1, 4-diamino-anthraquinone production wastewater purification treatment device based on wet oxidation

Abstract

The utility model discloses a 1, 4-diamino-anthraquinone production wastewater purification treatment device based on wet oxidation, which comprises a deamination cooling unit, a purification unit and a recovery unit, the deamination cooling unit comprises an ammonia extraction tower and a catalytic polymerization tank which are communicated with each other; the bottom end of the ammonia extraction tower is connected with a pipeline for introducing production wastewater; the ammonia extraction tower is connected with the catalytic polymerization tank, deaminated high-temperature wastewater is introduced into the catalytic polymerization tank, and a cooling catalytic coil pipe is arranged in the catalytic polymerization tank; and the purification unit comprises a filter press, a heat exchanger, a heater, a wet oxidation tower, a preheating tower, an ozone oxidation tower and an evaporator which are matched with the deamination cooling unit for use. According to the scheme, on the basis that wet oxidation is used as a main treatment process, pretreatment is performed in combination with activated carbon and ozone oxidation, the PH value, temperature and the like of inlet and outlet water in each stage are reasonably regulated and controlled, a good treatment effect on dye wastewater is achieved, and wastewater purification and salt resource recovery under low operation and investment cost are achieved.

Description

Technical Field

[0001] The utility model relates to the technical field of wastewater treatment, in particular to a 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation. Background Art

[0002] With the rapid development of dye production and printing and dyeing industry in my country, the discharge of dye industrial wastewater has also increased dramatically. The main components of dye production wastewater are about 5% ammonia, about 16% sodium sulfite and a small amount of anthraquinone organic matter. If the production wastewater is directly treated as hazardous waste, it will cause the loss of ammonia and sodium sulfite salt, and the cost of hazardous waste treatment is high.

[0003] The existing patent application numbers are: CN202220260549.4 and CN202221854283. The above schemes use the method of "evaporation of ammonia + resin adsorption + evaporation of salt" for the treatment of 1,4-diaminoanthraquinone production wastewater. The resin absorbs anthraquinone organic matter in the water, and the remaining water evaporates salt to recover sodium sulfite. The 1,4-diaminoanthraquinone production wastewater is strongly alkaline. The water recovered after ammonia stripping has a deep chromaticity, high viscosity and high pH. Direct resin adsorption has large flow resistance, high energy consumption, and the resin is prone to clogging and failure. At the same time, resin adsorption must be carried out under alkaline conditions. A large amount of sulfur dioxide will be generated during the acid adjustment process or resin acid precipitation, which is harmful to the environment and personal safety. The effluent after resin adsorption is directly evaporated, and the obtained sodium sulfite has low purity and poor chromaticity, and the TOC in the salt does not meet the requirements. At the same time, sodium sulfite is not easy to store and is easily oxidized by air into sodium sulfate, which reduces the purity.

[0004] In addition, some existing technologies use direct evaporation or incineration for treatment. When faced with the treatment of high-salinity, high-concentration, and high-chroma dye wastewater, direct evaporation will cause evaporator blockage and salt color dark agglomeration. At the same time, the cost of hazardous waste disposal is high, and direct incineration is expensive and unaffordable.

[0005] Therefore, it is urgent to propose a treatment system and method with good treatment effect, green economy to solve the above technical problems. Utility Model Content

[0006] The purpose of this section is to summarize some aspects of the embodiments of the utility model and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and utility model name of this application to avoid blurring the purpose of this section, specification abstract and utility model name, and such simplifications or omissions cannot be used to limit the scope of the utility model.

[0007] Therefore, in order to solve the above technical problems, the utility model provides the following technical solutions: a 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation, comprising a deammoniation cooling unit, a purification unit and a recovery unit;

[0008] The deamination and cooling unit comprises an ammonia extraction tower and a catalytic polymerization tank which are interconnected, wherein the bottom end of the ammonia extraction tower is connected to a pipeline for introducing production wastewater; the ammonia extraction tower is connected to the catalytic polymerization tank for introducing high-temperature wastewater after deamination into the catalytic polymerization tank, and a cooling catalytic coil is arranged inside the catalytic polymerization tank;

[0009] The purification unit includes a filter press, a heat exchanger, a heater, a wet oxidation tower, a preheating tower, an ozone oxidation tower and an evaporator used in conjunction with the deamination cooling unit. The catalytic polymerization tank is connected to the filter press, the filter press is connected to the heat exchanger, the heat exchanger is connected to the heater, and the heat exchanger is also connected to the ozone oxidation tower; the ozone oxidation tower is connected to the catalytic polymerization tank; the heater is connected to the wet oxidation tower, the wet oxidation tower is connected to the heat exchanger, the wet oxidation tower is also connected to the preheating tower, and the preheating tower is also connected to the catalytic polymerization tank; the preheating tower is also connected to the evaporator, the evaporator is connected to a salt outlet pipeline, and the evaporator is also connected to the wastewater inlet of the ammonia stripping tower; the steam outlet of the evaporator is connected to the bottom of the ammonia stripping tower for passing steam into the ammonia stripping tower, the water after heat exchange enters the preheating tower, and the ozone outlet water after heat exchange and temperature rise entering the cooling catalytic coil is further heated by the high-temperature air at the wet oxidation outlet, and then enters the evaporator through the third pump body for evaporation, and the outlet steam enters the ammonia stripping tower;

[0010] The recovery unit includes an ammonia concentration detector, a first regulating valve and a second regulating valve. The evaporator is connected to the inlet of the first pump body through a recovery pipeline. The recovery pipeline is connected to the ammonia concentration detector. The first regulating valve and the second regulating valve are arranged on the recovery pipeline.

[0011] As a preferred scheme of the 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation described in the utility model, wherein: the interiors of the ammonia extraction tower, the wet oxidation tower and the ozone oxidation tower are all arranged with fillers, and the fillers in the ammonia extraction tower are used to increase the steam action path and improve the ammonia removal effect.

[0012] As a preferred scheme of the 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation described in the utility model, wherein: the cooling catalytic coil adopts a metal hollow tube body, and the internal channel of the metal hollow tube body is used for the circulation of a cold source to exchange heat and cool the high-temperature wastewater. The cold source is the water discharged from the ozone oxidation tower, which is used to promote the high-temperature wastewater to form a small particle flow state solid-liquid mixture under the cooling catalytic effect of the cooling catalytic coil.

[0013] As a preferred solution of the 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation described in the utility model, the outer wall of the cooling catalytic coil is used for heat transfer, and the outer layer of the cooling catalytic coil is attached with a catalyst.

[0014] As a preferred scheme of the 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation described in the utility model, wherein: the device also includes a first pump body, a second pump body and a third pump body, the bottom end of the ammonia extraction tower is connected to the first pump body, the first pump body is used to connect to the wastewater source, the catalytic polymerization tank is connected to the second pump body, the second pump body is connected to the filter press, the preheating tower is connected to the third pump body, the third pump body is connected to the evaporator, the evaporator is connected to a salt outlet pipeline, and the evaporator is also connected to the inlet of the first pump body.

[0015] As a preferred scheme of the 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation described in the utility model, the catalyst is one or more of metal oxides such as Fe, Cu, Ti, Zn, Ce, La, etc. plated on the surface or attached with their metal sulfates, which is used to catalyze the polymerization and solidification of aminoanthraquinone.

[0016] Beneficial effects of the utility model:

[0017] This solution is to solve the technical problem that when the temperature is too high, the particles formed by catalytic polymerization are large, have poor fluidity, and block the pipeline. This solution uses the low temperature of the ozone effluent under the action of the low-temperature hollow catalytic conduit to control the temperature of the high-temperature effluent of the deamination tower through a cold source, and the temperature is controlled between 30 and 70°C. At the same time, a temperature gradient cylindrical distribution group is formed around the low-temperature hollow catalytic conduit. At the same time, the pH value of the wastewater is regulated to be between 8 and 9 through the catalyst on the outer layer of the conduit, so as to control the catalytic polymerization rate gradient and form a small particle mixture with good fluidity, which is convenient for flow and separation.

[0018] This scheme is to solve the problem that the conventional resin adsorption and activated carbon adsorption effects of the remaining soluble anthraquinone impurities are poor and the secondary pollution is serious. This scheme uses a wet oxidation process to simultaneously oxidize sulfite and soluble anthraquinone impurities. By controlling the wet oxidation reaction conditions, the temperature is between 120~180℃ and the pressure is between 0.25~1MPa. After the influent sulfite is oxidized to sulfate, an acidic sulfate environment system with a pH value maintained at 3~6 is formed. The formed sulfate free radicals are used to sulfonate and decompose the soluble aminoanthraquinone impurities to form small molecular sulfonates, small molecular aminosulfonates, carbon dioxide and water. At the same time, the chromaticity of the raw water is reduced to achieve ozone oxidation conditions, and then ozone is used to further oxidize and degrade it to form sulfate, ammonium, carbon dioxide and water, so that the effluent COD is lower than 50 mg / L, and the sodium sulfate salt meets the requirements of the production of "GB / T 6009-2014 Industrial Anhydrous Sodium Sulfate".

[0019] The relevant operating systems in this device adopt a heat recovery and reuse design to minimize the loss and waste of heat energy, achieve high-efficiency, low-energy consumption, and low-cost operation, and realize wastewater purification and salt resource recovery at lower operating and investment costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions of the embodiments of the present utility model, the following briefly introduces the drawings required for the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present utility model. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:

[0021] Figure 1 It is a schematic diagram of the overall structure of the utility model.

[0022] Figure 2 This is a comparison chart of water quality indicators before and after wastewater treatment in the utility model.

[0023] Figure 3 This is a comparison chart of salt output indicators before and after wastewater treatment in the utility model.

[0024] In the figure: 100, deamination cooling unit; 101, ammonia extraction tower; 102, catalytic polymerization tank; 103, cooling catalytic coil;

[0025] 200, purification unit; 201, filter press; 202, heat exchanger; 203, heater; 204, wet oxidation tower; 205, preheating tower; 206, ozone oxidation tower; 207, evaporator;

[0026] 300, recovery unit; 301, ammonia concentration detector; 302, first regulating valve; 303, second regulating valve; 304, recovery pipeline;

[0027] 400, first pump body;

[0028] 500, second pump body;

[0029] 600. The third pump body. DETAILED DESCRIPTION

[0030] In order to make the above-mentioned purposes, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the accompanying drawings.

[0031] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0032] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.

[0033] Secondly, the present invention is described in detail with reference to the schematic diagram. When describing the embodiments of the present invention, for the sake of convenience, the cross-sectional diagrams showing the device structure will not be partially enlarged according to the general scale, and the schematic diagrams are only examples, which should not limit the scope of protection of the present invention. In addition, in actual production, the three-dimensional dimensions of length, width and depth should be included.

[0034] Reference Figures 1 to 3 , which is an embodiment of the utility model, provides a 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation, including a deammoniation cooling unit 100, a purification unit 200 and a recovery unit 300;

[0035] The deamination and cooling unit 100 includes an ammonia extraction tower 101 and a catalytic polymerization tank 102 which are interconnected. A filler is arranged inside the ammonia extraction tower 101. The bottom end of the ammonia extraction tower 101 is connected to a first pump body 400, and the first pump body 400 is used to connect to a wastewater source; the ammonia extraction tower 101 is connected to the catalytic polymerization tank 102, and is used to introduce high-temperature wastewater after deamination into the catalytic polymerization tank 102. A cooling catalytic coil 103 is arranged inside the catalytic polymerization tank 102; the cooling catalytic coil 103 adopts a metal hollow tube body, and the internal channel of the metal hollow tube body is used for cold source circulation to perform heat exchange and cooling of the high-temperature wastewater; the outer wall of the cooling catalytic coil 103 is used for heat transfer, and a catalyst is attached to the outer layer of the cooling catalytic coil 103; the catalyst is one or more of metal oxides such as Fe, Cu, Ti, Zn, Ce, La, etc. plated on the surface or attached with metal sulfates thereof, and is used to catalyze the solidification of the polymerization of aminoanthraquinone;

[0036] When in use: 1,4-diaminoanthraquinone production wastewater passes through the first pump body 400 and enters the bottom of the ammonia extraction tower 101, and the outlet steam of the evaporator 207 also enters the bottom of the ammonia extraction tower 101, and the filler of the ammonia extraction tower 101 increases the steam action path, thereby improving the ammonia removal effect; the high-temperature wastewater after deammoniation enters the catalytic polymerization tank 102, and the pH in the catalytic polymerization tank 102 is controlled to be 8-9 (the pH is adjusted by one or more of H2SO4 / H2SO3 / NaHSO4 / H2S2O7); the catalytic polymerization tank 102 contains a cooling catalytic coil 103, and the coil is cooled by heat exchange through the outlet water of the ozone oxidation tower 206, and the outlet water temperature is controlled to be 30~70℃.

[0037] The purification unit 200 includes a filter press 201, a heat exchanger 202, a heater 203, a wet oxidation tower 204, a preheating tower 205, an ozone oxidation tower 206 and an evaporator 207 used in conjunction with the deamination cooling unit 100. The catalytic polymerization tank 102 is connected to the second pump body 500, the second pump body 500 is connected to the filter press 201, the preheating tower 205 is connected to the third pump body 600, the third pump body 600 is connected to the evaporator 207, the evaporator 207 is connected to a salt outlet pipeline, and the evaporator 207 is also connected to the inlet of the first pump body 400; the filter press 201 is connected to the heat exchanger 202, the heat exchanger 202 is connected to the heater 203, and the heat exchanger 202 is also connected to the ozone oxidation tower 206. The ozone oxidation tower 206 is connected to the catalytic polymerization tank 102; the heater 203 is connected to the wet oxidation tower 204, the wet oxidation tower 204 is connected to the heat exchanger 202, the wet oxidation tower 204 is also connected to the preheating tower 205, and the preheating tower 205 is also connected to the catalytic polymerization tank 102; the preheating tower 205 is also connected to the evaporator 207, the evaporator 207 is connected to the salt outlet pipeline, and the evaporator 207 is also connected to the wastewater inlet of the ammonia stripping tower 101; the steam outlet of the evaporator 207 is connected to the bottom of the ammonia stripping tower 101, for introducing steam into the ammonia stripping tower 101; the interiors of the wet oxidation tower 204 and the ozone oxidation tower 206 are both arranged with fillers;

[0038] When in use: under the cooling catalytic effect of the cooling catalytic coil 103, a small particle fluidized solid-liquid mixture is formed, which is pumped into the filter press 201 through the second pump body 500. The wastewater after the small particle polymer is separated by the filter press 201 enters the heat exchanger 202. The fluidity of the water discharged from the filter press 201 is significantly improved, and the small particle polymer is reused for product production.

[0039] The outlet water of the filter press 201 is heated by heat exchange with the outlet water of the wet oxidation tower 204, and then enters the wet oxidation tower 204 after being heated to 120-180°C. After the sulfurous acid is oxidized into sulfuric acid in the wet oxidation tower 204, the pH value of the formed acidic system is maintained at 3-6, and the remaining soluble anthraquinone impurities are oxidized into small molecular sulfonates, small molecular aminosulfonates, carbon dioxide and water by oxygen and sulfuric acid, and the chromaticity of the raw water is reduced at the same time;

[0040] The outlet water of the wet oxidation tower 204 enters the heat exchanger 202 and has a temperature of 30-60°C. It then enters the ozone oxidation tower 206. After oxidation in the ozone oxidation tower 206, the remaining trace small molecular sulfonates and aminosulfonates are further oxidized into sulfate, ammonium, carbon dioxide and water. The outlet water COD is less than 50 mg / L, the TOC is less than 20 mg / L, and the water is colorless.

[0041] The ozone oxidation effluent is connected to the cooling catalytic coil 103 in the catalytic polymerization tank 102 for heat exchange and cooling of the deammoniation effluent. The water after heat exchange enters the preheating tower 205. The high-temperature air at the outlet of the wet oxidation tower 204 further heats the ozone effluent entering the cooling catalytic coil 103 after heat exchange and heating. Then, the water enters the evaporator 207 through the third pump body 600 for evaporation. The outlet steam enters the ammonia stripping tower 101, and the outlet salt meets the production requirements of "GB / T 6009-2014 Industrial Anhydrous Sodium Sulfate".

[0042] The recovery unit 300 includes an ammonia concentration detector 301, a first regulating valve 302 and a second regulating valve 303. The evaporator 207 is connected to the inlet of the first pump body 400 through a recovery pipe 304. The recovery pipe 304 is connected to the ammonia concentration detector 301. The first regulating valve 302 and the second regulating valve 303 are arranged on the recovery pipe 304.

[0043] During use: the outlet mother liquor is detected by the ammonia concentration detector 301. When the concentration is lower than 1000 mg / L, the first regulating valve 302 is closed, the second regulating valve 303 is opened, and the mother liquor flows back to the front end of the water inlet of the ozone oxidation tower 206; when the concentration is higher than 1000 mg / L, the first regulating valve 302 is opened, the second regulating valve 303 is closed, and the mother liquor flows back to the front end of the water inlet of the ammonia extraction tower 101.

[0044] In this scheme, wet oxidation is used as the main treatment process, combined with catalytic polymerization, stripping and ozone oxidation for pretreatment, and the pH value, temperature, etc. of the inlet and outlet water in each stage are reasonably adjusted. It has a good treatment effect on dye wastewater, and the effluent can be reduced to colorless, the effluent salt is pure white, and the TOC per kilogram is less than 50 mg, and the sodium sulfate content is greater than 98%, achieving wastewater purification and salt resource recovery at lower operating and investment costs.

[0045] It should be noted that the above embodiments are only used to illustrate the technical solution of the utility model rather than to limit it. Although the utility model has been described in detail with reference to the preferred embodiments, ordinary technicians in the field should understand that the technical solution of the utility model can be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the utility model, which should be included in the scope of the claims of the utility model.

Claims

1. A 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation, characterized in that: It comprises a deamination cooling unit (100), a purification unit (200) and a recovery unit (300); The deammonification and cooling unit (100) comprises an ammonia extraction tower (101) and a catalytic polymerization tank (102) which are interconnected, wherein the ammonia extraction tower (101) is connected to a pipeline for introducing production wastewater; the ammonia extraction tower (101) is connected to the catalytic polymerization tank (102) for introducing high-temperature wastewater after deammonification into the catalytic polymerization tank (102), and a cooling catalytic coil (103) is arranged inside the catalytic polymerization tank (102); The purification unit (200) comprises a filter press (201) used in conjunction with the deamination and cooling unit (100), a heat exchanger (202), a heater (203), a wet oxidation tower (204), a preheating tower (205), an ozone oxidation tower (206) and an evaporator (207); the catalytic polymerization tank (102) is connected to the filter press (201), the filter press (201) is connected to the heat exchanger (202), the heat exchanger (202) is connected to the heater (203), and the heat exchanger (202) is also connected to the ozone oxidation tower (206); the ozone oxidation tower (206) is connected to the catalytic polymerization tank (102); The heater (203) is connected to the wet oxidation tower (204), the wet oxidation tower (204) is connected to the heat exchanger (202), the wet oxidation tower (204) is also connected to the preheating tower (205), and the preheating tower (205) is also connected to the catalytic polymerization tank (102); the preheating tower (205) is also connected to the evaporator (207), the evaporator (207) is connected to a salt outlet pipeline, and the evaporator (207) is also connected to the wastewater inlet of the ammonia stripping tower (101); the steam outlet of the evaporator (207) is connected to the bottom of the ammonia stripping tower (101) for introducing steam into the ammonia stripping tower (101); The recovery unit (300) comprises an ammonia concentration detector (301), a first regulating valve (302) and a second regulating valve (303); the evaporator (207) is connected to the inlet of the first pump body (400) via a recovery pipe (304); the recovery pipe (304) is connected to the ammonia concentration detector (301); and the first regulating valve (302) and the second regulating valve (303) are arranged on the recovery pipe (304).

2. The 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation according to claim 1, characterized in that: The interiors of the ammonia extraction tower (101), the wet oxidation tower (204) and the ozone oxidation tower (206) are all arranged with fillers.

3. The 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation according to claim 1, characterized in that: The cooling catalytic coil (103) adopts a metal hollow tube body, and the internal channel of the metal hollow tube body is used for the circulation of cold sources to perform heat exchange and cooling of high-temperature wastewater.

4. The 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation according to claim 1, characterized in that: The outer wall of the cooling catalytic coil (103) is used for heat transfer, and a catalyst is attached to the outer layer of the cooling catalytic coil (103).

5. The 1,4-diaminoanthraquinone production wastewater purification treatment device based on wet oxidation according to claim 1, characterized in that: The device further comprises a first pump body (400), a second pump body (500) and a third pump body (600); the bottom end of the ammonia extraction tower (101) is connected to the first pump body (400); the first pump body (400) is used to connect to a wastewater source; the catalytic polymerization tank (102) is connected to the second pump body (500); the second pump body (500) is connected to a filter press (201); the preheating tower (205) is connected to the third pump body (600); the third pump body (600) is connected to an evaporator (207); the evaporator (207) is connected to a salt outlet pipeline; and the evaporator (207) is also connected to the inlet of the first pump body (400).

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