with deacidification wastewater collected from the tower bottom of the deacidification tower 4 in a feed preheater 5 of the deacidification tower and enters the deacidification tower 4 at the temperature of 100 ℃. The volume ratio of the cold feed to the hot feed is 1:3, acid gases such as carbon dioxide, hydrogen sulfide, an extracting agent and the like are discharged from the top of the deacidification tower 4, and the acid gases are sent to a sulfur production device; deacidifying wastewater is extracted from the tower kettle 4 of the deacidifying tower, and the sulfide content of the wastewater is 50 mg/L.
(d) Stripping an extractant: the operation pressure of the water tower 6 is 0.3MPa, the operation temperature of the tower top is 105 ℃, and the operation temperature of the tower bottom is 140 ℃. The wastewater from tower 6 of water tower has COD content of 3500 mg/L.
(e) Stripping and deamination: removing ammonia from the wastewater removed in the step (d) by using a deamination tower 9, feeding the wastewater removed in the deamination tower 9 from the upper part of the deamination tower 9, wherein the operating pressure of the deamination tower 9 is 0.5MPa, the operating temperature of the top of the tower is 145 ℃, the operating temperature of the bottom of the tower is 160 ℃, and injecting a sodium hydroxide solution with the mass concentration of 32% and the flow of 15Kg/h into the deamination tower in a feed layer of the deamination tower 9; mixed gas containing ammonia is extracted from the top of the deamination tower 9 and is subjected to three-stage condensation flash evaporation to obtain a 99.5 percent by-product ammonia gas; deamination wastewater is extracted from the tower bottom 9 of the deamination tower, wherein the COD content is 3500mg/L, the ammonia nitrogen content is 130mg/L, the oil content is 100mg/L, the sulfide content is 50mg/L, and the solid dust content is 100 mg/L. The deamination wastewater is used as biochemical influent and completely meets various influent indexes of a biochemical system.
(f) Regeneration of an extracting agent: the operating pressure of the phenol tower 16 is normal pressure, the operating temperature of the tower top is 105 ℃, the operating temperature of the tower bottom is 201 ℃, a high-purity extractant is extracted from the tower top of the phenol tower 16, and the extractant is returned to the extraction tower 2 for recycling; phenol oil is extracted from the bottom of the phenol tower 16 and is taken as a byproduct to be sent into a storage tank.
Comparative example 1 a comparative example was designed, and the effect of the amount of the extraction tower 2 on the extraction dephenolization and oil removal of the phenol ammonia semi-coke wastewater and the removal of solid dust was examined through the comparative example.
Compared with the embodiment 1, the method adopts different numbers of extraction towers 2, has the same other process conditions, designs a comparative example, and finally obtains various indexes of the dephenolized and deoiled wastewater.
Compared with the embodiment 1, the method adopts different numbers of extraction towers 2, the other process conditions are the same, and the comparative example is designed to finally obtain various indexes of the deamination wastewater.
Compared with the embodiment 1, the method adopts different numbers of extraction towers 2, the other process conditions are the same, and the comparative example is designed to finally obtain the removal rate of each index of the deamination wastewater.
Example 2
The treatment capacity is 50t/h of phenol ammonia semi-coke wastewater raw material, the COD content is 39500mg/L, the oil content is 2700mg/L, the total phenol content is 8500mg/L, the ammonia nitrogen content is 5500mg/L, the sulfide content is 4000mg/L, the dust content is 2300mg/L, the PH value is 5.6, and the temperature is 45 ℃. The processing is carried out by adopting the process flow chart shown in the attached figure 1, and the main process parameters are as follows:
(a) oil removal and dust removal: the method comprises the following steps of adopting an oil separator 1 to primarily purify the phenol ammonia semi-coke wastewater, directly feeding the raw material of the phenol ammonia semi-coke wastewater into the oil separator 1, extracting light oil, heavy oil and impurities from an oil outlet, and extracting oil-separating dedusting wastewater from a water outlet, wherein the oil content is 1600mg/L, and the solid dust content is 300mg/L.
(b) Extracting, dephenolizing and deoiling: in the embodiment, 4 extraction towers 2 are adopted, the extraction stage number of each extraction tower 2 is 3, the extraction agent is a mixed extraction agent consisting of 40% of methyl isobutyl ketone, 30% of petroleum ether and 30% of ethyl acetate in volume ratio, the operation temperature of each extraction tower 2 is 45 ℃, the operation pressure of each extraction tower 2 is normal pressure, and the volume ratio of the extraction agent to the phenol ammonia semi-coke wastewater of each extraction tower 2 is 1: 6, the oil content in the dephenolization and oil removal wastewater extracted from the tower bottom of the No. 4 extraction tower is 80mg/L, the total phenol content is 750mg/L, and the dust content is 80mg/L.
(c) Stripping and deacidifying: the operation pressure of the deacidification tower 4 is 0.2MPa, the operation temperature of the tower top is 48 ℃, and the operation temperature of the tower bottom is 130 ℃. The dephenolizing and deoiling wastewater extracted from the tower bottom of the extraction tower 2 is two feeds, one of which is a cold feed and directly enters the deacidification tower 4; the other strand is hot feed, and the hot feed exchanges heat with deacidification wastewater collected from the tower bottom of the deacidification tower 4 and enters the deacidification tower 4 after reaching 90 ℃. The volume ratio of cold feed to hot feed was 1: 8. Acid gases such as carbon dioxide, hydrogen sulfide, extracting agent and the like are discharged from the top of the deacidification tower 4, and the acid gases are sent to a sulfur production device; deacidifying wastewater is extracted from the tower kettle 4 of the deacidifying tower, and the sulfide content of the wastewater is 55 mg/L.
(d) Stripping an extractant: the operation pressure of the water tower 6 is 0.1MPa, the operation temperature of the tower top is 78 ℃, and the operation temperature of the tower kettle is 120 ℃. The degreaser wastewater is extracted from the tower bottom of the water tower 6, the COD content is 3015mg/L, and the oil content is 80mg/L.
(e) Stripping and deamination: and (d) removing ammonia from the wastewater subjected to agent removal in the step (d) by using a deamination tower 9, wherein the wastewater subjected to agent removal enters the deamination tower 9 from the upper part of the deamination tower 9. The operating pressure of the deamination tower 9 is 0.2MPa, the operating temperature of the top of the tower is 125 ℃, the operating temperature of the bottom of the tower is 135 ℃, and sodium hydroxide solution with the mass concentration of 32% and the flow of 6Kg/h is injected into the deamination tower in the feed layer of the deamination tower 9; mixed gas containing ammonia is extracted from the top of the deamination tower 9 and is subjected to three-stage condensation flash evaporation to obtain a 99.3 percent by-product ammonia gas. Deamination wastewater is extracted from a tower bottom 9 of the deamination tower, and has the COD content of 2850mg/L, the ammonia nitrogen content of 120mg/L, the oil content of 80mg/L, the sulfide content of 55mg/L and the solid dust content of 80mg/L. The deamination wastewater is used as biochemical influent and completely meets various influent indexes of a biochemical system.
(f) Regeneration of an extracting agent: the operating pressure of the phenol tower 16 is-0.04 MPa, the operating temperature of the tower top is 82 ℃ and the operating temperature of the tower bottom is 173 ℃. Extracting a high-purity extractant from the top of the phenol tower 16, and returning the extractant to the extractant circulating tank 18 for recycling of the extraction tower 2; phenol oil is extracted from the phenol tower 16, and the phenol oil is taken as a byproduct and sent out of the storage tank.
Comparative example 2 a comparative example was designed, and the effect of the extraction agent combination ratio on the extraction dephenolization and oil removal of phenol ammonia semi-coke wastewater and the removal of solid dust was examined through the comparative example.
Compared with the embodiment 2, the method adopts different extraction agent proportions and other process conditions are the same, and designs a comparative example to finally obtain various indexes of the dephenolized and deoiled wastewater.
Compared with the embodiment 2, different extraction agent proportions are adopted, other process conditions are the same, a comparative example is designed, and different extraction agent proportions are adopted to finally obtain various indexes of the dephenolized and deoiled wastewater.
Compared with the embodiment 2, different extraction agent proportions are adopted, other process conditions are the same, a comparative example is designed, and different extraction agent proportions are adopted below to finally obtain various indexes of the deamination wastewater.
Compared with the embodiment 2, different extraction agent proportions are adopted, other process conditions are the same, a comparative example is designed, and different extraction agent proportions are adopted below to finally obtain various indexes of the deamination wastewater.
Compared with the example 2, different extractant proportions are adopted, the other process conditions are the same, a comparative example is designed, and the removal rate of each index of the deamination wastewater is finally obtained, wherein the extractants with comparative numbers 1, 2 and 3 are methyl isobutyl ketone, petroleum ether and ethyl acetate, and the extractants with comparative numbers 4, 5 and 6 are methyl isobutyl ketone, diisopropyl ether and dimethyl carbonate.
It can be seen from the data of the examples 1 and 2 and the data of various proportions that the oil remover 1 has a good effect of removing oil substances and dust impurities in the semi-coke wastewater, and greatly reduces the burden of blocking of subsequent treatment equipment, the removal effect of COD, sulfide and ammonia nitrogen is very obvious under the action of the extraction tower 2, the deacidification tower 4 and the deamination tower 9, and all indexes of deamination wastewater obtained by different extracting agents with different proportions can also meet the index of entering a biochemical system.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. The phenol ammonia semi-coke wastewater treatment device is characterized by comprising an oil separator (1), a plurality of extraction towers (2), a deacidification tower (4), a water tower (6), a deamination tower (9), an extractant circulating tank (18) and a phenol tower (16), wherein the oil separator (1) is communicated to the upper part of the extraction tower (2) through a pipeline, the top of the extraction tower (2) is connected with an extract conveying pipeline (20), the extract conveying pipeline (20) is connected with a phenol tower heat exchanger (17), the phenol tower heat exchanger (17) is connected with the phenol tower (16) through a pipeline, the bottom of the phenol tower (16) is connected with a phenol oil conveying pipeline (21), the extractant conveying pipeline (22) connected to the top of the phenol tower (16) is connected to the extractant circulating tank (18) after the phenol tower heat exchanger (17) exchanges heat, the extractant conveying pipeline (22) connected with the extractant circulating tank (18) is connected to the lower part of the extraction tower (2), the tower bottom of the extraction tower (2) is connected with a dephenolizing and deoiling wastewater conveying pipeline (3), each extraction tower (2) is sequentially connected in series, the dephenolizing and deoiling wastewater conveying pipeline (3) of the upper stage extraction tower (2) is connected to the upper part of the next stage extraction tower (2), the dephenolizing and deoiling wastewater conveying pipeline (3) connected at the tower bottom of the last stage extraction tower (2) is connected to a deacidification tower (4), the tower top of the deacidification tower (4) is connected with an acidic gas discharge pipeline (23), the acidic gas discharge pipeline (23) is communicated to a sulfur production device, the tower bottom of the deacidification tower (4) is connected with a deacidification wastewater conveying pipeline (24), the deacidification wastewater conveying pipeline (24) is connected to a water tower (6), the top of the water tower (6) is connected with a water tower condenser cooler (7) through a pipeline, the water tower condenser cooler (7) is connected with a water tower reflux, a water return pipe (25) is connected with a water tower (6), the top of a water tower reflux tank (19) is connected with an extracting agent recovery conveying pipeline (26), the extracting agent recovery conveying pipeline (26) is connected with an extracting agent circulation tank (18), the tower bottom of the water tower (6) is connected with a deliquescing wastewater conveying pipeline (27), the deliquescing wastewater conveying pipeline (27) is connected to the upper part of a deamination tower (9), a sodium hydroxide solution injection pipeline (15) is connected on the deamination tower (9), the tower top of the deamination tower (9) is connected with a mixed gas conveying pipeline, three groups of condensers (10) and separators (11) which are alternately connected are connected in series on the mixed gas conveying pipeline, ammonia gas separated by the separators (11) is conveyed to an ammonia refining system through a top connecting pipeline, condensate separated by the separators (11) is connected back to the deamination tower (9) through a pipeline, and the tower bottom of the deamination tower, the deamination waste water conveying pipeline (12) conveys the purified water to a biochemical treatment system.
2. The semi-coke wastewater treatment device for phenol ammonia according to claim 1, wherein the phenol and oil removal wastewater delivery pipeline (3) connected with the extraction tower (2) and the deacidification tower (4) is divided into two feeding pipelines, one is a cold feeding pipeline (13), the cold feeding pipeline (13) is connected to the top of the deacidification tower (4), the other is a hot feeding pipeline (14), and the hot feeding pipeline (14) is connected to the upper part of the deacidification tower (4).
3. The semi-coke phenolic wastewater treatment device according to claim 2, wherein the hot feed line (14) is connected with a deacidification tower feed preheater (5), and the deacidification tower feed preheater (5) is connected with a deacidification wastewater conveying line (24) output from the bottom of the deacidification tower (4) in a heat exchange manner.
4. The semi-coke wastewater treatment device of phenol ammonia according to claim 1, characterized in that the deamination tower feeding preheater (8) is connected to the wastewater delivery line (27), and the deamination tower feeding preheater (8) is connected to the deamination tower (9) through heat exchange with the deamination wastewater delivery line (12) output from the bottom of the deamination tower.
5. The semi-coke phenolic wastewater treatment device according to claim 1, wherein the number of the extraction towers (2) is 1-6, and the extraction towers (2) are connected in series and are 1# -6 # in sequence.
6. The semi-coke phenolic wastewater treatment device according to claim 1, wherein the extraction tower (2) has an extraction stage number of 1-5, and the extraction towers (2) have the same or different stage numbers.
7. A phenol ammonia semi-coke wastewater treatment method is characterized by comprising the following steps:
(a) oil removal and dust removal: allowing the phenol ammonia semi-coke raw material wastewater to enter an oil separator (1), adjusting the temperature to 25-50 ℃, and removing oil and dust impurities in the phenol ammonia semi-coke wastewater in the oil separator (1) to obtain oil-separating and dust-removing wastewater;
(b) extracting, dephenolizing and deoiling: feeding the oil-separating and dust-removing wastewater obtained in the step (a) into a No. 1 extraction tower from the upper part of an extraction tower (2), and feeding an extracting agent into the No. 1 extraction tower from the bottom of the No. 1 extraction tower; in the No. 1 extraction tower, continuously performing countercurrent extraction on the oil-separating and dust-removing wastewater and an extracting agent to obtain a No. 1 extract at the top of the No. 1 extraction tower and obtain No. 1 dephenolizing and oil-removing wastewater at the bottom of the No. 1 extraction tower; the 1# dephenolizing and deoiling wastewater enters a 2# extraction tower from the upper part of the 2# extraction tower, and an extracting agent enters the 2# extraction tower from the bottom of the 2# extraction tower; in a No. 2 extraction tower, continuously performing countercurrent extraction on the No. 1 dephenolizing and dedusting wastewater and an extracting agent to obtain a No. 2 extract at the top of the No. 2 extraction tower and obtain No. 2 dephenolizing and deoiling wastewater at the tower kettle of the No. 2 extraction tower; continuously feeding the No. 2 dephenolized oil-removing wastewater into a subsequent extraction tower (2) according to the same method to perform continuous countercurrent extraction with an extracting agent to obtain dephenolized oil-removing wastewater and extracts, wherein a mixture obtained by mixing the extracts of the towers is called an extraction mixture, and wastewater extracted from the tower kettle of the last-stage extraction tower (2) is called dephenolized oil-removing wastewater;
(c) stripping and deacidifying: dividing the dephenolized oil-removing wastewater extracted in the step (b) into two feed streams, wherein one feed stream is cold feed and directly enters a deacidification tower (4); the other strand is hot feed, exchanges heat with deacidification wastewater extracted from the tower kettle of the deacidification tower (4), and enters the deacidification tower (4); the temperature of cold feeding is 25-50 ℃, the temperature of hot feeding is 50-100 ℃, and the volume ratio of the cold feeding to the hot feeding is 1: 1-1: 10; the operating pressure of the deacidification tower (4) is 0.1-0.7 MPa; carbon dioxide and hydrogen sulfide acid gas are discharged from the top of the deacidification tower (4), and the acid gas is sent to a sulfur production device; deacidifying wastewater is extracted from the tower kettle of the deacidifying tower (4), the deacidifying wastewater contains a small amount of extracting agent and ammonia substances, and the deacidifying wastewater is conveyed to a water tower (6) to recover the extracting agent;
(d) and (3) recovering an extracting agent: conveying the deacidification wastewater produced in the step (c) to a water tower (6), recovering a trace amount of extractant dissolved in water by using the water tower (6), collecting a mixture of the extractant and water on the top of the water tower (6), passing the mixture through a water tower condensation cooler (7), then entering a water tower (6) reflux tank, layering the extractant and water in the water tower (6) reflux tank, collecting the extractant on the upper layer of the water tower (6) reflux tank to an extractant circulating tank (18), and recycling the extractant; the produced water at the lower layer of the reflux tank of the water tower (6) is returned to the water tower (6) as reflux liquid; the tower kettle of the water tower (6) extracts the wastewater of the removal agent. The operation pressure at the top of the water tower (6) is 0.01-0.6 MPa, the operation temperature at the top of the tower is 80-145 ℃, and the operation temperature at the bottom of the tower is 120-165 ℃;
(e) stripping and deamination: ammonia is removed from the wastewater subjected to agent removal in the step (d) by adopting a deamination tower (9), and the wastewater subjected to agent removal enters the deamination tower (9) from the upper part of the deamination tower (9); injecting a sodium hydroxide solution with the mass fraction of 5-36% into a deamination tower (9) below a feed layer or a feed layer of the deamination tower (9), and converting fixed ammonia into ammonia gas for removal; mixed gas containing water and ammonia is extracted from the top of the deamination tower (9), and is subjected to three-stage condensation through a condenser (10) and a separator (11), the pressure is reduced and the temperature is reduced step by step to obtain high-purity ammonia gas, the ammonia gas is sent to an ammonia refining system, and condensate returns to the deamination tower (9); the operation pressure at the top of the deamination tower (9) is 0.1-0.6 MPa, and the operation temperature at the top of the deamination tower is 85-150 ℃; deamination wastewater meeting the biochemical treatment requirement is extracted from the tower kettle of the deamination tower (9), and the deamination wastewater, namely purified water, is sent to a biochemical treatment system;
(f) regeneration of an extracting agent: feeding the extraction mixture obtained by the step (b) into a phenol tower (16); extracting a high-purity extractant from the top of the phenol tower (16), and returning the extractant to a circulating tank of the extraction tower (2) for use; phenol oil is extracted from the bottom of the phenol tower (16), and the phenol oil is taken as a byproduct and sent to a storage tank; the pressure at the top of the extraction tower (2) is-0.01-0.02 MPa, the operation temperature at the top of the extraction tower is 70-110 ℃, and the operation temperature at the bottom of the extraction tower is 150-.
8. The method for treating the semi-coke phenolic wastewater according to claim 7, wherein the number of the extraction towers (2) is 1-6, the extraction temperature of the extraction towers (2) is 25-50 ℃, the operation pressure is normal pressure, the pH value of the semi-coke phenolic wastewater is 3-11, and the semi-coke phenolic wastewater flows through the extraction towers (2) in series.
9. The method for treating phenol ammonia semi-coke wastewater according to claim 7, wherein the extracting agent is one or more of methyl isobutyl ketone, diisopropyl ether, butyl acetate, dimethyl carbonate and petroleum ether.
10. The method for treating the semi-coke waste water containing the phenol and the ammonia as the claim 7 shows, wherein the extractant entering each extraction tower (2) is a fresh extractant, the fresh extractant is in countercurrent contact with the semi-coke waste water containing the phenol and the ammonia, cross-flow extraction is formed between the extraction tower (2) and the extraction tower (2), the fresh extractant is a newly purchased extractant, a recycled extractant or a mixed extractant of the newly purchased extractant and the recycled extractant, and the proportion of the extractant in the extraction tower (2) to the semi-coke waste water containing the phenol and the ammonia is 1: 1-1: 10, the ratio of the extraction columns (2) can be identical or different.
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| CN115196805B (en) * | 2022-07-21 | 2024-02-27 | 中国科学院山西煤炭化学研究所 | Treatment method for deoiling, dedusting, deacidifying and deaminizing semi-coke wastewater |
| CN115838216A (en) * | 2022-09-21 | 2023-03-24 | 陕西煤业化工集团神木天元化工有限公司 | Coal chemical wastewater treatment method and system |
| WO2024060693A1 (en) * | 2022-09-21 | 2024-03-28 | 陕西煤业化工集团神木天元化工有限公司 | Coal chemical wastewater treatment method and system |
| CN116969638A (en) * | 2023-08-30 | 2023-10-31 | 江苏沃德凯环保科技有限公司 | Deamination treatment method of semi-coke wastewater |
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