TATB production wastewater resource utilization and treatment device

Abstract

The utility model discloses a TATB production wastewater resource utilization and treatment device, and belongs to the field of explosive and powder wastewater resource utilization. The device comprises an adjusting tank, a catalytic wet air oxidation device CWAO, an intermediate water tank, a membrane absorption device, an ammonium sulfate collecting tank, a water outlet tank, a biochemical system, an evaporation device and a pump. The method comprises the following steps: enabling TATB production wastewater to automatically flow into an adjusting tank, homogenizing, lifting into a precipitation tank by using a pump, removing suspended matters, and lifting into a catalytic wet air oxidation device CWAO by using a pump; under the conditions of high temperature and high pressure, toluene and aniline organic matters in the wastewater are degraded under the catalysis of a catalyst to obtain high-ammonia-nitrogen wastewater containing a trace amount of solvent, the CWAO effluent of the catalytic wet air oxidation device flows into an intermediate water tank, and the effluent of the intermediate water tank is fed into a membrane absorption device by a pump through a pipeline. Ammonia nitrogen is separated from wastewater through gas-phase membrane separation and sulfuric acid absorption, and a saturated ammonium sulfate solution and wastewater with B / C larger than or equal to 0.25 are obtained and can be discharged after reaching the standard.

Description

Technical Field

[0001] The utility model relates to a TATB production wastewater resource utilization and treatment device, in particular to a physicochemical method for recovering ammonia nitrogen in TATB production wastewater and a TATB production wastewater treatment device, belonging to the field of explosive wastewater resource utilization. Background Art

[0002] The main pollutants in TATB production wastewater are toluene, triaminotrinitrobenzene, trichlorotrinitrobenzene, ammonia water, acetone, etc., COD15000-25000mg / L, toluene concentration 1000-200mg / L, ammonia nitrogen concentration 15000-2000mg / L, B / C<0.01. Currently, the wastewater is treated by incineration, which is costly and polluting.

[0003] CWAO has the characteristics of mild reaction conditions, high treatment efficiency, fast reaction speed, recyclable resources and low secondary pollution, so it is known as water treatment technology 4.0 and can effectively treat high-concentration organic wastewater. However, on the one hand, inorganic salts in wastewater have a toxic effect on traditional commercial catalysts (RuO2 / TiO2), and on the other hand, given the high price of precious metal catalysts, the development of salt-resistant, efficient and economical CWAO catalysts is the key to the application of CWAO technology in the treatment of TATB wastewater.

[0004] At present, the modification work on CWAO catalysts can be divided into two categories: one is optimization, which is mainly based on the modification of Ru-based catalysts. Ru itself has redox ability and stability, and the main focus is on how to improve the dispersion of Ru and the oxygen accommodation capacity of the catalyst. Among them, TiO2-CeO2-RuO2 is considered to be an optimized system that can take into account the dispersion and oxygen accommodation capacity of the catalyst; the other is transition metal oxides. Since precious metal catalysts are expensive, non-precious metal-based high-performance catalysts have always been a research hotspot in CWAO technology. There are unfilled d electron orbits in transition metals, which are easy to hybridize with the 2p electron orbit of O and have strong oxygen adsorption and activation functions, so they are used as active components in CWAO catalysts. However, these catalysts are all composite catalysts. The adsorption of oxygen and substrates and the electron transfer between active components and oxidants require a combination of carriers, oxygen absorbing aids and active substances to complete. This puts high demands on the uniform distribution of active components and oxygen absorbing aids on the carrier, and has high requirements on the preparation and standby process of the catalyst.

[0005] Perovskite oxides have excellent redox ability (the B-site transition metal with variable valence is usually the redox couple Mn + / M (n-1)+) and oxygen surface exchange and oxygen transport performance. And under certain conditions, the metals doped at the A and B positions of the perovskite oxide can achieve in-situ desolvation and segregation, thereby forming nano-alloy particles on the oxide surface. The nanoparticles have high dispersibility and confinement, ensuring that the active components will not agglomerate and lose, which will improve the catalytic activity and stability of the catalyst to a certain extent. Therefore, based on the regulation mechanism of perovskite oxides, through reasonable doping modification and control of the preparation process, perovskite-type catalysts with multifunctional sites can be designed and prepared, while achieving selective adsorption of organic matter and oxygen and electron transfer between oxidants and active components, without the need for carriers and additives, simplifying the preparation process of the catalyst while hopefully increasing the rate of the CWAO reaction at the atomic level. Utility Model Content

[0006] The utility model aims to provide a TATB production wastewater resource utilization and treatment device; through the device, the high-concentration ammonia nitrogen in TATB production wastewater can be effectively recovered and utilized and the wastewater can be treated, a saturated ammonium sulfate solution can be obtained, and the B / C of the discharged wastewater is ≥0.25. The saturated ammonium sulfate solution can be evaporated to obtain ammonium sulfate solid, and the discharged wastewater can meet the discharge standards after biochemical treatment.

[0007] The purpose of the utility model is achieved through the following technical problems.

[0008] The utility model discloses a TATB production wastewater resource utilization and treatment device, comprising a regulating tank, a catalytic wet air oxidation device CWAO, an intermediate water tank, a membrane absorption device, an ammonium sulfate collection tank, a water outlet tank, a biochemical system, an evaporation device and a pump.

[0009] The outlet of the regulating tank is connected to the lifting pump by a pipeline, and the lifting pump is connected to the water inlet of the filter by a pipeline. The wastewater in the regulating tank is lifted into the filter through the pipeline by the pump, and the suspended matter is removed in the filter;

[0010] The water outlet of the filter is connected to the water inlet of the catalytic wet air oxidation device CWAO by a pipeline, and the water outlet of the filter is lifted into the catalytic wet air oxidation device CWAO through the pipeline by a pump.

[0011] The water outlet of the catalytic wet air oxidation device CWAO is connected to the water inlet of the middle water tank by a pipeline, and the high-ammonia nitrogen wastewater discharged by the catalytic wet air oxidation device CWAO flows into the middle water tank through the pipeline;

[0012] The middle water tank is provided with a pH meter, which is connected to the drug outlet of the sodium hydroxide storage tank by a pipeline, and the sodium hydroxide in the sodium hydroxide storage tank flows into the middle water tank through the pipeline;

[0013] The outlet of the intermediate water tank is connected to the intermediate water pump, the intermediate water pump is connected to the inlet of the membrane absorption system through a pipeline, the waste water in the intermediate water tank is lifted into the membrane absorption system by a pump, the outlet of the membrane absorption system is connected to the sulfuric acid circulation pump through a pipeline, the sulfuric acid circulation pump is connected to the water inlet of the sulfuric acid storage tank through a pipeline, the outlet of the sulfuric acid storage tank is connected to the sulfuric acid circulation pump through a pipeline, and the sulfuric acid circulation pump is connected to the membrane absorption system through a pipeline to realize the circulation of the solution between the membrane absorption system and the sulfuric acid storage tank.

[0014] The water outlet of the sulfuric acid storage tank is connected to the ammonium sulfate storage tank through a pipeline, the ammonium sulfate storage tank is connected to the ammonium sulfate supply pump through a pipeline, the ammonium sulfate lifting pump is connected to the water inlet of the evaporation device through a pipeline, and the ammonium sulfate is evaporated to obtain solid ammonium sulfate;

[0015] The effluent from the membrane absorption system is connected to the water inlet of the biochemical system through a pipe. The wastewater flows into the biochemical system through the pipe and the organic matter is degraded by the metabolism of microorganisms.

[0016] The outlet of the biochemical system is connected to the inlet of the water outlet pool by a pipe. After the wastewater flows into the water outlet pool from the biochemical system, it is discharged in compliance with the standards.

[0017] The TATB production wastewater flows into the regulating tank by gravity, and after being homogenized and equalized, it is pumped into the sedimentation tank. After removing the suspended matter, it is pumped into the catalytic wet air oxidation device CWAO. Under high temperature and high pressure conditions, under the catalysis of the catalyst, the toluene and aniline organic matter in the wastewater are degraded to obtain high ammonia nitrogen wastewater containing trace solvents. The effluent of the catalytic wet air oxidation device CWAO flows into the intermediate water tank, and the effluent of the intermediate water tank is pumped into the membrane absorption device through the pipeline. The ammonia nitrogen is separated from the wastewater by gas phase membrane separation and sulfuric acid absorption to obtain saturated ammonium sulfate solution and wastewater with B / C ≥ 0.25.

[0018] Furthermore, for TATB production wastewater, the catalytic wet air oxidation device CWAO uses a catalytic wet air oxidation perovskite self-regenerating catalyst for catalysis. The efficient perovskite catalyst has multifunctional sites, and the following three measures are adopted to improve the reaction rate of CWAO in degrading organic matter and the stability of the catalyst: a. Introducing high-valent ions with large ionic radius to reduce the poisoning of active atoms by inorganic salts, effectively protecting active atoms through steric hindrance effects, increasing the yield of hydroxyl radicals, and improving the degradation efficiency of organic pollutant molecules; b. By regulating the ratio of introduced inert ions and active ions, the redox potential of active ions is regulated to improve the removal rate of TOC; c. Through in-situ precipitation of active components, the high dispersion and confinement of active metal nanoparticles on the catalyst surface are achieved to improve the electron transfer ability and catalyst stability. The confinement refers to the difficulty in agglomeration and loss.

[0019] Preferably, the perovskite-type self-regenerating catalyst is a CaMO3-type perovskite, and M is two or more of Mn, Fe, Co, Ni, Ti, Zr, Ru, Pt, and Pd.

[0020] As a further preferred embodiment, the CaMO3 type perovskite self-regeneration catalyst is preferably CaFe x Ru y Zr 1-x-y O 3-δ series.

[0021] Preferably, CaFe x Ru y Zr 1-x-y O 3-δ The series of perovskite-type self-regenerating catalysts are prepared by a co-precipitation method, preferably x=0.01-0.1, y=0.001-0.1.

[0022] CaFe 0.05 Ru 0.05 Zr 0.9 O 3-δ The catalyst has a COD removal rate of more than 80% and a toluene removal rate of more than 99% for toluene and aniline mixed wastewater; the catalyst has good stability, and after 1000h long-term operation, the catalyst deactivation rate is less than 0.01%.

[0023] The utility model discloses a TATB production wastewater resource utilization and treatment device. The working method is as follows: the TATB production wastewater flows into the regulating tank by gravity, after homogenization and equalization, it is pumped into the sedimentation tank, after the suspended matter is removed, it is pumped into the catalytic wet air oxidation device (CWAO), the CWAO device is composed of a storage and delivery unit, a heat exchange unit, a reaction unit and a gas-liquid separation unit. Under high temperature and high pressure conditions, under the catalysis of the catalyst, with air as an oxidant, toluene and aniline substances are oxidized and decomposed into inorganic substances or small molecular organic substances to obtain high ammonia nitrogen wastewater containing trace solvents, the CWAO effluent flows into the middle water tank by gravity, and the effluent of the middle water tank is pumped into the membrane absorption device through a pipeline, the membrane absorption device is composed of a membrane absorption system mainly composed of a PTFE hollow fiber membrane component, an alkali addition system, an acid circulation system, an ammonium salt treatment system, and a cleaning system, the membrane cavity is CWAO effluent, the outer side of the membrane is H2SO4 absorption liquid, and the ionized NH4+ in the wastewater is converted into free volatile NH3 by adjusting the pH of the wastewater. Driven by the difference in NH3 concentration between the inside and outside of the membrane, NH3 in the wastewater volatilizes at the wastewater-microporous membrane interface. Gaseous NH3 diffuses along the membrane micropores to the other side of the membrane, and is absorbed by the H2SO4 solution at the absorption liquid-microporous membrane interface, reacting quickly to generate non-volatile ammonium sulfate and being recovered. After the ammonium sulfate solution is saturated, it is discharged into the ammonium sulfate storage tank to obtain saturated ammonium sulfate and wastewater with B / C ≥ 0.25. The saturated ammonium sulfate enters the evaporation device, and solid ammonium sulfate is obtained after evaporation. The wastewater is discharged in compliance with the standards after subsequent biochemical treatment.

[0024] The utility model can realize the resource utilization and treatment of TATB production wastewater. After treatment by the device, a saturated ammonium sulfate solution can be obtained, and the B / C of the discharged wastewater is ≥ 0.25. The saturated ammonium sulfate solution can be evaporated to obtain ammonium sulfate solid, and the discharged wastewater can meet the requirements of the "Water Quality Standard for Sewage Discharged into Urban Sewers" (GB / T31962-2015) after biochemical treatment.

[0025] Beneficial effects:

[0026] 1. The utility model discloses a TATB production wastewater resource utilization and treatment device, which uses a CWAO device to pre-treat TATB production wastewater, reduce the toluene concentration in the wastewater, and maintain the ammonia nitrogen concentration basically unchanged, thereby avoiding toluene corrosion on the PTFE hollow fiber membrane in the membrane absorption device, increasing the service life of the membrane assembly, and reducing the operating cost.

[0027] 2. The utility model discloses a TATB production wastewater resource utilization and treatment device, which can convert ammonia nitrogen in TATB wastewater into ammonium sulfate, thus turning TATB production wastewater into treasure.

[0028] 3. The utility model discloses a TATB production wastewater treatment device. After being treated by the device, the TATB production wastewater can meet the requirements of the water quality standard for sewage discharge into urban sewers (GB / T31962-2015). BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of the device of Example 1. DETAILED DESCRIPTION

[0030] The utility model is further explained below in conjunction with the accompanying drawings and embodiments.

[0031] Example 1

[0032] The present embodiment discloses a TATB production wastewater resource utilization and treatment device, comprising: a regulating tank, a catalytic wet air oxidation device, an intermediate water tank, a membrane absorption device, an ammonium sulfate collection tank, a water outlet tank and a pump.

[0033] The TATB production wastewater flows by gravity into the regulating tank, is pumped into the sedimentation tank, and is pumped into the catalytic wet air oxidation device (CWAO). The CWAO effluent flows by gravity into the intermediate water tank, and the effluent from the intermediate water tank is pumped into the membrane absorption device through a pipeline. The saturated ammonium sulfate solution in the membrane absorption device enters the collection tank, and the effluent enters the effluent tank.

[0034] Collect wastewater with COD21770mg / L, ammonia nitrogen 5580mg / L, and toluene concentration 580mg / L.

[0035] Take 50LTATB of production wastewater and flow it into the wastewater regulating tank. After homogenization and equalization, it is pumped into the sedimentation tank. After removing the suspended matter, it is pumped into the catalytic wet air oxidation device (CWAO). The CWAO device consists of a storage and delivery unit, a heat exchange unit, a reaction unit and a gas-liquid separation unit. Under high temperature and high pressure conditions, under the catalysis of the catalyst, with air as the oxidant, toluene and aniline substances are oxidized and decomposed into inorganic substances or small molecular organic substances to obtain high ammonia nitrogen wastewater containing trace solvents. The CWAO effluent flows into the intermediate water tank by gravity. The effluent from the intermediate water tank is pumped into the membrane absorption device through a pipeline. The membrane absorption device is composed of a membrane absorption system mainly composed of a PTFE hollow fiber membrane component, an alkali addition system, an acid circulation system, an ammonium salt treatment system, and a cleaning system. The membrane cavity is CWAO effluent, and the outer side of the membrane is H2SO4 absorption liquid. By adjusting the pH of the wastewater, the ionic NH4 +It is converted into free volatile NH3. Driven by the difference in NH3 concentration inside and outside the membrane, NH3 in the wastewater volatilizes at the wastewater-microporous membrane interface. Gaseous NH3 diffuses along the membrane micropores to the other side of the membrane, and is absorbed by the H2SO4 solution at the absorption liquid-microporous membrane interface. It reacts quickly to generate non-volatile ammonium sulfate and is recovered. After the ammonium sulfate solution is saturated, it is discharged into the ammonium sulfate storage tank to obtain saturated ammonium sulfate and wastewater with a B / C of 0.29. The saturated ammonium sulfate enters the evaporation device, and solid ammonium sulfate is obtained after evaporation. The wastewater is discharged in compliance with the standards after subsequent biochemical treatment.

[0036] The specific implementation data of wastewater treatment are as follows:

[0037]

[0038] Example 2

[0039] Synthesis of CaFe by coprecipitation method 0.05 Ru 0.05 Zr 0.9 O 3-δ Catalyst, used for TATB production wastewater treatment, wastewater COD21770mg / L, ammonia nitrogen 5580mg / L, toluene concentration 580mg / L. The catalytic wet oxidation unit treatment effect is as follows:

[0040] COD(mg / L) Toluene (mg / L) Raw water quality 21770 580 Catalytic wet oxidation unit 3045 ≤0.02

[0041] Example 3

[0042] Synthesis of CaFe by coprecipitation method 0.05 Ru 0.01 Zr 0.94 O 3-δ Catalyst, used for TATB production wastewater treatment, wastewater COD21770mg / L, ammonia nitrogen 5580mg / L, toluene concentration 580mg / L. The catalytic wet oxidation unit treatment effect is as follows:

[0043] COD(mg / L) Toluene (mg / L) Raw water quality 21770 580 Catalytic wet oxidation unit 4087 ≤0.02

[0044] Example 3

[0045] Synthesis of CaFe by coprecipitation method 0.08 Ru 0.03 Zr 0.89 O 3-δ Catalyst, used for TATB production wastewater treatment, wastewater COD21770mg / L, ammonia nitrogen 5580mg / L, toluene concentration 580mg / L. The catalytic wet oxidation unit treatment effect is as follows:

[0046] COD(mg / L) Toluene (mg / L) Raw water quality 21770 580 Catalytic wet oxidation unit 3846 ≤0.02

[0047] Example 4

[0048] Synthesis of CaFe by coprecipitation method 0.05 Ru 0.05 Zr 0.9 O 3-δ Catalyst, used for TATB production wastewater treatment, wastewater COD21770mg / L, ammonia nitrogen 5580mg / L, toluene concentration 580mg / L. Catalytic wet oxidation unit catalyst operation stability test results are as follows:

[0049]

[0050]

[0051] The specific description above further illustrates in detail the purpose, technical solutions and beneficial effects of the utility model. It should be understood that the above description is only a specific embodiment of the utility model and is not intended to limit the scope of protection of the utility model. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the utility model should be included in the scope of protection of the utility model.

Claims

1. A TATB production wastewater resource utilization and treatment device, characterized by: It includes a regulating tank, a catalytic wet air oxidation device CWAO, an intermediate water tank, a membrane absorption device, an ammonium sulfate collection tank, a water outlet tank, a biochemical system, an evaporation device and a pump; The outlet of the regulating tank is connected to the lifting pump by a pipeline, and the lifting pump is connected to the water inlet of the filter by a pipeline. The wastewater in the regulating tank is lifted into the filter through the pipeline by the pump, and the suspended matter is removed in the filter; The water outlet of the filter is connected to the water inlet of the catalytic wet air oxidation device CWAO by a pipeline, and the water outlet of the filter is lifted into the catalytic wet air oxidation device CWAO through the pipeline by a pump; The water outlet of the catalytic wet air oxidation device CWAO is connected to the water inlet of the middle water tank by a pipeline, and the high-ammonia nitrogen wastewater discharged by the catalytic wet air oxidation device CWAO flows into the middle water tank through the pipeline; The middle water tank is provided with a pH meter, which is connected to the drug outlet of the sodium hydroxide storage tank by a pipeline, and the sodium hydroxide in the sodium hydroxide storage tank flows into the middle water tank through the pipeline; The outlet of the intermediate water tank is connected to the intermediate water pump, the intermediate water pump is connected to the inlet of the membrane absorption system through a pipeline, the wastewater in the intermediate water tank is lifted into the membrane absorption system by a pump, the outlet of the membrane absorption system is connected to the sulfuric acid circulation pump through a pipeline, the sulfuric acid circulation pump is connected to the water inlet of the sulfuric acid storage tank through a pipeline, the outlet of the sulfuric acid storage tank is connected to the sulfuric acid circulation pump through a pipeline, and the sulfuric acid circulation pump is connected to the membrane absorption system through a pipeline, so as to realize the circulation of the solution between the membrane absorption system and the sulfuric acid storage tank; The water outlet of the sulfuric acid storage tank is connected to the ammonium sulfate storage tank through a pipeline, the ammonium sulfate storage tank is connected to the ammonium sulfate supply pump through a pipeline, the ammonium sulfate lifting pump is connected to the water inlet of the evaporation device through a pipeline, and the ammonium sulfate is evaporated to obtain solid ammonium sulfate; The effluent from the membrane absorption system is connected to the water inlet of the biochemical system through a pipe, and the wastewater flows into the biochemical system through the pipe, where the metabolism of microorganisms is used to degrade organic matter. The outlet of the biochemical system is connected to the inlet of the water outlet pool by a pipe. After the wastewater flows into the water outlet pool from the biochemical system, it is discharged in compliance with the standards.

2. The TATB production wastewater resource utilization and treatment device according to claim 1, characterized in that: The CWAO device consists of a storage and delivery unit, a heat exchange unit, a reaction unit and a gas-liquid separation unit.

3. The TATB production wastewater resource utilization and treatment device according to claim 1, characterized in that: The membrane absorption device is composed of a membrane absorption system mainly consisting of a PTFE hollow fiber membrane component, an alkali addition system, an acid circulation system, an ammonium salt disposal system, and a cleaning system.

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