Membrane integrated treatment device for TMQ production wastewater

Abstract

The utility model discloses a membrane integrated treatment device for TMQ production wastewater. A waste liquid outlet of a wastewater adjusting tank of the membrane integrated treatment device is communicated with a membrane pretreatment device through a conveying pump, and a penetrating fluid outlet and a concentrated liquid outlet of the membrane pretreatment device are communicated with a membrane separation device and a COD deep treatment device respectively; a concentrated solution outlet of the membrane separation device is communicated with the membrane purification device through a delivery pump; a penetrating fluid outlet and the concentrated solution outlet of the membrane separation device are respectively communicated with the membrane concentration device and the COD advanced treatment device; a penetrating fluid outlet of the membrane purification device is communicated with a waste liquid inlet of the wastewater adjusting tank; a concentrated solution outlet of the membrane concentration device is communicated with a feeding hole of the centrifugal separation device; a crude salt outlet of the centrifugal separation device is communicated with the recovered salt drying device; a steam outlet of the recovered salt drying device is communicated with the heat exchange recovery device. The membrane treatment device is used for osmotic filtration and concentration, the generated waste heat steam is continuously recovered, and the final penetrating fluid is used as reuse water, so that the device has the advantages of low energy consumption and high efficiency.

Description

Technical Field

[0001] The utility model relates to a membrane integrated treatment device for TMQ production wastewater, belonging to the field of industrial wastewater resource treatment. Background Art

[0002] With the country's increasing environmental protection requirements, "green chemistry and clean production" have become the future development trend and mainstream for chemical manufacturers. This inevitably places higher demands on manufacturers to reduce consumption, pollutant emissions, and control production costs. The rubber industry is inextricably linked to people's daily lives. TMQ (di-, tri-, and tetramers of 2,2,4-trimethyl-1,2-dihydroquinoline) used in the natural rubber, synthetic rubber, and latex processing industries is widely used as a rubber antioxidant both domestically and internationally due to its excellent antioxidant properties.

[0003] However, a large amount of production wastewater is generated during the TMQ synthesis process, which contains organic substances such as TMQ oligomers, aniline, and acetone. The wastewater is highly toxic and rich in sodium chloride, making it difficult to treat industrial high-salt wastewater. The current treatment methods for TMQ production wastewater mainly include: In the application of patent number CN 112661331 A, the oil-water phase is separated by neutralization reaction and standing, and then the separated aqueous phase is distilled to recover its useful components, thereby significantly reducing the COD of TMQ wastewater and recycling materials. In the application of patent number CN 105502740 A, an extraction method is adopted. The neutralized TMQ wastewater is allowed to stand for stratification, and then an extractant is added to the aqueous phase containing flocculent matter. After extraction, the aqueous phase is allowed to stand for stratification, and the aqueous phase enters the sewage treatment system for unified treatment. The oil phase is returned to the polycondensation reactor for reuse, thereby achieving the purpose of improving the TMQ yield and reducing the concentration of pollutants in the wastewater. Patent application number CN 214142146 U relates to a device for recovering materials from wastewater containing the antioxidant TMQ. The device comprises a sequentially connected reactor, a flotation tank, a static separation tank, an alkaline wash separator, a distillation tower, and a product storage tank. Air is pumped into the flotation tank via a pressurized air pump, and suspended organic matter in the wastewater is combined with the air to form an effective stratification. The resulting viscous material is then allowed to stand for separation and then washed with dilute alkaline water to separate the strata. The stratified layers are then distilled to separate the water, aniline, monomer, isopropyldiphenylamine, and other substances, thereby obtaining a qualified finished antioxidant TMQ product.

[0004] Among existing treatment methods, CN 112661331 A and CN 214142146 U both use distillation or rectification to separate organic components. This process not only consumes a lot of energy, but also results in unstable composition, concentration, and purity of the separated organic matter, requiring extensive monitoring and adjustment work for reuse. In CN 105502740 A, the extractant is aniline, TMQ synthetic monomer, or synthetic liquid. When aniline is the extractant, it has a certain solubility in the aqueous phase and enters the sewage system with the aqueous phase, resulting in material waste and increased sewage treatment difficulty. When TMQ synthetic monomer or synthetic liquid is the extractant, hydrochloric acid is used in TMQ synthesis, so the extractant is acidic. Furthermore, the presence of chloride ions accelerates corrosion of treatment equipment, increasing equipment maintenance and upkeep costs.

[0005] In summary, the treatment of TMQ production wastewater has become a bottleneck in the development of the industry. It is urgent to develop a low-energy, high-efficiency, and highly automated TMQ production wastewater treatment process with considerable economic and social benefits. Utility Model Content

[0006] In order to solve the problems of high energy consumption and low efficiency in TMQ production wastewater treatment in the prior art, the present application proposes a membrane integrated treatment device for TMQ production wastewater, which is characterized by comprising a wastewater regulating tank, a membrane pretreatment device, a membrane separation device, a membrane purification device, a membrane concentration device, a COD deep treatment device, a centrifugal separation device, a salt recovery drying device and a heat exchange recovery device; wherein the wastewater regulating tank is provided with a waste liquid inlet and a waste liquid outlet, the waste liquid outlet is connected to the feed inlet of the membrane pretreatment device via a first delivery pump, the permeate outlet of the membrane pretreatment device is connected to the feed inlet of the membrane separation device via a second delivery pump, and the concentrated liquid outlet of the membrane pretreatment device is connected to the feed inlet of the COD deep treatment device;

[0007] The concentrated liquid outlet of the membrane separation device is connected to the feed inlet of the membrane purification device through the third delivery pump, and the permeate outlet of the membrane separation device is connected to the feed inlet of the membrane concentration device through the fourth delivery pump; the concentrated liquid outlet of the membrane purification device is connected to the feed inlet of the COD deep treatment device, and the permeate outlet of the membrane purification device is connected to the waste liquid inlet of the wastewater regulating tank; the concentrated liquid outlet of the membrane concentration device is connected to the feed inlet of the centrifugal separation device, and the permeate outlet of the membrane concentration device is connected to the recycled water network; the filtrate outlet of the centrifugal separation device is connected to the inlet of the fourth delivery pump, and the crude salt outlet of the centrifugal separation device is connected to the material inlet of the salt recovery drying device; the salt recovery drying device is provided with a dry salt outlet and a steam outlet, and the steam outlet is connected to the heat medium pipe inlet of the heat exchange recovery device.

[0008] In this application, a multi-stage membrane treatment device is designed, and the concentrated liquid and permeate produced by each stage of the membrane treatment device are treated separately. The solid recovered salt finally obtained is sodium chloride, and this sodium chloride meets the refined industrial salt - industrial dry salt level 2 and above standards in GB / T 5462-2015 "Industrial Salt", and can be sold as commercial salt or used as salt for the company's own use. Since this application mainly uses membrane treatment devices for osmotic filtration and concentration, it has the advantages of low energy consumption and high efficiency, and the waste heat steam generated by the salt recovery drying device is further recovered, reducing energy consumption. The final permeate is used as recycled water and recycled, reducing water consumption. The COD deep treatment device preferably uses an activated carbon adsorption tank.

[0009] Furthermore, in order to prevent the wastewater in the wastewater regulating tank from settling and causing the waste liquid outlet of the wastewater regulating tank to be blocked, a speed-regulating agitator is installed in the wastewater regulating tank.

[0010] Furthermore, to facilitate uniform liquid delivery, the permeate outlet of the membrane pretreatment unit is connected to the liquid inlet of a first storage tank, the liquid outlet of which is connected to the feed inlet of a membrane separation unit via a second delivery pump. The concentrate outlet of the membrane separation unit is connected to the liquid inlet of a second storage tank, the liquid outlet of which is connected to the feed inlet of a membrane purification unit via a third delivery pump. The permeate outlet of the membrane separation unit is connected to the liquid inlet of a third storage tank, the liquid outlet of which is connected to the feed inlet of a membrane concentration unit via a fourth delivery pump. These first, second, and third storage tanks are used to address uneven operating loads or temporary production stoppages caused by fluctuations in wastewater volume during production.

[0011] Furthermore, the filtrate outlet of the centrifugal separation device is connected to the liquid inlet of the third storage tank. This design can reduce the fluctuation of the inlet concentration of the membrane concentration device caused by the addition of filtrate.

[0012] Furthermore, in order to facilitate cleaning due to accidents or the need for cleaning, the liquid outlet of the first storage tank, the liquid outlet of the second storage tank and the liquid outlet of the third storage tank are all connected to drain pipes, and drain valves are installed on the drain pipes.

[0013] Specifically, the membrane materials installed in the membrane pretreatment unit, membrane separation unit, membrane purification unit, and membrane concentration unit are all selected from at least one of flat sheet membrane, tubular membrane, mesoporous fiber membrane, or spiral wound membrane. In actual production, the membrane material selection can be based on the specific wastewater conditions and the environment in which it is present.

[0014] In general, compared with the existing technology of treating TMQ production wastewater by distillation, rectification or extraction, the present application greatly reduces heat energy consumption, reduces costs and reduces carbon emissions; since no extractant is introduced, the corrosion damage of the extractant to the equipment is reduced, and at the same time, the problem of difficulty in subsequent treatment caused by the extractant partially dissolved in the wastewater is avoided; and through the integrated combination of membrane systems with different functions and different configurations, the graded treatment of TMQ production wastewater is achieved, and organic matter, salts and process-grade recycled water are recovered separately, thereby improving the treatment accuracy and effect of TMQ production wastewater, and increasing the wastewater recovery and treatment rate and economic value. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a schematic diagram of an apparatus according to an embodiment of the present invention. DETAILED DESCRIPTION

[0016] See also Figure 1 A membrane-integrated treatment device for TMQ production wastewater includes a wastewater conditioning tank 1, a membrane pretreatment device 3, a membrane separation device 6, a membrane purification device 9, a membrane concentration device 13, a COD deep treatment device 10, a centrifugal separation device 14, a recovered salt drying device 15, and a heat exchange recovery device 16. The wastewater conditioning tank is provided with a waste liquid inlet 18 and a waste liquid outlet 19, and a speed-adjustable agitator 20 is installed inside the wastewater conditioning tank.

[0017] The waste liquid inlet is connected to a waste liquid inlet pipe 17, through which TMQ production wastewater can enter the wastewater regulating tank 1 for mixing and agitation. The waste liquid outlet 19 is connected to the inlet of the first delivery pump 2, the outlet of which is connected to the first feed inlet 31 of the membrane pretreatment device 3. The first permeate outlet 33 of the membrane pretreatment device is connected to the first inlet 41 of the first storage tank 4. The first outlet 42 of the first storage tank 4 is connected to the inlet of the second delivery pump 5, and the outlet of the second delivery pump 5 is connected to the second feed inlet 61 of the membrane separation device 6. The first concentrated liquid outlet 32 ​​of the membrane pretreatment device 3 is connected to the fifth feed inlet 101 of the COD deep treatment device 10. In this embodiment, the COD deep treatment device is specifically an activated carbon adsorption tank.

[0018] The second concentrated liquid outlet 63 of the membrane separation device 6 is connected to the second liquid inlet 71 of the second storage tank 7. The second liquid outlet 72 of the second storage tank 7 is connected to the inlet of the third delivery pump 8. The outlet of the third delivery pump 8 is connected to the third feed inlet 91 of the membrane purification device 9. The third concentrated liquid outlet 92 of the membrane purification device 9 is connected to the fifth feed inlet 101 of the COD deep treatment device. The third permeate outlet 93 of the membrane purification device is connected to the waste liquid inlet 18 of the wastewater regulating tank.

[0019] The second permeate outlet 62 of the membrane separation device 6 is connected to the third liquid inlet 111 of the third storage tank 11 , the third liquid outlet 112 of the third storage tank 11 is connected to the inlet of the fourth delivery pump 12 , and the outlet of the fourth delivery pump 12 is connected to the fourth feed inlet 131 of the membrane concentration device 13 .

[0020] The fourth concentrated liquid outlet 133 of the membrane concentration device 13 is connected to the feed port of the centrifugal separation device 14 , and the fourth permeate outlet 132 of the membrane concentration device 13 is connected to the recycled water pipe network 135 .

[0021] The filtrate outlet 141 of the centrifugal separation device 14 is connected to the third liquid inlet 111 of the third storage tank 11 , so that the filtrate outlet 141 of the centrifugal separation device 14 is indirectly connected to the inlet of the fourth delivery pump via the third storage tank 11 .

[0022] The crude salt outlet 143 of the centrifugal separation device 14 is connected to the material inlet 151 of the salt recovery drying device 15. The salt recovery drying device 15 is provided with a dry salt outlet 152 and a steam outlet 154. The steam outlet 154 is connected to the heat medium pipe inlet 161 of the heat exchange recovery device 16. The heat medium pipe outlet 162 of the heat exchange recovery device 16 is connected to the gas treatment device 163.

[0023] In order to facilitate the cleaning of each storage tank, the liquid outlet at the bottom of each storage tank is connected to a drain pipe, and a drain valve is installed on each drain pipe.

[0024] The first liquid outlet 42 of the first storage tank is connected to a first drain pipe 44, on which a first drain valve 46 is installed. A first inlet valve 45 is installed in the pipeline from the first liquid outlet to the second delivery pump. The second liquid outlet 72 of the second storage tank is connected to a second drain pipe 74, on which a second drain valve 76 is installed. A second inlet valve 75 is installed in the pipeline from the second liquid outlet to the third delivery pump. The third liquid outlet 112 of the third storage tank is connected to a third drain pipe 114, on which a third drain valve 116 is installed. A third inlet valve 115 is installed in the pipeline from the third liquid outlet to the fourth delivery pump.

[0025] In this embodiment, the membrane material configurations used by the membrane pretreatment device and the membrane purification device are both roll-type organic membranes, and the membrane material configurations used by the membrane separation device and the membrane concentration device are both tubular ceramic membranes.

[0026] During operation of this embodiment, TMQ production wastewater enters wastewater conditioning tank 1 through the wastewater inlet pipe. After being uniformly stirred, it is pumped to membrane pretreatment unit 3 for concentration via a first delivery pump. The concentrated liquid produced by membrane pretreatment unit 3 enters COD advanced treatment unit 10 for adsorption treatment. The permeate produced by membrane pretreatment unit 3 enters the first storage tank for temporary storage. When the first storage tank needs to be emptied, the first inlet valve 45 is closed and the first drain valve 46 is opened. The wastewater discharged from the first storage tank enters the wastewater treatment system.

[0027] The liquid in the first storage tank is pumped into the membrane separation device via the second transfer pump for concentration. The concentrated liquid produced by the membrane separation device is then temporarily stored in the second storage tank. When the second storage tank needs to be emptied, the second inlet valve 75 is closed and the second drain valve 76 is opened. The wastewater discharged from the second storage tank enters the wastewater treatment system.

[0028] The liquid in the second storage tank is pumped into the membrane purification device for concentration by the third delivery pump. The concentrated liquid produced by the membrane purification device enters the COD deep treatment device for treatment. The permeate produced by the membrane purification device is returned to the wastewater conditioning tank 1 through the waste liquid inlet 18 for further treatment.

[0029] The permeate produced by membrane separation unit 6 is temporarily stored in a third storage tank. The liquid in the third storage tank is pumped into the membrane concentration unit via a fourth transfer pump for concentration. When the third storage tank needs to be emptied, the third inlet valve 115 is closed and the third drain valve 116 is opened. The wastewater discharged from the third storage tank enters the wastewater treatment system.

[0030] The concentrated liquid produced by the membrane concentration device enters the centrifugal separation device for centrifugal filtration, and the filtrate produced is returned to the third storage tank 11 through the third liquid inlet 111 for further processing. The crude salt produced by the centrifugal separation device enters the salt recovery drying device 15 for drying. The dried crude salt is discharged from the dry salt outlet 152 of the salt recovery drying device 15. After cooling, the crude salt is used as salt for self-use or sold. The steam generated during the drying process of the salt recovery drying device 15 is discharged from the steam outlet 154 and then enters the heat exchange device 16 for heat energy recovery. The steam after completing the heat exchange is discharged from the gas outlet 162 and enters the gas treatment device 163 for processing. The permeate produced by the membrane concentration device 13 enters the recycled water pipe network 135 for recycling.

Claims

1. A membrane integrated treatment device for TMQ production wastewater, characterized in that: It includes wastewater regulating tank, membrane pretreatment device, membrane separation device, membrane purification device, membrane concentration device, COD deep treatment device, centrifugal separation device, salt recovery drying device and heat exchange recovery device; The wastewater regulating tank is provided with a waste liquid inlet and a waste liquid outlet, the waste liquid outlet is connected to the feed inlet of the membrane pretreatment device through a first delivery pump, the permeate outlet of the membrane pretreatment device is connected to the feed inlet of the membrane separation device through a second delivery pump, and the concentrated liquid outlet of the membrane pretreatment device is connected to the feed inlet of the COD deep treatment device; The concentrated liquid outlet of the membrane separation device is connected to the feed inlet of the membrane purification device through the third delivery pump, and the permeate outlet of the membrane separation device is connected to the feed inlet of the membrane concentration device through the fourth delivery pump; The concentrated liquid outlet of the membrane purification device is connected to the feed inlet of the COD deep treatment device, and the permeate outlet of the membrane purification device is connected to the waste liquid inlet of the wastewater regulating tank; The concentrated liquid outlet of the membrane concentration device is connected to the feed inlet of the centrifugal separation device, and the permeate outlet of the membrane concentration device is connected to the recycled water network; The filtrate outlet of the centrifugal separation device is connected to the inlet of the fourth delivery pump, and the crude salt outlet of the centrifugal separation device is connected to the material inlet of the salt recovery drying device; The salt recovery drying device is provided with a dry salt outlet and a steam outlet, and the steam outlet is connected to the heat medium pipe inlet of the heat exchange recovery device.

2. The membrane integrated treatment device according to claim 1, characterized in that: A speed-regulating agitator is installed in the wastewater regulating tank.

3. The membrane integrated treatment device according to claim 1, characterized in that: The permeate outlet of the membrane pretreatment device is connected to the liquid inlet of the first storage tank, and the liquid outlet of the first storage tank is connected to the feed inlet of the membrane separation device through the second delivery pump; The concentrated liquid outlet of the membrane separation device is connected to the liquid inlet of the second storage tank, and the liquid outlet of the second storage tank is connected to the feed inlet of the membrane purification device through the third delivery pump; The permeate outlet of the membrane separation device is connected to the liquid inlet of the third storage tank, and the liquid outlet of the third storage tank is connected to the feed inlet of the membrane concentration device through the fourth delivery pump.

4. The membrane integrated treatment device according to claim 3, characterized in that: The filtrate outlet of the centrifugal separation device is connected to the liquid inlet of the third storage tank.

5. The membrane integrated treatment device according to claim 3, characterized in that: The liquid outlet of the first storage tank, the liquid outlet of the second storage tank and the liquid outlet of the third storage tank are all connected with drain pipes, and drain valves are installed on the drain pipes.

6. The membrane integrated treatment device according to claim 1, characterized in that: The membrane materials installed in the membrane pretreatment device, the membrane separation device, the membrane purification device and the membrane concentration device are at least one of flat membrane, tubular membrane, mesoporous fiber membrane or spiral membrane.

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