WO2021169912A1

WO2021169912A1 - Device and method for treating sulfur-containing organic wastewater by means of wet oxidation

Info

Publication number: WO2021169912A1
Application number: PCT/CN2021/077225
Authority: WO
Inventors: 杨强; 许萧; 王俊杰; 钱运东; 王磊; 王志强; 孟敏; 李裕东
Original assignee: 华东理工大学; 上海米素环保科技有限公司
Priority date: 2020-02-28
Filing date: 2021-02-22
Publication date: 2021-09-02
Also published as: CN111362451B; CN111362451A

Abstract

A device for treating sulfur-containing organic wastewater by means of wet oxidation. The device comprises an aggregation oil removal unit (1), an oxidation reaction unit (2), a cyclone degassing unit (3), and a closed sludge discharge unit (4). Also provided is a method for treating sulfur-containing organic wastewater by means of wet oxidation by using the device. The method comprises: first performing high-efficiency oil removal treatment on the sulfur-containing organic wastewater, then performing chemical oxidation treatment on a sulfide by using an air oxidation method, performing deep gas-liquid separation on a reaction product which enters the cyclone degassing unit (3), and hermetically discharging sludge by means of a sludge discharger.

Description

Device and method for wet oxidation treatment of sulfur-containing organic wastewater

Technical field

The invention belongs to the technical field of wet oxidation, and specifically relates to a device and method for wet oxidation treatment of sulfur-containing organic wastewater.

Background technique

Wet oxidation technology, namely Wet Air Oxidation (WAO), is an important method for treating toxic, harmful, and high-concentration organic wastewater. Under the conditions of 100-373 degrees Celsius and 0.5-10 MPa, using oxygen in the air as the oxidant, the oxygen in the air is used to oxidize the sulfide in the waste lye into sodium thiosulfate or sulfate to eliminate the odor; in the liquid phase It oxidizes pollutants into inorganic substances or small molecular organic substances, reduces the COD concentration in waste lye, and is suitable for COD in the range of thousands to hundreds of thousands (mg/L). The applicable organic pollutant concentration is between the incineration treatment concentration and the biochemical treatment concentration.

Taking the wet oxidation reaction of organic matter as an example, the wet oxidation reaction is a free radical reaction, including four stages: induction period, proliferation period, degradation period and end period. In the induction period, molecular oxygen reacts with organic matter to generate hydrocarbyl radicals. In the proliferation period, hydrocarbyl radicals continue to react with molecular oxygen, and the resulting ester radicals react with organic substances to generate low-molecular acids and hydroxyl radicals. Molecular acid decomposes into ether radicals, hydroxyl radicals and hydrocarbyl radicals. Hydroxyl radicals have strong oxidizing properties, and then deoxidize organic pollutants. At the end of the period, the energy between the free radicals is combined and the reaction stops.

At present, the problems encountered in the treatment of wastewater by wet oxidation reactions include the presence of hydrocarbon oil in the wastewater, low oxidation efficiency, difficulty in degassing reaction products, and failure to meet the standard for closed slag discharge.

Surrounding raw material wastewater with hydrocarbon oil, the hydrocarbons from the alkaline washing process and the butter produced in the alkaline washing tower are entrained in the waste lye. The waste lye with oil causes the temperature and pressure of the oxidation reactor to fluctuate, causing the reactor to fly , Coking occurs, and even the residual oxygen content at the outlet of the reactor drops sharply. In addition, the violent fluctuations caused serious entrainment of gas mist at the outlet of the reactor, which made the on-line oxygen meter malfunction. Because the lye and oil system is very easy to emulsify, the current common methods such as inclined plate sedimentation, cyclone separation, and filter element coalescence cannot meet the requirements of long-period, high-efficiency lye degreasing.

Around the lack of oxidation efficiency, within the applicable COD range, a large amount of oxygen needs to be consumed, and the mass transfer of oxygen between air and liquid phase is the main control step of the reaction. It is necessary to strengthen the gas-liquid mass transfer and improve the efficiency of organic oxidation. In order to improve the oxidation efficiency, membrane aeration, advanced oxidation, catalytic oxidation and other means are usually used. However, there are not many cases that meet engineering applications. Take the oxidation process of Siemens as an example. In the wet air oxidation process, the reactor pressure is 2.5～2.7MPa and the temperature is 200～215 degrees Celsius. In this process, the reactor liquid phase residence time is too long. Long, the equipment is too large, and the reactor material is expensive, and the one-time investment in the device is too large.

It is difficult to degas around the reaction product. In fact, the wet oxidation reactor contains a large number of fine-sized bubbles. However, the smaller bubbles in the reaction product have higher fluid followability. In the gas-liquid separation stage of the reaction product, the fine bubbles are difficult to peel off from the liquid phase, and the vapor phase mist entrainment is serious. In addition, due to the need to strictly control the gas-liquid contact time to avoid excessive reaction to produce impurities and coking, the volume of the gas-liquid separator cannot be too large, which poses new challenges to the traditional sedimentation gas-liquid separation technology.

Around the closed slag discharge that does not meet the standard, the liquid phase product will produce a certain amount of sludge precipitation after neutralization, which needs to be discharged regularly. The reaction pressure of wet oxidation is usually greater than 1 MPa, containing acid, alkali, and toxic organic components. Under the trend of increasingly stringent environmental protection and safety requirements, higher requirements are put forward on the technology of airtight cleaning of sludge.

Summary of the invention

In view of the importance of the above process steps and the current state of the art that cannot meet the requirements of wet oxidation reaction, the present invention provides a wet oxidation treatment device for sulfur-containing organic wastewater, and a method for achieving this effect.

The technical solutions of the present invention to solve the above technical problems are as follows: a device for wet oxidation treatment of sulfur-containing organic wastewater, the device includes a coalescing and degreasing unit, an oxidation reaction unit, a cyclone degassing unit and a closed sludge discharge unit;

The coalescing and degreasing unit includes a coalescer, and the coalescer includes a first shell and an oil removing device in the first shell; the top surface of the first shell is provided with a liquid inlet and oil Phase outlet; the bottom of the first shell below the oil phase outlet is provided with a first drain;

The oxidation reaction unit includes a reactor, the reactor includes a second shell, a partition is fixed in the second shell, and more than one fractal internals are fixed on the partition; The second shell is provided with a gas inlet and a liquid inlet, the liquid inlet is communicated with the first liquid outlet, and the upper part of the second shell is provided with a first gas-liquid outlet; the fractal inner piece It includes a cylinder body, a bottom plate is fixed at the bottom of the cylinder body, a liquid inlet is opened on the cylinder body above the bottom plate, and an air inlet pipe pointing to the bottom plate is fixed on the side wall of the cylinder body. The bottom of the air inlet pipe is sealed, the air inlet pipe is provided with a plurality of aeration micropores, the liquid inlet and the air inlet pipe are both located below the partition, and the top of the cylinder is a second air-liquid outlet ；

The cyclone degassing unit includes a third housing and a cyclone deaerator in the third housing, a gas-liquid two-phase inlet is provided on the side of the third housing, and the gas-liquid two-phase inlet Communicating the cyclone deaerator and the second gas-liquid outlet, a second liquid discharge port is provided at the bottom of the third casing, and a gas phase discharge port is provided on the top of the third casing;

The airtight mud drain unit includes a fourth shell and a mud drain provided at the bottom of the fourth shell. The fourth shell is provided with a liquid inlet and a mud outlet, and the liquid inlet It is in communication with the second liquid discharge port, and the sludge discharger is in communication with the sludge discharge port.

The present invention is further provided that the oil removal device includes a fluid rectifier, an X-shaped fiber layer and a corrugated plate layer which are sequentially arranged between the liquid inlet and the oil phase outlet.

The present invention is further provided that the X-type fiber layer includes lipophilic and hydrophobic fibers and hydrophilic and oleophobic fibers, wherein the lipophilic and hydrophobic fibers are made of polyimide, polytetrafluoroethylene or polyparaphenylene. Phthalamide, the hydrophilic and oleophobic fiber material is 316 alloy, 321 alloy or 20 alloy.

The present invention is further provided that the corrugated plate layer includes a plurality of zigzag corrugated plates arranged side by side, the distance between adjacent corrugated plates is 5-25mm, and the wave crest is provided with a circular hole with a diameter of 5-10mm. The spacing between the holes is 50 to 300 mm.

The present invention is further provided that a throat is fixed in the second gas-liquid outlet, the middle of the throat is a through hole with a small middle and two large ends, and the minimum inner diameter of the throat is 6-100 mm.

The present invention is further provided that a circulating pump is provided on the outside of the reactor, and two ends of the circulating pump are respectively connected to the inside of the reactor located above and below the partition.

The present invention is further provided that the upper part of the fourth housing is provided with a liquid discharge outlet; the sludge discharger includes a main pipe, a branch pipe, and a sludge discharge pipe connected in sequence; and the fourth housing is provided with high-pressure water Inlet, the main pipeline is connected to the high-pressure water inlet, the sludge discharge pipe is connected to the sludge discharge port; the sub-pipe is connected with an open blocking plate, and the opening of the blocking plate is connected with an ejector Nozzle, the axis of the ejection nozzle and the sub-pipe are coincident; the ejection nozzle and the main pipe are connected with a mud mixing nozzle outside the sub-pipe, and the ejection nozzle and the mud discharge The sub-pipe between the pipes is provided with a mud-inducing chamber, and the sub-pipe between the ejection nozzle and the mud-inducing chamber is communicated with an umbrella-shaped suction cup.

The present invention is further provided that more than one sub-pipe is connected between the main pipe and the sludge discharge pipe, and the cross-sectional area of the main pipe is the sum of the cross-sectional areas of all the sub-pipes.

The present invention is further provided that the diameter of the sub-pipe is 20-200 mm, the mud mixing nozzle and the sub-pipe have an included angle of 30-80°; the umbrella-shaped suction cup has an expansion angle of 90-160 degrees.

The present invention is further provided that the top of the umbrella-shaped suction cup has a hole, and a straight pipe with a diameter of 30-100 mm is welded to the opening of the sub-pipe, and the length of the straight pipe is 50-80 mm.

The present invention is further provided that the high-pressure water inlet is communicated with a booster pump.

The present invention also provides a method for wet oxidation treatment of sulfur-containing organic wastewater using the above-mentioned device. The core steps include the degreasing of the raw material liquid, the enhancement of gas-liquid reaction mass transfer, the improvement of the gas-liquid separation efficiency of the reaction product, and the closed slag discharge, including the following step:

(1) Use coalescing degreasing unit to degreasing treatment of sulfur-containing organic wastewater;

(2) The degreasing wastewater enters the liquid inlet of the fractal internals, air is filled into the inlet pipe, the wastewater fully reacts with oxygen in the air, and the reacted gas-liquid two-phase material is discharged from the first gas-liquid outlet into the swirling flow Degasser

(3) The cyclone degasser separates the gas-liquid two-phase material;

(4) The formed sludge enters the fourth housing through the liquid inlet, and is discharged from the sludge outlet through the sludge discharger.

The present invention is further configured that, in step (1), the temperature of the sulfur-containing organic wastewater is 4 to 210 degrees Celsius, and the oil content after treatment is reduced to 0.1 to 20 mg/L.

The present invention is further provided that the gas-liquid ratio in the fractal internals is 0.1-30, the apparent gas velocity is 0.001-0.1 m/s, the bubble diameter is 0.02-20 mm, and the liquid phase residence time is 1.5-2.5 hours.

The present invention is further configured that, in step (4), a booster pump is used to provide sufficient power to the high-pressure water inlet, and the booster pump has a pressure of 0.2-2 MPa.

In summary, the present invention has the following beneficial effects:

(1) After the coalescing and degreasing unit treatment, the reaction feed has a good degreasing protection effect, and it is not easy to coke and fly over temperature.

(2) After the oxidation reaction unit is processed, the bubbles in the reactor are finer, which is beneficial to speed up the oxidation speed and deepen the reaction accuracy.

(3) After the cyclone degassing unit is processed, the fine bubbles in the reaction product have a good separation effect, and the gas-liquid separation efficiency is high.

(4) After being processed by a closed sludge discharge unit, the closed slag discharge is conducive to clean production.

Description of the drawings

Figure 1 is a schematic diagram of the overall structure of the present invention;

Figure 2 is a schematic diagram of the structure of the fractal internals;

Figure 3 is a schematic diagram of the structure of a cyclone degasser;

Figure 4A is a schematic diagram of the structure of the mud discharging device (single mud discharging device);

Figure 4B is a schematic diagram of the structure of the sludge discharging device (the sludge discharging device is installed in parallel);

Figure 5 is a schematic diagram of the structure of the oxidation reaction unit (with a circulating pump);

Fig. 6 is a schematic diagram of a partial structure of the corrugated board layer.

Among them, 1 coalescing and degreasing unit; 1-1 fluid rectifier; 1-2X type fiber layer; 1-3 corrugated board layer; 1-3-1 corrugated board;

2 Oxidation reaction unit; 2-1 fractal internals; 2-1-1 second gas-liquid outlet; 2-1-2 throat; 2-1-3 aeration micropores; 2-1-4 air inlet plug ; 2-1-5 mixing chamber; 2-1-6 air inlet; 2-1-7 liquid inlet; 2-1-8 bottom plate; 2-2 partition;

3 Cyclone degassing unit; 3-1 Cyclone deaerator; 3-1-1 liquid and gas inlet; 3-1-2 column cavity; 3-1-3 liquid phase outlet; 3-1-4 overflow pipe Conical port; 3-1-5 first overflow pipe column cavity; 3-1-6 secondary liquid outlet; 3-1-7 annular slot; 3-1-8 second overflow pipe column cavity;

4 Closed mud discharge unit; 4-1 mud discharge device; 4-1-1 ejection nozzle; 4-1-2 mud mixing nozzle; 4-1-3 umbrella-shaped suction cup; 4-1-4 mud chamber; 4 -1-5 main pipeline; 4-1-6 branch pipeline; 4-1-7 mud channel;

5 booster pump; 6 mixer; 7 circulation pump.

Detailed ways

As an embodiment of the present invention, a device for wet oxidation treatment of sulfur-containing organic wastewater, the device includes a coalescing and degreasing unit 1, an oxidation reaction unit 2, a cyclone degassing unit 3, and a closed sludge discharge unit 4, see figure 1.

First, referring to Fig. 1, the coalescing and degreasing unit includes a coalescer, and the coalescer includes a first housing and a degreasing device in the first housing. The top surface of the first shell is provided with a liquid inlet and an oil phase outlet; the bottom of the first shell below the oil phase outlet is provided with a first liquid outlet.

The oil removal device includes a fluid rectifier 1-1, an X-shaped fiber layer 1-2 and a corrugated plate layer 1-3 arranged in sequence between the liquid inlet and the oil phase outlet. Referring to Fig. 6, the corrugated board layer 1-3 includes a plurality of zigzag corrugated boards 1-3-1 arranged side by side, the distance between adjacent corrugated boards 1-3-1 is 5-25mm, and the wave crest has a diameter of 5-10mm. The distance between the round holes is 50～300mm. The structure of the X-type fiber layer 1-2 in the present invention is consistent with the structure of the X-type fiber layer in the patent CN201410211202.0. The X-type fiber layer 1-2 includes lipophilic and hydrophobic fibers and hydrophilic and oleophobic fibers. The lipophilic and hydrophobic fibers are made of polyimide, polytetrafluoroethylene or poly(p-phenylene terephthalamide). The hydrophilic and oleophobic fiber material is 316 alloy, 321 alloy or 20 alloy.

The treatment process of the coalescing and degreasing unit is: after the sulfur-containing organic wastewater enters the coalescer, the wastewater is rectified by the fluid rectifier 1-1, so that the fluid is evenly distributed in the radial cross section of the fluid flow; the rectified wastewater is uniform Into the X-shaped braided layer 1-2 formed by the interlaced weaving of lipophilic and hydrophobic fibers and hydrophilic and oleophobic fibers, in the X-shaped braid 1-2, oil droplets are captured, coalesced and grown, and a trace oil-in-water emulsion is formed Demulsification and separation; the coalesced and separated oil and water enter the corrugated sheet layer 1-3 for rapid growth and separation of oil droplets; after the process of separation, the oil content in the wastewater is reduced to 0.1-20mg/L.

Second, the oxidation reaction unit includes a reactor. See Fig. 2. The reactor includes a second shell. A partition 2-2 is fixed in the second shell, and more than one fractal inner part 2-1 is fixed on the partition 2-2. , The fractal internals 2-1 can be fixed in parallel. A gas inlet and a liquid inlet are provided on the second shell located under the partition 2-2, the liquid inlet is connected with the first liquid discharge port, and the upper part of the second shell is provided with a first gas-liquid outlet. The fractal inner part 2-1 includes a cylinder, the bottom of the cylinder is fixed with a bottom plate 2-1-8, the cylinder above the bottom plate 2-1-8 is provided with a liquid inlet 2-1-7, and the side wall of the cylinder An intake pipe pointing to the bottom plate 2-1-8 is fixed on the top. The bottom of the intake pipe can be sealed by an intake plug 2-1-4. There are multiple aeration micropores 2-1-3, the liquid inlet 2-1-7 and the air inlet 2-1-6 are located under the partition 2-2, and the top of the cylinder is the second gas-liquid outlet 2. -1-1. The minimum flow channel size of the fractal inner part 2-1 is 1.2-12mm. Runner refers to all circulation areas except equipment.

Further, a throat pipe 2-1-2 is fixed in the second gas-liquid outlet 2-1-1, and the middle of the throat pipe 2-1-2 is a through hole with a small middle and two large ends, and the minimum inner diameter of the throat pipe is 6～ 100mm.

The present invention also provides a circulating feed system for the oxidation reaction unit. Referring to Fig. 5, a circulating pump 7 is provided on the outside of the reactor, and the two ends of the circulating pump 7 are respectively connected to the inside of the reactor located above and below the partition plate 2-2. The reacted product part is injected into the fractal inner part 2-1 again through the circulating pump 7, so that the reacted liquid phase reacts with fresh air for a second time, so as to achieve the purpose of improving the oxidation efficiency.

The treatment process of the oxidation reaction unit is: the sulfur-containing organic wastewater after coalescing and degreasing is pressurized by the booster pump and then enters the liquid inlet of the fractal inner part 2-1. At the same time, fresh air enters the inlet pipe through the compressor. Port 2-1-6 is blown into the fractal inner part 2-1. After the gas enters the air inlet pipe, bubbles are generated through the aeration micropores 2-1-3. The bubbles and sulfur-containing organic wastewater are fully uniform in the mixing chamber 2-1-5 After mixing, it is sprayed out through the throat 2-1-2, and the oxygen in the fractal bubble fully reacts with the sulfide in the sulfur-containing organic waste water to oxidize it into sodium thiosulfate or sulfate.

All equipment parts in the reactor are large-sized channels and static parts. There is no flow dead zone in the device, which can avoid a large amount of potential fouling deposits in the oxidation reaction. The waste lye and compressed air are used as kinetic energy sources, and the water contained in the upper cavity of the partition is a continuous phase fluid, which causes the gas-liquid to mix with the existing liquid in the upper cavity of the partition, so that the temperature of the device is more uniform. With the above-mentioned reactor, most of the gas size is small, which prevents the gas from rising rapidly due to its low density relative to the surrounding liquid. This smaller bubble lengthens the contact time between the gas and the liquid, and greatly improves the oxygen utilization rate. In the above-mentioned reactor, a part of the gas size is relatively large, and a gas-liquid flow state of local turbulence and overall flat plug flow is formed in the device. This larger bubble promotes the renewal of the gas-liquid interface. As the reaction deepens, the bubble oxygen partial pressure continues to decrease. This method makes it easier for the low partial pressure oxygen to be transferred to the liquid phase.

Third, the swirling flow degassing unit includes a third shell and a swirling flow deaerator 3-1 in the third shell (the structure of the swirling flow deaerator 3-1 is similar to the use of swirling or centrifugal field in the patent CN201310037577.5 It is consistent with the structure of the pressure gradient field coupling device for liquid degassing), the side of the third shell is provided with a gas-liquid two-phase inlet, and the gas-liquid two-phase inlet communicates with the cyclone degasser 3-1 and the second gas-liquid Outlet 2-1-1, a second liquid discharge port is provided at the bottom of the third casing, and a gas-phase discharge port is provided on the top of the third casing.

The processing process of the cyclone degassing unit is: combined with the cyclonic deaerator in Figure 3, the reacted gas-liquid mixture enters the device from the liquid gas inlet 3-1-1 under a certain pressure, and under the action of the centrifugal field, The gas in the liquid migrates to the center position of the column cavity 3-1-2, generating a pressure gradient field, and the gas dissolved in the inlet liquid migrates to the center axis position of the column cavity 3-1-2 under the action of the pressure gradient field, and The gas separated from the centrifugal field at the 3-1-4 section of the conical port at the end of the first overflow pipe is mixed and discharged through the first overflow pipe column cavity 3-1-5, and the liquid entrained by the gas is discharged through the second overflow The annular slot 3-1-7 on the column cavity 3-1-8 performs secondary separation, and the purified gas is discharged from the upper opening of the second overflow pipe column cavity 3-1-8, entraining the recovered secondary liquid It is discharged through the secondary liquid outlet 3-1-6, and the degassed purified liquid is discharged from the liquid-phase outlet 3-1-3.

Fourth, the closed mud discharge unit includes a fourth shell and a mud drain 4-1 arranged at the bottom of the fourth shell. The fourth shell is provided with a liquid inlet and a mud outlet, and the liquid inlet and the second The two liquid discharge ports are connected, and the mud discharging device 4-1 is connected to the mud discharging port, see Figure 4A.

Further, the upper part of the fourth shell is provided with a liquid discharge outlet; the sludge discharger includes a main pipe 4-1-5, a sub-pipe 4-1-6, and a sludge discharge pipe 4-1-7 that are connected in sequence; the fourth shell The body is provided with a high-pressure water inlet, the main pipeline is connected to the high-pressure water inlet, the high-pressure water inlet is connected to the booster pump 5, and the mud discharge pipe 4-1-7 is connected to the mud discharge port; the sub-pipe 4-1-6 is connected with an opening The ejection nozzle 4-1-1 is connected to the opening of the blocking plate. The axis of the ejection nozzle 4-1-1 and the sub-pipe 4-1-6 coincide; the ejection nozzle 4-1-1 and The branch pipe 4-1-6 between the main pipe 4-1-5 is connected with the mud mixing nozzle 4-1-2, the ejection nozzle 4-1-1 and the mud pipe 4-1-7 are connected with each other. The pipe 4-1-6 is provided with a mud-inducing chamber 4-1-4, and the sub-pipe 4-1-6 between the ejection nozzle 4-1-1 and the mud-inducing chamber 4-1-4 is connected with an umbrella outside. Suction cup 4-1-3.

The closed sludge discharging unit of the present invention can be further equipped with a parallel installation mode of sludge discharging devices to increase the processing capacity. Specifically, referring to Fig. 4B, there are more than one sub-pipes 4-1-6 connected between the main pipe 4-1-5 and the sludge discharge pipe 4-1-7, and the cross-sectional area of the main pipe 4-1-5 is all The sum of the cross-sectional area of the sub-pipe 4-1-6.

The diameter of the sub-pipe 4-1-6 is 20-200mm, the mud mixing nozzle 4-1-2 and the sub-pipe are at an angle of 30-80°; the expansion angle of the umbrella-shaped suction cup 4-1-3 is 90-160 degrees. Umbrella suction cup 4-1-3 has a hole on the top, and a straight pipe with a diameter of 30-100mm is welded to the opening of the sub-pipe 4-1-6, and the length of the straight pipe is 50-80mm.

The treatment process of the closed sludge discharge unit is: the liquid phase feed and neutralization reaction after degassing by the cyclone degassing unit. The neutralization reaction can be carried out in the mixer 6 or artificially added and adjusted, and the neutralized liquid enters the closed discharge In the mud unit, after gravity sedimentation, the treated waste liquid is discharged, and the sludge is deposited on the bottom and needs to be discharged regularly. When the mud is discharged, the booster pump is turned on, the high-pressure water flows into the main pipe 4-1-5, one water flow is sprayed out through the mud mixing nozzle 4-1-2 to loosen the deposited mud, and the other water flow passes through the ejection nozzle 4-1 -1 is ejected, and negative pressure is formed in the pipeline when the high-pressure water jet is sprayed. The loose mud is sucked into the pipeline through the umbrella-shaped suction cup 4-1-3, and is discharged after being mixed with the high-pressure water flow in the mud discharge channel 4-1-7.

The method of the present invention for wet oxidation treatment of sulfur-containing organic wastewater using the above-mentioned device can be summarized as follows: firstly, the sulfur-containing organic wastewater is subjected to high-efficiency degreasing treatment, and the sulfide is chemically oxidized by the air oxidation method, and the reaction product enters the cyclone. Degasser for deep gas-liquid separation. The desulfurized wastewater is neutralized, and the neutralized waste liquid flows to the closed sludge discharge unit to precipitate out suspended solids and some colloids. The sludge settled at the bottom is regularly discharged through the sludge discharger. Specifically, it includes the following steps:

(1) Use coalescing degreasing unit to deoil sulfur-containing organic wastewater with a temperature of 4 to 210 degrees Celsius, and reduce the oil content to 0.1 to 20 mg/L after treatment;

(2) The degreasing wastewater enters the liquid inlet of the fractal internals, and air is filled into the intake pipe. The gas-liquid ratio entering the fractal internals is 0.1-30, the apparent gas velocity is 0.001-0.1m/s, and the bubble diameter It is 0.02-20mm, and the liquid phase residence time is 1.5-2.5 hours. The wastewater fully reacts with the oxygen in the air, and the reacted gas-liquid two-phase product is discharged from the first gas-liquid outlet into the cyclone degasser;

(3) The cyclone degasser separates the gas-liquid two-phase material, and then carries out the neutralization treatment;

(4) The formed sludge enters the fourth shell through the liquid inlet, and the high-pressure water is pumped into the bottom mud drain through the high-pressure water inlet by the booster pump (control pressure is 0.2～2MPa), after the high-pressure water enters the pipeline It is divided into two paths, one of which is sprayed out through mud mixing nozzle to make the sludge deposited at the bottom loose and uniform, and the other is through the ejection nozzle to generate a high-speed jet to form a vacuum in the sludge chamber, and the sludge at the bottom of the fourth shell passes through The mud chamber is sucked in, mixed with the high-speed jet in the pipeline and discharged.

The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. Inside.

Claims

A device for wet oxidation treatment of sulfur-containing organic wastewater, characterized in that the device comprises a coalescing and degreasing unit, an oxidation reaction unit, a cyclone degassing unit and a closed sludge discharge unit;

The coalescing and degreasing unit includes a coalescer, and the coalescer includes a first shell and an oil removing device in the first shell; the top surface of the first shell is provided with a liquid inlet and oil Phase outlet; the bottom of the first shell below the oil phase outlet is provided with a first drain;

The oxidation reaction unit includes a reactor, the reactor includes a second shell, a partition is fixed in the second shell, and more than one fractal internals are fixed on the partition; The second shell is provided with a gas inlet and a liquid inlet, the liquid inlet is communicated with the first liquid outlet, and the upper part of the second shell is provided with a first gas-liquid outlet; the fractal inner piece It includes a cylinder body, a bottom plate is fixed at the bottom of the cylinder body, a liquid inlet is opened on the cylinder body above the bottom plate, and an air inlet pipe pointing to the bottom plate is fixed on the side wall of the cylinder body. The bottom of the air inlet pipe is sealed, the air inlet pipe is provided with a plurality of aeration micropores, the liquid inlet and the air inlet pipe are both located below the partition, and the top of the cylinder is a second air-liquid outlet ；

The cyclone degassing unit includes a third housing and a cyclone deaerator in the third housing, a gas-liquid two-phase inlet is provided on the side of the third housing, and the gas-liquid two-phase inlet Communicating the cyclone deaerator and the second gas-liquid outlet, a second liquid discharge port is provided at the bottom of the third casing, and a gas phase discharge port is provided on the top of the third casing;

The airtight mud drain unit includes a fourth shell and a mud drain provided at the bottom of the fourth shell. The fourth shell is provided with a liquid inlet and a mud outlet, and the liquid inlet It is in communication with the second liquid discharge port, and the sludge discharger is in communication with the sludge discharge port.
The device according to claim 1, wherein the oil removal device comprises a fluid rectifier, an X-shaped fiber layer and a corrugated plate layer which are sequentially arranged between the liquid inlet and the oil phase outlet.
The device according to claim 2, wherein the corrugated board layer comprises a plurality of zigzag corrugated boards arranged side by side, the distance between adjacent corrugated boards is 5-25mm, and the wave crest has a diameter of 5-10mm. The distance between the circular holes is 50-300mm.
The device according to claim 1, wherein a throat pipe is fixed in the second gas-liquid outlet, and the middle of the throat pipe is a through hole with a small middle and two large ends, and the minimum inner diameter of the throat pipe is 6 ~100mm.
The device according to claim 1, wherein a circulating pump is provided on the outside of the reactor, and two ends of the circulating pump are respectively connected to the inside of the reactor located above and below the partition.
The device according to claim 1, wherein the upper part of the fourth housing is provided with a liquid discharge outlet; the sludge discharger comprises a main pipe, a branch pipe and a sludge discharge pipe connected in sequence; the fourth The casing is provided with a high-pressure water inlet, the main pipe is connected to the high-pressure water inlet, and the mud discharge pipe is connected to the mud discharge port; An ejection nozzle is connected to the opening, and the axis of the ejection nozzle coincides with the axis of the sub-pipe; a mud mixing nozzle is connected outside the sub-pipe between the ejection nozzle and the main pipe. The sub-pipe between the jet nozzle and the mud-discharging pipe is provided with a mud-inducing chamber, and an umbrella-shaped suction cup is connected outside the sub-pipe between the jet nozzle and the mud-inducing chamber.
The device according to claim 6, wherein more than one sub-pipe is connected between the main pipe and the sludge discharge pipe, and the cross-sectional area of the main pipe is one of the cross-sectional areas of all the sub-pipes. with.
The device according to claim 6, wherein the diameter of the sub-pipe is 20-200mm, the mud mixing nozzle and the sub-pipe are at an angle of 30-80°; the umbrella-shaped suction cup expands The angle is 90 to 160 degrees.
The method for wet oxidation treatment of sulfur-containing organic wastewater using the device of any one of claims 1-8, characterized in that it comprises the following steps:

(1) Use coalescing degreasing unit to degreasing treatment of sulfur-containing organic wastewater;

(2) The degreasing wastewater enters the liquid inlet of the fractal internals, air is filled into the inlet pipe, the wastewater fully reacts with oxygen in the air, and the reacted gas-liquid two-phase material is discharged from the first gas-liquid outlet into the swirling flow Degasser

(3) The cyclone degasser separates the gas-liquid two-phase material;

(4) The formed sludge enters the fourth housing through the liquid inlet, and is discharged from the sludge outlet through the sludge discharger.
The method according to claim 9, wherein the gas-liquid ratio in the fractal internals is 0.1-30, the apparent gas velocity is 0.001-0.1m/s, the bubble diameter is 0.02-20mm, and the liquid phase residence time is 1.5 ~2.5 hours.