A kind of phenol ammonia blue charcoal wastewater treatment device and treatment method
Through the countercurrent extraction and series extraction technology of the oil spacer and extraction tower combination device, the problems of equipment blockage and product failure in the treatment of phenolam carbon wastewater are solved, and efficient oil, dust and phenol removal is achieved, satisfying emissions and The standard for reuse water reduces energy consumption and costs.
Patent Information
- Application Number
- CN202010614575.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2020-06-30
- Publication Date
- 2024-12-17
- Estimated Expiration
- 2040-06-30
AI Technical Summary
The existing phenolam carbon wastewater treatment process is poor in the treatment of wastewater with high oil, dust and phenol, resulting in the failure of water effluent standards, equipment blockage and unqualified recycling products.
Using a combination device of oil separator and extraction tower, the oil, dust and phenol in the phenol ammonia wastewater are removed through countercurrent extraction and series extraction technology, combined with deacid and deaminogenic processes, and the extraction agent is recovered and regenerated, thereby improving the treatment effect and equipment stability. sex.
It effectively reduces the risk of equipment blockage, improves treatment effect and product quality, meets the standards for emission and reuse of water, and reduces energy consumption and operating costs.
Smart Images
Figure CN111732254B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of wastewater treatment, and in particular to a phenol ammonia blue charcoal wastewater treatment device and a treatment method. Background Art
[0002] my country's resources are characterized by "rich in coal, short of oil and little gas". Coal is the main energy consumption in my country, and low-rank coal reserves account for more than 55% of the country's proven coal reserves. Improving the quality of low-rank coal is an important measure to promote the clean and efficient utilization of my country's coal and ensure national energy security. It uses coal as raw material and adopts the method of thermal decomposition and dry distillation to produce clean fuels and basic chemical raw materials. Under the conditions of medium and low temperature dry distillation (about 600-800℃), low-rank coal is used to produce (semi-coke) semi-coke clean fuel and coal gasification. During the process, a difficult-to-degrade, high CODVS industrial wastewater, namely phenol-ammonia semi-coke wastewater, is produced. This wastewater contains There are a large number of difficult-to-degrade and highly toxic pollutants, such as phenols, polycyclic aromatic hydrocarbons, benzene series, nitrogen-oxygen heterocycles, ammonia nitrogen, sulfides, cyanides, thiocyanates and other organic pollutants and inorganic pollutants. In addition, due to the low temperature of the low-rank coal distillation process, the phenol-ammonia charcoal wastewater also contains a large amount of macromolecular emulsified oil; therefore, phenol-ammonia charcoal wastewater is a typical highly polluted and highly toxic industrial wastewater. If this wastewater cannot be effectively treated, it will not only pose a great threat to humans, aquatic products, crops, etc., but also restrict the development of my country's coal chemical industry. Therefore, it must be treated before it can be discharged or reused to alleviate the shortage of water resources.
[0003] The treatment of phenol ammonia blue charcoal wastewater is difficult to reach the discharge standard by simply adopting physical and chemical methods. It is usually completed by chemical separation pretreatment, biochemical treatment, and reuse water treatment combination. That is, the pretreatment method is preferred to reduce the dust particles, phenol, ammonia nitrogen, oil and other harmful substances in the phenol ammonia blue charcoal wastewater, and recycle them, and then further adopt biochemical treatment and reuse water treatment process to make the wastewater reach the discharge standard and reuse water standard. The existing sodium phenol wastewater pretreatment method is basically: deacidification-deamination-extraction dephenolization or deacidification deamination-extraction dephenolization route. At present, the existing phenol ammonia wastewater treatment process route is designed for the process route of coking phenol ammonia wastewater with low oil content, low dust or no oil and no dust, that is, deacidification and deamination are before extraction dephenolization, but this treatment process has problems such as unqualified effluent index, easy blockage of treatment equipment, and unqualified recovered products for the treatment of phenol ammonia blue charcoal wastewater with high oil, dust and phenol content. Summary of the invention
[0004] The present invention provides a device and method for treating blue charcoal phenol-ammonia wastewater containing high levels of oil, dust and phenol generated in the process of producing blue charcoal by fractionating and utilizing low-rank coal. The device and method adopt an oil remover and an extraction oil removal method to remove organic matter such as oil, dust, phenol and impurities in the phenol-ammonia raw material wastewater, thereby solving the problems of device blockage, unqualified recovered product indicators and substandard effluent in the traditional blue charcoal phenol-ammonia wastewater treatment process.
[0005] The technical solution adopted by the present invention is:
[0006] 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 circulation tank and a phenol tower, wherein the oil separator is connected to the upper part of the extraction tower through a pipeline, the top of the extraction tower is connected to an extract delivery pipeline, the extract delivery pipeline is connected to a phenol tower heat exchanger, the phenol tower heat exchanger is connected to the phenol tower through a pipeline, the bottom of the phenol tower is connected to a phenol oil delivery pipeline, the extractant delivery pipeline connected to the top of the phenol tower is connected to the extractant circulation tank after heat exchange in the phenol tower heat exchanger, the extractant delivery pipeline connected to the extractant circulation tank is connected to the lower part of the extraction tower, the bottom of the extraction tower is connected to a dephenolization and oil removal wastewater delivery pipeline, the extraction towers are connected in series in sequence, the dephenolization and oil removal wastewater delivery pipeline of the upper extraction tower is connected to the upper part of the next extraction tower, the dephenolization and oil removal wastewater delivery pipeline connected to the bottom of the last extraction tower is connected to the deacidification tower, the top of the deacidification tower is connected to an acid gas exhaust pipeline, the acid gas exhaust pipeline is connected to a sulfur production device, the bottom of the deacidification tower is The deacidification wastewater delivery pipeline is connected, and the deacidification wastewater delivery pipeline is connected to the water tower. The top of the water tower is connected to the water tower condenser cooler through a pipeline, and the water tower condenser cooler is connected to the water tower reflux tank through a pipeline. The bottom of the water tower reflux tank is connected to a water reflux pipe, and the water reflux pipe is connected to the water tower. The top of the water tower reflux tank is connected to the extractant recovery delivery pipeline, and the extractant recovery delivery pipeline is connected to the extractant circulation tank. The water tower kettle is connected to the deacidification wastewater delivery pipeline, and the deacidification wastewater delivery pipeline is connected to the upper part of the deammonification tower. The deammonification tower is connected to the sodium hydroxide solution injection pipeline, and the top of the deammonification tower is connected to the mixed gas delivery pipeline. Three groups of condensers and separators are connected alternately in series on the mixed gas delivery pipeline. The ammonia separated by the separator is transported to the ammonia refining system through the top connecting pipeline, and the condensate separated by the separator is returned to the deammonification tower through a pipeline connection. The bottom of the deammonification tower is connected to the deammonification wastewater delivery pipeline, and the deammonification wastewater delivery pipeline transports purified water to the biochemical treatment system.
[0007] The dephenolization and oil removal wastewater conveying pipeline connecting the extraction tower and the deacidification tower is divided into two feed pipelines, one is a cold feed pipeline connected to the top of the deacidification tower, and the other is a hot feed pipeline connected to the upper part of the deacidification tower.
[0008] The hot feed pipeline is connected with a deacidification tower feed preheater, and the deacidification tower feed preheater is connected with the deacidification wastewater conveying pipeline output from the bottom of the deacidification tower through heat exchange.
[0009] The deamination wastewater conveying pipeline is connected with a deamination tower feed preheater, and the deamination tower feed preheater is connected with the deamination wastewater conveying pipeline output from the bottom of the deamination tower through heat exchange.
[0010] The number of the extraction towers is 1 to 6, and the extraction towers are connected in series and are sequentially 1# to 6# extraction towers.
[0011] The extraction tower has an extraction stage number of 1 to 5, and the stages of each extraction tower may be the same or different.
[0012] A method for treating phenol-ammonia blue charcoal wastewater, comprising the following steps:
[0013] (a) Oil separation and dust removal: The phenol ammonia charcoal raw material wastewater enters the oil separator, and the temperature is adjusted to 25°C-50°C. The oil and dust impurities in the phenol ammonia charcoal wastewater are removed in the oil separator to obtain oil separation and dust removal wastewater;
[0014] (b) extractive dephenolization and oil removal: the oil-removal and dust-removal wastewater obtained in step (a) enters the 1# extraction tower from the upper part of the extraction tower, and the extractant enters from the bottom of the 1# extraction tower; in the 1# extraction tower, the oil-removal and dust-removal wastewater and the extractant are continuously countercurrently extracted to obtain the 1# extract at the top of the 1# extraction tower, and obtain the 1# dephenolization and oil-removal wastewater in the kettle of the 1# extraction tower; the 1# dephenolization and oil-removal wastewater enters the 2# extraction tower from the upper part of the 2# extraction tower, and the extractant enters the 2# extraction tower from the bottom of the 2# extraction tower; In the 2# extraction tower, the 1# dephenolization and dust removal wastewater is continuously countercurrently extracted with the extractant, and the 2# extract is obtained at the top of the 2# extraction tower, and the 2# dephenolization and oil removal wastewater is obtained in the 2# extraction tower kettle; the 2# dephenolization and oil removal wastewater continues to enter the subsequent extraction towers in the same way to be continuously countercurrently extracted with the extractant to obtain dephenolization and oil removal wastewater and extracts, and the mixture after the extracts of each tower are mixed is called the extraction mixture, and the wastewater produced from the kettle of the last stage extraction tower is called dephenolization and oil removal wastewater;
[0015] (c) stripping deacidification: the dephenolization and deoiling wastewater produced in step (b) is divided into two feeds, one of which is a cold feed and directly enters the deacidification tower; the other is a hot feed, which is heat-exchanged with the deacidification wastewater produced from the deacidification tower kettle before entering the deacidification tower; the temperature of the cold feed is 25-50°C, the hot feed is 50-100°C, and the volume ratio of the cold feed to the hot feed is 1:1-1:10; the operating pressure of the deacidification tower is 0.1-0.7MPa; carbon dioxide and hydrogen sulfide acidic gas are discharged from the top of the deacidification tower, and the acidic gas is sent to the sulfur production device; the deacidification wastewater produced from the deacidification tower kettle contains a small amount of extractant and ammonia, and the deacidification wastewater is transported to a water tower to recover the extractant;
[0016] (d) Extraction agent recovery: The deacidification wastewater produced in step (c) is sent to a water tower, and the water tower is used to recover the trace amount of extraction agent dissolved in the water. The mixture of extraction agent and water is produced from the top of the water tower, and enters the reflux tank of the water tower after passing through the condenser cooler of the water tower. The extraction agent and water are separated in the reflux tank of the water tower. The extraction agent is produced from the upper layer of the reflux tank of the water tower to the extraction agent circulation tank, and the extraction agent is recycled; the water is produced from the lower layer of the reflux tank of the water tower, and it is returned to the water tower as reflux liquid; the deacidification wastewater is produced from the bottom of the water tower. The operating pressure at the top of the water tower is 0.01-0.6MPa, the operating temperature at the top of the tower is 80-145°C, and the operating temperature at the bottom of the tower is 120-165°C.
[0017] (e) stripping deamination: the deamination wastewater of step (d) is deammonified by a deamination tower, and the deamination wastewater enters the deamination tower from the upper part; a sodium hydroxide solution with a mass fraction of 5-36% is injected into the deamination tower at or below the feed layer of the deamination tower to convert fixed ammonia into ammonia gas for removal; a mixed gas containing water and ammonia is produced from the top of the deamination tower, and is condensed in three stages by a condenser and a separator, and is gradually reduced in pressure and temperature to obtain high-purity ammonia gas, which is sent to an ammonia refining system, and the condensate is returned to the deamination tower; the operating pressure at the top of the deamination tower is 0.1-0.6MPa, and the operating temperature at the top of the tower is 85°C-150°C; the deamination tower kettle produces deammonified wastewater that meets the requirements of biochemical treatment, and the deammonified wastewater, i.e., purified water, is sent to the biochemical treatment system;
[0018] (f) Regeneration of the extractant: the extraction mixture obtained in step (b) is fed into a phenol tower; a high-purity extractant is extracted from the top of the phenol tower and returned to a circulation tank of the extraction tower for use; phenol oil is extracted from the bottom of the phenol tower and is sent to a storage tank as a by-product; the top pressure of the extraction tower is -0.01 to 0.02 MPa, the top operating temperature is 70-110° C., and the bottom operating temperature is 150-210° C.
[0019] The number of the extraction towers is 1 to 6, the extraction temperature of the extraction towers is 25 to 50° C., the operating pressure is normal pressure, the pH value of the semi-carbon phenol-ammonia wastewater is 3 to 11, and the semi-carbon phenol-ammonia wastewater flows through each extraction tower in series.
[0020] The extractant is one of methyl isobutyl ketone, diisopropyl ether, butyl acetate, dimethyl carbonate, petroleum ether or a combination thereof.
[0021] The extractant entering each extraction tower is a fresh extractant, which is countercurrently contacted with the phenol-ammonia blue charcoal wastewater, and a cross-current extraction is formed between the extraction towers. The fresh extractant can be a newly purchased extractant, a recycled circulating extractant, or a mixture of the two.
[0022] The ratio of the extractant entering each extraction tower to the phenol-ammonia blue charcoal wastewater is 1:1 to 1:10, and this ratio of each extraction tower can be the same or different.
[0023] The beneficial effects of the present invention are as follows: firstly, an oil separator is used to effectively remove oil substances and dust impurities in phenol ammonia charcoal wastewater, thereby reducing the burden of clogging of subsequent treatment equipment, reducing the COD of wastewater, and improving the treatment effect; placing an extraction tower before the deacidification and deamination process not only effectively removes phenol in the phenol ammonia charcoal wastewater, but also extracts and removes the "emulsified oil" in the phenol ammonia charcoal wastewater, which is beneficial to improving the quality index of the product liquid ammonia or ammonia water, facilitating the stable operation of the deacidification and deamination tower or the deacidification tower and the deamination tower, and is beneficial to improving the operating efficiency and reducing the operating cost; combining countercurrent extraction with series extraction to give full play to their respective advantages to achieve dephenolization and oil removal, that is, phenol ammonia charcoal Carbon wastewater passes through various extraction towers in series, and the interior of a single extraction tower is countercurrent contact; the extractant entering each extraction tower is fresh, which improves the effect of extraction dephenolization and deoiling and reduces the loss of extractant; the deacidification, deammoniation, extractant recovery (water tower), and extractant regeneration (phenol tower) are treated separately, which improves the stability of the device operation, improves the product: ammonia water or liquid ammonia, phenol oil quality indicators, and improves the operation efficiency; reduces the reflux ratio of each tower operation, reduces the energy consumption per ton of water treatment, and makes the de-biochemical treatment water quality indicators better; the operating pressure of the extractant recovery and regeneration (phenol tower) can be either negative pressure or positive pressure, making the applicability more flexible and more practical. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 It is a schematic diagram of the processing device of the present invention.
[0025] Among them: 1-oil separator; 2-extraction tower; 3-dephenolization and oil removal wastewater transportation pipeline; 4-deacidification tower; 5-deacidification tower feed preheater; 6-water tower; 7-water tower condenser cooler; 8-deammonification tower feed preheater; 9-deammonification tower; 10-condenser; 11-separator; 12-deammonification wastewater transportation pipeline; 13-cold feed pipeline; 14-hot feed pipeline; 15-sodium hydroxide solution injection pipeline; 16-phenol tower; 17-phenol tower heat exchanger; 18-extractant circulation tank; 19-water tower reflux tank; 20-extractant transportation pipeline; 21-phenol oil transportation pipeline; 22-extractant transportation pipeline; 23-acid gas discharge pipeline; 24-deacidification wastewater transportation pipeline; 25-water reflux pipe; 26-extractant recovery transportation pipeline; 27-deacidification wastewater transportation pipeline. DETAILED DESCRIPTION
[0026] 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 deammoniation tower 9, an extractant circulation tank 18 and a phenol tower 16, wherein the oil separator 1 is connected to the upper part of the extraction tower 2 through a pipeline, the top of the extraction tower 2 is connected to an extract delivery pipeline 20, the extract delivery pipeline 20 is connected to a phenol tower heat exchanger 17, the phenol tower heat exchanger 17 is connected to the phenol tower 16 through a pipeline, the bottom of the phenol tower 16 is connected to a phenol oil delivery pipeline 21, and the extractant delivery pipeline 22 connected to the top of the phenol tower 16 is connected to the phenol tower heat exchanger 17 after heat exchange. The extractant circulation tank 18 is connected to the extractant conveying pipeline 22 connected to the extractant circulation tank 18 and connected to the lower part of the extraction tower 2. The bottom of the extraction tower 2 is connected to the dephenolization and oil removal wastewater conveying pipeline 3. The extraction towers 2 are connected in series in sequence. The dephenolization and oil removal wastewater conveying pipeline 3 of the upper extraction tower 2 is connected to the upper part of the next extraction tower 2. The dephenolization and oil removal wastewater conveying pipeline 3 connected to the bottom of the last extraction tower 2 is connected to the deacidification tower 4. The top of the deacidification tower 4 is connected to the acid gas exhaust pipeline 23. The acid gas exhaust pipeline 23 is connected to the sulfur production device. The deacidification tower The bottom of the tower 4 is connected to a deacidification wastewater delivery pipeline 24, which is connected to a water tower 6. The top of the water tower 6 is connected to a water tower condenser cooler 7 through a pipeline. The water tower condenser cooler 7 is connected to a water tower reflux tank 19 through a pipeline. The bottom of the water tower reflux tank 19 is connected to a water reflux pipe 25, which is connected to the water tower 6. The top of the water tower reflux tank 19 is connected to an extractant recovery delivery pipeline 26, which is connected to an extractant circulation tank 18. The kettle of the water tower 6 is connected to a deacidification wastewater delivery pipeline 27, and the deacidification wastewater delivery pipeline 28 is connected to the extractant circulation tank 18. The water delivery pipeline 27 is connected to the upper part of the deamination tower 9, the sodium hydroxide solution injection pipeline 15 is connected to the deamination tower 9, the top of the deamination tower 9 is connected to the mixed gas delivery pipeline, three groups of condensers 10 and separators 11 are connected in series and alternately connected, the ammonia separated by the separator 11 is delivered to the ammonia refining system through the top connecting pipeline, the condensate separated by the separator 11 is returned to the deamination tower 9 through the pipeline connection, the bottom of the deamination tower 9 is connected to the deamination wastewater delivery pipeline 12, and the deamination wastewater delivery pipeline 12 delivers the purified water to the biochemical treatment system.
[0027] The dephenolization and oil removal wastewater conveying pipeline 3 connecting the extraction tower 2 and the deacidification tower 4 is divided into two feed pipelines, one is a cold feed pipeline 13, which is connected to the top of the deacidification tower 4, and the other is a hot feed pipeline 14, which is connected to the upper part of the deacidification tower 4.
[0028] The hot feed pipeline 14 is connected to the deacidification tower feed preheater 5, and the deacidification tower feed preheater 5 is connected to the deacidification wastewater conveying pipeline 24 output from the bottom of the deacidification tower 4 through heat exchange.
[0029] The deamination wastewater delivery pipeline 27 is connected to a deamination tower feed preheater 8 , and the deamination tower feed preheater 8 is connected to a deamination wastewater delivery pipeline 12 output from the bottom of a deamination tower 9 through heat exchange.
[0030] The number of the extraction towers 2 is 1 to 6, and the extraction towers 2 are connected in series and are sequentially 1# to 6# extraction towers.
[0031] The extraction tower 2 has an extraction stage number of 1 to 5, and the stage numbers of the extraction towers 2 may be the same or different.
[0032] A method for treating phenol-ammonia blue charcoal wastewater, comprising the following steps:
[0033] (a) Oil separation and dust removal: The phenol ammonia blue charcoal raw material wastewater enters the oil separator 1, and the temperature is adjusted to 25-50°C. Impurities such as oil and dust are collected from the oil outlet of the oil separator 1, and oil separation and dust removal wastewater is collected from the water outlet of the oil separator 1.
[0034] (b) extractive dephenolization and deoiling: the oil-removal and dust-removal wastewater obtained in step (a) enters the 1# extraction tower 2 from the upper part of the extraction tower 2, and the extractant in the extractant delivery pipeline 22 enters the 1# extraction tower from the bottom of the extraction tower 2; in the 1# extraction tower, the oil-removal and dust-removal wastewater is in countercurrent contact with the extractant; 1# extract and 1# dephenolization and oil-removal wastewater are respectively extracted at the top of the 1# extraction tower and the kettle of the 1# extraction tower, and the 1# dephenolization and dust-removal wastewater enters the 2# extraction tower from the upper part of the extraction tower 2 along the dephenolization and oil-removal wastewater delivery pipeline 3, and the extractant is removed from the extraction tower 2; The bottom of tower 2 is taken and enters the 2# extraction tower; in the 2# extraction tower, the 1# dephenolization and oil removal wastewater is continuously countercurrently extracted with the extractant, and the 2# extract and 2# dephenolization and oil removal wastewater are obtained at the top and bottom of the 2# extraction tower respectively. The 2# dephenolization wastewater continues to enter the subsequent extraction tower 2 in the same way to be continuously countercurrently extracted with the extractant, and the extracts taken from the top of each extraction tower 2 are mixed and used as the feed of the phenol tower 16; the wastewater taken from the bottom of the last stage extraction tower 2 is called dephenolization and oil removal wastewater, and the dephenolization and oil removal wastewater is used as the feed of the water tower. The number of extraction towers 2 is 1 to 6, and the ratio of the extractant entering each extraction tower 2 to the phenol ammonia blue carbon wastewater is 1:1 to 1:10.
[0035] (c) Stripping and deacidification: The dephenolization and deoiling wastewater produced from the bottom of the extraction tower 2 in step (b) is divided into two feeds, one of which is a cold feed and directly enters the deacidification tower 4 along the cold feed pipeline 13; the other is a hot feed, and the hot feed is preheated by the deacidification tower feed preheater 5 in the hot feed pipeline 14. The hot feed is heat-exchanged with the deacidification wastewater produced from the bottom of the deacidification tower 4 in the deacidification tower feed preheater 5 to enter the deacidification tower 4 at a temperature of 50-100°C. The volume ratio of the cold feed to the hot feed is 1:1 to 1:10; the operating pressure of the deacidification tower 4 is 0.1-0.7MPa. Acid gases such as carbon dioxide and hydrogen sulfide are discharged from the top of the deacidification tower 4, and the acid gases are transported to the sulfur production device along the acid gas discharge pipeline 23; the deacidification wastewater is produced from the bottom of the deacidification tower 4, and the deacidification wastewater is used as the feed of the water tower.
[0036] (d) Extraction agent recovery: The deacidification wastewater extracted in step (c) is transported to the water tower 6 along the deacidification wastewater conveying pipeline 24, and the water tower 6 is used to recover the trace amount of extraction agent dissolved in the water. The extraction agent and water mixture is extracted from the top of the water tower 6, and the mixture is condensed and cooled by the water tower condenser cooler 7 and enters the water tower reflux tank 19. The extraction agent and water are separated in the water tower reflux tank 19, and the extraction agent is extracted from the upper layer of the water tower reflux tank 19 to the extraction agent circulation tank 18, and the extraction agent is recycled; the water is extracted from the lower layer of the water tower reflux tank 19, and it is returned to the water tower 6 as reflux liquid; the deacidification wastewater is extracted from the bottom of the water tower 6. The operating pressure at the top of the water tower 6 is 0.01-0.6MPa, the operating temperature at the top of the tower is 80-145°C, and the operating temperature at the bottom of the tower is 120-165°C.
[0037] (e) Stripping deamination: The deamination wastewater of step (d) is deammonified by using a deammonification tower 9, and the deammonification wastewater enters the deammonification tower 9 from the upper part. At the feed layer or below the feed layer of the deammonification tower 9, a sodium hydroxide solution with a mass fraction of 5-36% is injected into the deammonification tower 9 to convert fixed ammonia into ammonia gas for removal; a mixed gas containing water and ammonia is produced from the top of the deammonification tower 9, and is subjected to three-stage condensation and three-stage flash evaporation in a condenser 10 and a separator 11, and is gradually reduced in pressure and cooled, and flashed to finally obtain high-purity ammonia gas, which is sent to the ammonia refining system, and the condensate in the flash tank is returned to the deammonification tower 9; the operating pressure at the top of the deammonification tower 9 is 0.1-0.6MPa, and the operating temperature at the top of the tower is 85°C-150°C; the deammonification wastewater that meets the requirements of biochemical treatment is produced from the bottom of the deammonification tower 9, and the deammonification wastewater, i.e., purified water, is sent to the biochemical treatment system.
[0038] (f) Extraction agent regeneration: The extraction mixture obtained in step (b) is used as the feed of phenol tower 16, and is preheated to 65°C in phenol tower feed preheater 17 before entering phenol tower 16. High-purity extraction agent is extracted from the top of phenol tower 16, and the extraction agent returns to extraction agent circulation tank 18 to be recycled by extraction tower 2; phenol oil is extracted from the bottom of phenol tower 16, and phenol oil is sent to a storage tank as a by-product. The top pressure of phenol tower 16 is -0.01 to 0.02 MPa, the top operating temperature is 70-120°C, and the bottom operating temperature is 150-210°C.
[0039] The present invention will be described in detail below with reference to specific embodiments:
[0040] Example 1
[0041] The processing capacity is 100t / h of phenol-ammonia blue carbon wastewater raw material, COD content is 41500mg / L, oil content is 3800mg / L, total phenol content is 11800mg / L, ammonia nitrogen content is 8000mg / L, sulfide content is 2500mg / L, dust content is 1500mg / L, pH value is 9.5, temperature is 25℃. Figure 1 The middle treatment device is processed according to the processing steps, and the main process parameters are as follows:
[0042] (a) Oil separation and dust removal: The phenol ammonia charcoal wastewater is initially purified by using an oil separator 1. The phenol ammonia charcoal wastewater raw material directly enters the oil separator 1, and light oil, heavy oil and impurities are extracted from the oil outlet. The oil separation and dust removal wastewater is extracted from the water outlet, and its oil content is 2000 mg / L and the solid dust content is 150 mg / L.
[0043] (b) Extraction dephenolization and oil removal: This example uses 3 extraction towers 2, each extraction tower 2 has 4 extraction stages, the extractant is a mixed extractant composed of 60% methyl isobutyl ketone and 40% petroleum ether by volume, the operating temperature of each extraction tower 2 is 40°C, the operating pressure of each extraction tower 2 is normal pressure, and the volume ratio of the extractant of each extraction tower 2 to the phenol-ammonia blue charcoal wastewater is 1:3. The oil content in the dephenolization and oil removal wastewater extracted from the reactor of the 3# extraction tower is 100 mg / L, and the total phenol content is 800 mg / L.
[0044] (c) Steam stripping and deacidification: The operating pressure of the deacidification tower 4 is 0.5MPa, the operating temperature of the tower top is 50℃, and the operating temperature of the tower bottom is 150℃. The dephenolization and deoiling wastewater produced from the tower bottom of the extraction tower 2 is divided into two feeds, one of which is a cold feed, which directly enters the deacidification tower 4 along the cold feed pipeline 13; the other is a hot feed, and the hot feed and the deacidification wastewater produced from the tower bottom of the deacidification tower 4 are heat-exchanged in the deacidification tower feed preheater 5 to 100℃ before entering the deacidification tower 4. The volume ratio of the cold feed to the hot feed is 1:3, and the top of the deacidification tower 4 discharges acidic gases such as carbon dioxide, hydrogen sulfide, and extractant, and the acidic gases are sent to the sulfur production device; the deacidification wastewater produced from the tower bottom of the deacidification tower 4 has a sulfide content of 50mg / L.
[0045] (d) Stripping extractant: The operating pressure of water tower 6 is 0.3 MPa, the operating temperature of the tower top is 105° C., and the operating temperature of the tower bottom is 140° C. The stripping wastewater produced in the tower bottom of water tower 6 has a COD content of 3500 mg / L.
[0046] (e) Stripping deamination: Step (d) The deamination wastewater is deammonified by using a deamination tower 9, and the deamination wastewater enters the deamination tower 9 from the upper part of the deamination tower 9. The operating pressure of the deamination tower 9 is 0.5MPa, the operating temperature of the tower top is 145°C, and the operating temperature of the tower bottom is 160°C. A sodium hydroxide solution with a mass concentration of 32% and a flow rate of 15Kg / h is injected into the deamination tower at the feed layer of the deamination tower 9; the ammonia-containing mixed gas is produced from the top of the deamination tower 9, and 99.5% by-product ammonia gas is obtained through three-stage condensation flash evaporation; the deamination wastewater produced from the tower bottom of the deamination tower 9 has a COD content of 3500mg / L, an ammonia nitrogen content of 130mg / L, an oil content of 100mg / L, a sulfide content of 50mg / L, and a solid dust content of 100mg / L. The deamination wastewater is used as biochemical influent, which fully meets the various influent indicators of the biochemical system.
[0047] (f) Regeneration of extractant: The operating pressure of phenol tower 16 is atmospheric pressure, the operating temperature of the tower top is 105° C., and the operating temperature of the tower bottom is 201° C. A high-purity extractant is extracted from the top of phenol tower 16 and returned to extraction tower 2 for recycling; phenol oil is extracted from the bottom of the phenol tower 16 and is sent to a storage tank as a by-product.
[0048] A comparative example is designed to compare embodiment 1, and the effect of the number of extraction towers 2 on the extraction, dephenolization and oil removal of phenol-ammonia blue charcoal wastewater and the removal of solid dust is examined through the comparative example.
[0049] Compared with Example 1, a different number of extraction towers 2 are used, and other process conditions are the same. A comparative example is designed to finally obtain various indicators of dephenolization and oil removal wastewater.
[0050]
[0051] Compared with Example 1, a different number of extraction towers 2 are used, and other process conditions are the same. A comparative example is designed to finally obtain various indicators of deammoniation wastewater.
[0052]
[0053] Compared with Example 1, a different number of extraction towers 2 are used, and other process conditions are the same. A comparative example is designed to finally obtain the removal rate of various indicators of deammoniation wastewater.
[0054]
[0055] Example 2
[0056] The processing capacity is 50t / h of phenol-ammonia blue carbon wastewater raw material, COD content is 39500mg / L, oil content is 2700mg / L, total phenol content is 8500mg / L, ammonia nitrogen content is 5500mg / L, sulfide content is 4000mg / L, dust content is 2300mg / L, pH value is 5.6, temperature is 45℃. Figure 1 The main process parameters are as follows:
[0057] (a) Oil separation and dust removal: The phenol-ammonia charcoal wastewater is initially purified by using an oil separator 1. The phenol-ammonia charcoal wastewater raw material directly enters the oil separator 1, and light oil, heavy oil and impurities are extracted from the oil outlet. The oil separation and dust removal wastewater is extracted from the water outlet, and its oil content is 1600 mg / L and the solid dust content is 300 mg / L.
[0058] (b) Extraction dephenolization and oil removal: This example uses 4 extraction towers 2, each of which has 3 extraction stages. The extractant is a mixed extractant composed of 40% methyl isobutyl ketone, 30% petroleum ether and 30% ethyl acetate in a volume ratio. The operating temperature of each extraction tower 2 is 45°C, and the operating pressure of each extraction tower 2 is normal pressure. The volume ratio of the extractant of each extraction tower 2 to the phenol-ammonia blue charcoal wastewater is 1:6. The oil content in the dephenolization and oil removal wastewater extracted from the kettle of the 4# extraction tower is 80mg / L, the total phenol content is 750mg / L, and the dust is 80mg / L.
[0059] (c) Steam stripping and deacidification: The operating pressure of deacidification tower 4 is 0.2MPa, the operating temperature of the tower top is 48℃, and the operating temperature of the tower bottom is 130℃. The dephenolization and deoiling wastewater produced from the bottom of extraction tower 2 is two feeds, one of which is cold feed and directly enters deacidification tower 4; the other is hot feed, which is heat exchanged with the deacidification wastewater produced from the bottom of deacidification tower 4 to 90℃ and enters deacidification tower 4. The volume ratio of cold feed to hot feed is 1:8. Acid gases such as carbon dioxide, hydrogen sulfide, and extractant are discharged from the top of deacidification tower 4, and the acid gases are sent to the sulfur production device; the deacidification wastewater produced from the bottom of deacidification tower 4 has a sulfide content of 55mg / L.
[0060] (d) Stripping extractant: The operating pressure of water tower 6 is 0.1MPa, the operating temperature of the tower top is 78℃, and the operating temperature of the tower bottom is 120℃. The stripping wastewater produced from the tower bottom of water tower 6 has a COD content of 3015mg / L and oil of 80mg / L.
[0061] (e) Stripping deamination: In step (d), the deamination wastewater is treated with a deamination tower 9 to remove ammonia, and the deamination wastewater enters the deamination tower 9 from the upper part. The operating pressure of the deamination tower 9 is 0.2MPa, the operating temperature of the tower top is 125°C, and the operating temperature of the tower bottom is 135°C. A sodium hydroxide solution with a mass concentration of 32% and a flow rate of 6Kg / h is injected into the deamination tower at the feed layer of the deamination tower 9; the ammonia-containing mixed gas is produced from the top of the deamination tower 9, and 99.3% by-product ammonia gas is obtained through three-stage condensation flash evaporation. The deamination wastewater produced from the bottom of the deamination tower 9 has a COD content of 2850mg / L, an ammonia nitrogen content of 120mg / L, an oil content of 80mg / L, a sulfide content of 55mg / L, and a solid dust content of 80mg / L. The deamination wastewater is used as biochemical influent, which fully meets the various influent indicators of the biochemical system.
[0062] (f) Extractant regeneration: The operating pressure of the phenol tower 16 is -0.04 MPa, the operating temperature of the tower top is 82° C., and the operating temperature of the tower bottom is 173° C. A high-purity extractant is extracted from the top of the phenol tower 16, and the extractant is returned to the extractant circulation tank 18 for recycling in the extraction tower 2; phenol oil is extracted from the bottom of the phenol tower 16, and the phenol oil is sent to the storage tank as a by-product.
[0063] A comparative example is designed to compare Example 2, and the effect of the combination ratio of the extractants on the extraction, dephenolization and oil removal of phenol-ammonia blue charcoal wastewater and the removal of solid dust is investigated through the comparative example.
[0064] Compared with Example 2, a different ratio of extractant is used, and other process conditions are the same. A comparative example is designed to finally obtain various indicators of dephenolization and oil removal wastewater.
[0065]
[0066] Compared with Example 2, different extractant ratios are used, and other process conditions are the same. A comparative example is designed, and different extractant ratios are used as follows to finally obtain various indicators of dephenolization and oil removal wastewater.
[0067]
[0068] Compared with Example 2, different extractant ratios are used, and other process conditions are the same. A comparative example is designed, and different extractant ratios are used as follows to finally obtain various indicators of deammoniation wastewater.
[0069]
[0070] Compared with Example 2, different extractant ratios are used, and other process conditions are the same. A comparative example is designed, and different extractant ratios are used as follows to finally obtain various indicators of deammoniation wastewater.
[0071]
[0072] Compared with Example 2, different ratios of extractants were used, and the other process conditions were the same. Comparative examples were designed, and finally the removal rates of various indicators of deammoniation wastewater were obtained. The extractants for comparison numbers 1, 2, and 3 were methyl isobutyl ketone, petroleum ether, and ethyl acetate, and the extractants for comparison numbers 4, 5, and 6 were methyl isobutyl ketone, diisopropyl ether, and dimethyl carbonate.
[0073]
[0074] From the data of Example 1 and Example 2 and the comparative examples, it can be seen that the oil remover 1 has a very good effect on removing oil substances and dust impurities in the phenol ammonia blue charcoal wastewater, which greatly reduces the burden of clogging of subsequent treatment equipment. After the action of the extraction tower 2, the deacidification tower 4 and the deamination tower 9, the removal effect of COD, sulfide and ammonia nitrogen is also very obvious. The various indicators of the deammoniation wastewater obtained by different extractants in different proportions can also meet the indicators for entering the biochemical system.
[0075] The embodiments of the present invention are described in detail above, but the contents described are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.
Claims
1. A phenol-ammonia blue charcoal wastewater treatment device, characterized in that: The invention comprises an oil separator (1), a plurality of extraction towers (2), a deacidification tower (4), a water tower (6), a deammoniation tower (9), an extractant circulation tank (18) and a phenol tower (16); the oil separator (1) is connected to the upper part of the extraction tower (2) through a pipeline; the top of the extraction tower (2) is connected to an extract delivery pipeline (20); the extract delivery pipeline (20) is connected to a phenol tower heat exchanger (17); the phenol tower heat exchanger (17) is connected to the phenol tower (16) through a pipeline; the bottom of the phenol tower (16) is connected to a phenol oil delivery pipeline (21); the extractant delivery pipeline (22) connected to the top of the phenol tower (16) is connected to the phenol tower heat exchanger (17) after heat exchange with the phenol tower heat exchanger (17); The extractant circulation tank (18) is connected to an extractant conveying pipeline (22) connected to the extractant circulation tank (18) and connected to the lower part of the extraction tower (2). The bottom of the extraction tower (2) is connected to a dephenolization and oil removal wastewater conveying pipeline (3). The extraction towers (2) are connected in series in sequence. The dephenolization and oil removal wastewater conveying pipeline (3) of the upper extraction tower (2) is connected to the upper part of the next extraction tower (2). The dephenolization and oil removal wastewater conveying pipeline (3) connected to the bottom of the last extraction tower (2) is connected to a deacidification tower (4). The top of the deacidification tower (4) is connected to an acid gas exhaust pipeline (23). The acid gas exhaust pipeline (23) is connected to a sulfur production device. The deacidification tower (4) is connected to a sulfur production device. ) The bottom of the tower is connected to a deacidification wastewater delivery pipeline (24), the deacidification wastewater delivery pipeline (24) is connected to a water tower (6), the top of the water tower (6) is connected to a water tower condenser cooler (7) through a pipeline, the water tower condenser cooler (7) is connected to a water tower reflux tank (19) through a pipeline, the bottom of the water tower reflux tank (19) is connected to a water reflux pipe (25), the water reflux pipe (25) is connected to the water tower (6), the top of the water tower reflux tank (19) is connected to an extractant recovery delivery pipeline (26), the extractant recovery delivery pipeline (26) is connected to an extractant circulation tank (18), and the bottom of the water tower (6) is connected to a deacidification wastewater delivery pipeline (27). The deamination wastewater delivery pipeline (27) is connected to the upper part of the deamination tower (9), the deamination tower (9) is connected to the sodium hydroxide solution injection pipeline (15), the top of the deamination tower (9) is connected to the mixed gas delivery pipeline, three groups of condensers (10) and separators (11) are connected in series and alternately connected, the ammonia separated by the separator (11) is delivered to the ammonia refining system through the top connecting pipeline, the condensate separated by the separator (11) is returned to the deamination tower (9) through the pipeline connection, the bottom of the deamination tower (9) is connected to the deamination wastewater delivery pipeline (12), and the deamination wastewater delivery pipeline (12) delivers the purified water to the biochemical treatment system.
2. The phenol-ammonia blue charcoal wastewater treatment device according to claim 1, characterized in that: The dephenolization and deoiling wastewater conveying pipeline (3) connecting the extraction tower (2) and the deacidification tower (4) is divided into two feed pipelines, one of which is a cold feed pipeline (13), which is connected to the top of the deacidification tower (4), and the other is a hot feed pipeline (14), which is connected to the upper part of the deacidification tower (4).
3. The phenol-ammonia blue charcoal wastewater treatment device according to claim 2, characterized in that: The hot feed pipeline (14) is connected to a deacidification tower feed preheater (5), and the deacidification tower feed preheater (5) is connected to a deacidification wastewater delivery pipeline (24) output from the bottom of the deacidification tower (4) through heat exchange.
4. The phenol-ammonia blue charcoal wastewater treatment device according to claim 1, characterized in that: The deamination wastewater delivery pipeline (27) is connected to a deamination tower feed preheater (8), and the deamination tower feed preheater (8) is connected to a deamination wastewater delivery pipeline (12) output from the bottom of the deamination tower (9) through heat exchange.
5. The phenol-ammonia blue charcoal wastewater treatment device according to claim 1, characterized in that: The number of the extraction towers (2) is 1 to 6, and the extraction towers (2) are connected in series and are sequentially 1# to 6# extraction towers.
6. The phenol-ammonia blue charcoal wastewater treatment device according to claim 1, characterized in that: The extraction tower (2) has an extraction stage number of 1 to 5, and the stages of each extraction tower (2) may be the same or different.
7. A method for treating phenol ammonia charcoal wastewater using the phenol ammonia charcoal wastewater treatment device according to any one of claims 1 to 6, characterized in that: The steps are: (a) Oil separation and dust removal: The phenol ammonia charcoal raw material wastewater enters the oil separator (1), and the temperature is adjusted to 25°C-50°C. The oil and dust impurities in the phenol ammonia charcoal wastewater are removed in the oil separator (1) to obtain oil separation and dust removal wastewater; (b) extractive dephenolization and oil removal: the oil-removing and dust-removing wastewater obtained in step (a) enters the 1# extraction tower from the upper part of the extraction tower (2), and the extractant enters from the bottom of the 1# extraction tower; in the 1# extraction tower, the oil-removing and dust-removing wastewater and the extractant are continuously subjected to countercurrent extraction, and a 1# extract is obtained at the top of the 1# extraction tower, and a 1# dephenolization and oil-removing wastewater is obtained in the kettle of the 1# extraction tower; the 1# dephenolization and oil-removing wastewater enters the 2# extraction tower from the upper part of the 2# extraction tower, and the extractant enters the 2# extraction tower from the bottom of the 2# extraction tower; #In the extraction tower, the 1# dephenolization and dust removal wastewater is subjected to continuous countercurrent extraction with the extractant, and the 2# extract is obtained at the top of the 2# extraction tower, and the 2# dephenolization and oil removal wastewater is obtained in the bottom of the 2# extraction tower; the 2# dephenolization and oil removal wastewater continues to enter the subsequent extraction tower (2) in the same manner to be subjected to continuous countercurrent extraction with the extractant to obtain dephenolization and oil removal wastewater and extract, and the mixture after the extracts of each tower are mixed is called the extraction mixture, and the wastewater produced from the bottom of the last stage extraction tower (2) is called the dephenolization and oil removal wastewater; (c) Steam stripping and deacidification: the dephenolization and deoiling wastewater produced in step (b) is divided into two feeds, one of which is a cold feed and directly enters the deacidification tower (4); the other is a hot feed, which is heat-exchanged with the deacidification wastewater produced from the bottom of the deacidification tower (4) before entering the deacidification tower (4); the temperature of the cold feed is 25-50°C, the hot feed is 50-100°C, and the volume ratio of the cold feed to the hot feed is 1:1-1:10; the operating pressure of the deacidification tower (4) is 0.1-0.7MPa; carbon dioxide and hydrogen sulfide acidic gas are discharged from the top of the deacidification tower (4), and the acidic gas is sent to the sulfur production device; the deacidification wastewater produced from the bottom of the deacidification tower (4) contains a small amount of extractant and ammonia substances, and the deacidification wastewater is sent to the water tower (6) to recover the extractant; (d) Extraction agent recovery: the deacidification wastewater obtained in step (c) is sent to a water tower (6), and the water tower (6) is used to recover the trace amount of extraction agent dissolved in the water. The mixture of extraction agent and water is obtained from the top of the water tower (6), and enters the reflux tank of the water tower (6) after passing through the water tower condenser cooler (7). The extraction agent and water are separated into layers in the reflux tank of the water tower (6). The extraction agent is obtained from the upper layer of the reflux tank of the water tower (6) and is transferred to the extraction agent circulation tank (18), and the extraction agent is recycled; water is obtained from the lower layer of the reflux tank of the water tower (6), and is returned to the water tower (6) as reflux liquid; the deacidification wastewater is obtained from the bottom of the water tower (6); the operating pressure at the top of the water tower (6) is 0.01-0.6 MPa, the operating temperature at the top of the tower is 80-145° C., and the operating temperature at the bottom of the tower is 120-165° C.; (e) stripping deamination: the deamination wastewater of step (d) is deammonified by using a deamination tower (9), and the deamination wastewater enters the deamination tower (9) from the upper part; a sodium hydroxide solution with a mass fraction of 5 to 36% is injected into the deamination tower (9) at or below the feed layer of the deamination tower (9) to convert fixed ammonia into ammonia gas for removal; a mixed gas containing water and ammonia is produced from the top of the deamination tower (9), and is subjected to three-stage condensation in a condenser (10) and a separator (11), and is gradually reduced in pressure and temperature to obtain high-purity ammonia gas, which is sent to an ammonia refining system, and the condensate is returned to the deamination tower (9); the operating pressure at the top of the deamination tower (9) is 0.1 to 0.6 MPa, and the operating temperature at the top of the deamination tower (9) is 85° C. to 150° C.; the deamination wastewater that meets the requirements of biochemical treatment is produced from the bottom of the deamination tower (9), and the deamination wastewater, i.e., purified water, is sent to the biochemical treatment system; (f) Regeneration of the extractant: the extraction mixture obtained in step (b) is fed into a phenol tower (16); a high-purity extractant is extracted from the top of the phenol tower (16) and returned to the circulation tank of the extraction tower (2) for use; phenol oil is extracted from the bottom of the phenol tower (16) and sent to a storage tank as a by-product; the top pressure of the extraction tower (2) is -0.01 to 0.02 MPa, the top operating temperature is 70-110° C., and the bottom operating temperature is 150-210° C.
8. The method for treating phenol-ammonia blue charcoal wastewater according to claim 7, wherein: The number of the extraction towers (2) is 1 to 6, the extraction temperature of the extraction towers (2) is 25 to 50°C, the operating pressure is normal pressure, the pH value of the semi-carbon phenol-ammonia wastewater is 3 to 11, and the semi-carbon phenol-ammonia wastewater flows through each extraction tower (2) in series.
9. The method for treating phenol-ammonia blue charcoal wastewater according to claim 7, wherein: The extractant is one or more combinations of methyl isobutyl ketone, diisopropyl ether, butyl acetate, dimethyl carbonate and petroleum ether.
10. The method for treating phenol-ammonia blue charcoal wastewater according to claim 7, characterized in that: The extractant entering each extraction tower (2) is a fresh extractant, which is in countercurrent contact with the phenol-ammonia blue charcoal wastewater, and a cross-current extraction is formed between the extraction towers (2) and the extraction towers (2). The fresh extractant is a newly purchased extractant, a recycled recycled extractant, or a mixture of the two. The ratio of the extractant in the extraction tower (2) to the phenol-ammonia blue charcoal wastewater is 1:1 to 1:10, and this ratio of each extraction tower (2) is the same or different.