JP6977207B1 - Wastewater treatment system for pyridine multicyclic compounds and their processes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wastewater treatment system for a pyridine polycyclic compound and a process thereof, which can not only effectively decompose pyridine polycyclic contaminants in wastewater but also avoid the loss of filler in a filler absorption tower. .. SOLUTION: A fixed bed reactor including a waste liquid storage tank 1, a fixed bed reactor 2, a heat exchanger 3, a filler absorption tower 4 and a primary water storage tank 5 connected in order, and containing a ruthenium-based catalyst is installed. , The reduction reaction with the pyridine polycyclic compound in the waste water is easily caused, the nitrogen in the pyridine ring is decomposed in the form of ammonia, and the pyridine polycyclic contaminant in the waste water is removed. A two-layer spiral thermal insulation jacket is provided on the outside of each reaction branch tube to make the temperature distribution more uniform and to cause local charring of the catalyst in the reaction branch tube caused by direct contact with the side wall of the reaction branch tube by heat. It is possible to avoid the influence on the catalyst performance. [Selection diagram] Fig. 1

Description

The present invention belongs to the technical field of wastewater treatment, and specifically relates to a wastewater treatment system for a pyridine polycyclic compound and a process thereof.

Pyridines and pyridine derivatives are a very important class of microchemical raw materials or products.
Widely used in industrial solvents, pharmaceuticals, pesticides, feeds, dyes and other fields, it is known as the "chip" for heterocyclic drugs, pesticides and veterinary drugs. Due to its wide range of applications, pyridine and pyridine derivatives can be detected in many industrial wastewaters. Pyridines and pyridine derivatives are often malodorous and irritating, some of which have potential carcinogenic effects, bioaccumulation or high mobility, and have specific toxic effects on the human body and natural microorganisms. Therefore, it is important to be able to efficiently remove such organic wastewater.

Due to the stable chemistry of lysine heterocyclic compounds, incineration is the only method that can industrially treat organic wastewater containing pyridine heterocyclic compounds. However, since the pyridine ring contains nitrogen atoms _{, not only a large amount of CO 2} is generated during the incineration process, but also a large amount of NOx
As a result, the exhaust gas treatment load and emission concentration of the incinerator increase, and at the same time, a large amount of energy is required for the incinerator treatment, and to some extent, its drawbacks limit the further development of incinerator technology. Therefore, considering the application needs of wastewater treatment of pyridine polycyclic compounds and the characteristics of pyridine polycyclic compounds, the development of wastewater treatment systems and their processes with high treatment efficiency, thorough decomposition, energy saving and environmental protection has been developed. , Good application prospects are expected.

An object of the present invention is a wastewater treatment system for a pyridine polycyclic compound and a process thereof, which can not only effectively decompose pyridine polycyclic contaminants in wastewater but also avoid the loss of filler in a filler absorption column. Is to provide.

As a technical solution of the present invention, there is provided a wastewater treatment system for a pyridine polycyclic compound including the following.
The wastewater storage tank filters and agitates the temporarily stored wastewater, removes large solid impurities in the wastewater, and the impurities clog the pipeline or invade subsequent equipment, making cleaning difficult. By continuously stirring the wastewater, it is possible to avoid exacerbating the pollution of the wastewater due to the lack of oxygen at the bottom end due to the delay in the treatment of the wastewater.
The fixed-bed reactor connected to the waste liquid storage tank is provided with a flow meter and a waste liquid charge pump at the connection points with the waste liquid storage tank, respectively, and the flow meter is an electronic flow meter, and the flow meter and the waste liquid charge pump are provided. Electrically connected to an external intelligent control element, the external intelligent control element detects the magnitude of the water flow in the flow chamber, controls the on / off of the waste liquid feed pump, and at the same time, other electricity as described in the specification. The element is also electrically connected to an external intelligent control element, and the fixed bed reactor is a reaction shell including a first reaction chamber, a partition chamber and a second reaction chamber in order from top to bottom, respectively. A reaction tube rack provided in the first reaction chamber and the second reaction chamber, and a heating element provided in the partition chamber are included, and waste water inlets are provided on the side walls of the first reaction chamber and the second reaction chamber, respectively. And a discharge bubble is provided, outlets are provided at the bottom ends of the first reaction chamber and the second reaction chamber, and the first reaction chamber and the second reaction chamber simultaneously treat waste water in two batches and waste water. Increase processing efficiency.

The reaction tube rack is located between the upper connection plate, the lower connection plate, and the upper connection plate and the lower connection plate, and a plurality of reaction branch tubes are provided so that both upper and lower ends penetrate the upper connection plate and the lower connection plate, respectively. A plurality of guide plates are cross-distributed along the vertical direction in each of the reaction branch pipes, and a spiral heat insulating jacket 1 and a spiral heat insulating jacket 2 are provided outside the reaction branch pipe from the inside to the outside, respectively. , The spiral heat insulating jacket 1 and the spiral heat insulating jacket 2
A spiral heat-retaining heating chamber is configured between them, and the installation of the spiral heat-retaining heating chamber causes heat to come into direct contact with the catalyst in the reaction branch tube, causing the temperature at the contact point to be too high and causing a local burning phenomenon. It affects the catalytic performance of the catalyst and avoids reducing the treatment effect of the entire wastewater treatment system.

Each of the heating elements is connected to penetrate the bottom end of each spiral heat insulating heating chamber.
The heat exchanger connected to the fixed bed reactor forms a circulation loop with the fixed bed reactor, and by designing the circulation loop, the water after the catalytic reaction treatment is exchanged by the heat exchanger heat, and the water is replaced. Heat can be collected and flowed into the fixed bed reactor through the circulation loop weight and reused, which has the advantages of energy saving and environmental protection.

A gasometer is connected to the filler absorption tower connected to the heat exchanger via a water-sealed tank.
The primary water storage tank connected to the filler absorption tower and provided with a water replenishment circulation pump at the connection point supplies water to the water-sealed tank, and a liquid level gauge is provided in the primary water storage tank.

Further, a homogenizing disk is provided at the bottom end of the wastewater inlet corresponding to the second reaction chamber of the first reaction chamber, and a one-to-one correspondence with the reaction branch pipe is provided at the bottom end of each homogenizing disk. An outlet is provided, the upper end of each reaction branch tube penetrates the upper connection plate and extends outward, and the outlet is inserted into the outer wall of the upper end of the corresponding reaction branch tube and is provided with a uniformized disk. , The wastewater that has entered the first reaction chamber and the second reaction chamber is evenly distributed at the upper end of the reaction tube rack, and at the same time, the upper end of each reaction branch tube is connected to the corresponding outlet, and the wastewater is uniform. At the same time, it can enter the corresponding reaction branch pipe more accurately, enhance the treatment effect of wastewater, and prevent the wastewater from spilling on the inner wall of the fixed bed reactor and causing contamination of internal devices.

Further, access ports are provided on the side walls of the first reaction chamber, the partition chamber and the second reaction chamber, respectively, a ruthenium-based catalyst is arranged in each of the reaction branch tubes, and the pyridine plural cyclic compound is oxidized. Select a ruthenium-based catalyst that is difficult but easily reduced and easily undergoes a reduction reaction, and escapes nitrogen in the pyridine ring in the form of ammonia.
Other carbon, hydrogen, and oxygen atoms are also _{released in the form of CO 2} , CH ₄ , and H ₂ O, achieving the purpose of removing pyridine multi-ring contaminants in wastewater, and by installing access ports in each reaction branch tube. The ruthenium-based catalysts placed in the water are replaced as needed to enhance the treatment effect of wastewater.
Further, a horizontal filter is provided in the waste liquid storage tank, a sludge discharge port is provided in the center of the bottom end of the waste liquid storage tank, the bottom end of the waste liquid storage tank has an arcuate structure, and the sludge is at the bottom end. Multiple sludge guide grooves distributed along the circumferential direction of the discharge port are provided, and
Solid impurities in the wastewater are filtered by a horizontal filter, and the settled sludge in the wastewater is sent to the sludge discharge port through each sludge guide groove by the multiple sludge guide grooves distributed along the circumferential direction of the sludge discharge port. It is guided and discharged to improve sludge discharge efficiency.

Further, the filler absorption tower includes an absorption shell having an air inlet at the bottom end and an air outlet at the upper end, and a spray member, a filler press member and a filler layer distributed in the absorption shell in order from top to bottom. The filler press member is an adjustment frame provided symmetrically on both the left and right sides of the absorption shell and uniformly provided with a plurality of engaging circular holes from top to bottom on the side wall, and the filler layer in the absorption shell. A press frame located at the upper end, each of which includes two arcuate buckle plates provided on the left and right sides of the outer wall of the absorption shell and fixedly connected to each of the left and right sides of the press frame, and is a side wall of the absorption shell. A vertical limiting groove is provided at the position of the arcuate buckle plate, the arcuate buckle plate is connected to the outer wall of the adjustment frame via a slide sleeve, and a fixing circular hole is provided on the slide sleeve. The fixing circular hole is connected to the engaging circular hole via a bolt, and by adjusting the height of the slide sleeve from the adjustment frame, it is necessary to adjust the distance between the press frame and the filler layer and replace the filler layer. If there is, move the slide sleeve upwards on the adjustment frame, insert the bolt into the fixing circular hole and the engaging circular hole of the corresponding height to fix, separate the press frame and the filler layer, and then replace. Once done and the exchange is complete,
Move the slide sleeve downwards on the adjustment frame and insert bolts into the fixing and engaging circular holes of the corresponding height for fixation, press the filler layer with the press frame and under the filler absorption tower. Even when the airflow rising from is large, the press frame does not shift and the filler layer can be sufficiently pressed.

Further, the height of the vertical limiting groove is equal to the distance between the uppermost and lowermost engaging circular holes, the height of the arcuate buckle plate is higher than the height of the vertical limiting groove, and the arcuate buckle plate. By installing an arc-shaped buckle plate whose length is larger than the vertical limiting groove, the vertical limiting groove is not blocked while the press frame is moving up and down, and air leakage occurs. , It is possible to avoid affecting the normal use of the filler absorption tower.
Furthermore, a water quality detector and a stirring element are provided in the primary water storage tank, and the stirring element may be an existing stirring paddle, and whether the quality of the water treated by the water quality detector meets the standard. Is detected, secondary contamination is prevented, and the treated water is agitated by a stirring element.
Secondary pollution due to lack of oxygen at the bottom of the water due to treatment delays can be avoided.

The process of the wastewater treatment system for the above pyridine polycyclic compound specifically comprises the following steps.
S1: When the wastewater flows into the wastewater storage tank, the solid impurities in the wastewater are filtered by a horizontal filter and then temporarily stored in the wastewater storage tank.
S2: The heating element is started, and the fixed bed reactor is heated by the heating element. At this time, heat flows into the inside of each spiral heat insulation heating chamber through the bottom end of each spiral heat insulation heating chamber, and spirals along the spiral heat insulation heating chamber. The spiral heat insulating jacket 2 is arranged away from the reaction branch tube, and heat is indirectly transferred to the reaction branch tube via the spiral heat insulating jacket 2 to heat the inside thereof, and heat can be directly transferred to the inside of the reaction branch tube. It avoids contacting the side wall of the reaction branch tube and causing local charring of the catalyst in the reaction branch tube, which affects the catalytic performance.
S3: When the temperature inside the fixed bed reactor reaches 350 ° C, stabilize for 30 to 60 minutes, start the waste liquid feed pump, and use the waste liquid charge pump to drain the waste water from the waste liquid storage tank through the two waste water inlets. At the same time, the pumping amount is controlled by a flow meter so that the temperature stability of the fixed bed catalyst bed layer can be ensured at the same time as pumping to the upper end inside the first reaction chamber and the second reaction chamber, respectively, and at this time, the water flow is controlled. Is uniformly dispersed in various reaction branch pipes from the insertion port at the bottom end of the homogenized disk, waste water reacts with the ruthenium-based catalyst in the reaction branch pipe, and the water after the reduction reaction enters the heat exchanger. After heat exchange and cooling, it enters the filler absorption tower, the water in the filler absorption tower absorbs the ammonia after the reaction and is collected as ammonia water, and the gas containing methane and carbon dioxide enters the gasometer and is stored, and after treatment. Water enters and is stored in the primary water storage tank.
S4: When the heat in the above heat exchanger can be recovered and re-injected into the fixed bed reactor, and the water quality detector is used to detect whether the treated water quality meets the standard and does not meet the standard. , Water may be pumped up to the filler absorption tower again by the water replenishment circulation pump.

The present invention has the following beneficial effects.
(1) The pyridine multicyclic compound of the present invention undergoes a reduction reaction in a fixed bed reactor of a ruthenium-based catalyst, escapes nitrogen in the pyridine ring in the form of ammonia, and other carbon, hydrogen, and oxygen atoms are also CO. _2, CH 4, is released in the form of _H 2 _O, effectively degrade pyridine plurality rings contaminants in waste water, with the solution to treatment of the organic waste water is difficult industry problems including pyridine plurality ring, the present invention The system has the advantages of high processing efficiency, thorough disassembly and energy saving and environmental protection, so it can be applied in a wide range of fields.
(2) Two reaction chambers are provided in the fixed bed reactor of the present invention, and wastewater is treated separately in two batches, and at the same time, a plurality of reaction branch tubes containing a ruthenium-based catalyst are provided in each reaction chamber. The upper end of each reaction branch pipe is connected to the corresponding outlet, and at the same time, the waste water is evenly distributed, and at the same time, it can enter more accurately in the corresponding reaction branch pipe, enhancing the treatment effect of the waste water, and the waste water is discharged from the fixed bed reactor. To avoid spilling on the inner wall and contaminating the internal devices, a two-layer spiral heat insulating jacket is also provided on the outside of each reaction branch tube to make the temperature distribution more uniform and heat is directly applied to the reaction branch tube. The direct contact with the side wall causes local charring of the catalyst in the reaction branch tube, avoiding affecting its catalytic performance, and the spiral heat-retaining jacket prolongs the time it takes for heat to pass through the spiral heat-retaining heating chamber. , Ensuring sufficient heating.
(3) A plurality of guide plates are cross-distributed in each reaction branch pipe of the present invention along the vertical direction, and by installing the guide plates, wastewater passes through the reaction branch pipe with a sufficient residence time, and inside the guide plate. The contaminants can be completely decomposed.
(4) In the present invention, since the press frame is provided in the filler absorption tower and the distance between the press frame and the filler layer can be adjusted at the same time, the press frame is displaced even when the airflow rising from the bottom of the filler absorption tower is large. This can cause filler loss and avoid problems.

It is a structural schematic diagram of this invention. It is an internal top view of the waste liquid storage tank of this invention. It is a schematic diagram of the internal structure of the fixed bed reactor of this invention. It is sectional drawing of the reaction branch tube of this invention. It is a structural schematic diagram of the filler absorption tower of this invention. It is a structural schematic diagram of the arc-shaped buckle plate of this invention.

[Explanation of sign]
1 Wastewater storage tank 10 Horizontal filter 11 Sludge discharge port 110 Sludge guide groove 2 Fixed floor reactor 20 Flow meter 21 Wastewater supply pump 22 Reaction shell 220 First reaction chamber 221 Partition chamber 222 Second reaction chamber 223 Wastewater inlet 224 Discharge Bubble 225 Outlet 226 Uniformized disk 2260 Outlet 227 Access port 23 Reaction tube rack 230 Upper connection plate 231 Lower connection plate 232 Reaction branch tube 2320 Guide plate 2321 Spiral heat insulation jacket 1
2322 Spiral heat insulation jacket 2
2323 Spiral heat insulation heating chamber 24 Heating element 3 Heat exchanger 4 Filler absorption tower 40 Absorption shell 400 Air inlet 401 Air outlet 402 Vertical limiting groove 41 Spray member 42 Filler press member 420 Adjustment frame 4200 Engagement circular hole 421 Press frame 422 yen Arc-shaped buckle plate 4220 Slide sleeve 4221 Fixing circular hole 4222 Seal adhesion layer 43 Filler layer 5 Primary water storage tank 50 Supplementary water circulation pump 51 Liquid level gauge 52 Water quality detector 53 Stirring element 6 Water sealing tank 60 Gasometer

Example 1
Wastewater treatment systems for pyridine multicyclic compounds include:
The waste liquid storage tank 1 is provided with a horizontal filter 10 inside, a sludge discharge port 11 is provided at the center of the bottom end of the waste liquid storage tank 1, and the bottom end of the waste liquid storage tank 1 has an arcuate structure. A plurality of sludge guide grooves 11 distributed along the circumferential direction of the sludge discharge port 11 at the ends.
0 is provided,
The fixed floor reactor 2 connected to the waste liquid storage tank 1 is provided with a flow meter 20 and a waste liquid supply pump 21 at the connection points with the waste liquid storage tank 1, respectively, and the fixed floor reactor 2 is internally from top to bottom. The first reaction chamber 220, the reaction shell 22 provided with the partition chamber 221 and the second reaction chamber 222, and the reaction tube rack 23 provided in the first reaction chamber 220 and the second reaction chamber 222, respectively, in this order. A heating element 24 provided in the partition chamber 221 is included, and a waste water inlet 223 and a discharge bubble 224 are provided on the side walls of the first reaction chamber 220 and the second reaction chamber 222, and the first reaction chamber 220 and the second reaction chamber 220 are provided. An outlet 225 is provided at the bottom end of the reaction chamber 222 of the above.
The reaction tube rack 23 is located between the upper connection plate 230, the lower connection plate 231 and the upper connection plate 230, and the lower connection plate 231. A plurality of guide plates 2320 intersecting and distributed along the vertical direction in each reaction branch tube 232 including the reaction branch tube 232, and the spiral heat insulating jacket 1 2321 and the spiral heat insulating jacket 1 2321 from the inside to the outside of the reaction branch tube 232, respectively. Spiral heat insulation jacket 2 232
2 is provided, and the spiral heat insulating jacket 1 2321 and the spiral heat insulating jacket 2 23
A spiral heat insulating heating chamber 2323 is configured between 22.
The heating elements 24 are connected through the bottom end of each spiral heat insulating heating chamber 2323, and the wastewater inlet 22 corresponding to the second reaction chamber 222 of the first reaction chamber 220 is connected.
A homogenizing disk 226 is provided at the bottom end of each of 3, a reaction branch tube 232 and a one-to-one corresponding insertion port 2260 are provided at the bottom end of each homogenizing disk 226, and the upper end of each reaction branch tube 232 is provided. Each of them penetrates the upper connecting plate 230 and extends to the outside, and the insertion port 2260 is inserted into the outer wall of the upper end of the corresponding reaction branch pipe 232.
The heat exchanger 3 connected to the fixed bed reactor 2 has a circulation loop formed with the fixed bed reactor 2 on the side walls of the first reaction chamber 220, the partition chamber 221 and the second reaction chamber 222. Each access port 227 is provided, and a nickel catalyst is arranged in each reaction branch tube 232.
The filler absorption tower 4 connected to the heat exchanger 3 is connected to the gasometer 60 via the water sealing tank 6, and the filler absorption tower 4 adopts the existing filler absorption tower.
The primary water storage tank 5 connected to the filler absorption tower 4 and provided with a water replenishment circulation pump 50 at the connection point supplies water to the water sealing tank 6, and a liquid level gauge 51 is provided on the primary water storage tank 5 to provide primary water storage. A water quality detector 52 and a stirring element 53 are provided in the tank 5, and the stirring element 53 may be an existing stirring paddle.

The process of the wastewater treatment system for the above pyridine multicyclic compound specifically comprises the following steps:
S1: When the wastewater flows into the wastewater storage tank 1, the solid impurities in the wastewater are filtered by the horizontal filter 10 and then temporarily stored in the wastewater storage tank 1.
S2: The heating element 24 is started, and the fixed bed reactor 2 is heated by the heating element 24. At this time, heat flows into the spiral heat insulating heating chamber 2323 through the bottom end of each spiral heat insulating heating chamber, and the spiral heat insulating heating chamber is heated. Spiral upwards along 2323, spiral insulation jacket 2 2322 is located away from the reaction branch tube 232 and heat is spiral insulation jacket 2
It is indirectly transmitted to the reaction branch tube 232 via 2322 and can heat the inside thereof, and the heat directly contacts the side wall of the reaction branch tube 232 and causes local charring of the catalyst in the reaction branch tube 232, and the catalyst thereof. Avoid affecting performance,
S3: When the temperature in the fixed bed reactor 2 reaches 250 ° C., stabilize for 30 minutes, start the waste liquid charge pump 21, and use the waste liquid charge pump 21 to drain the waste water from the waste liquid storage tank 1 to the two waste water inlets 223. The pumping amount is controlled by the flow meter 20 so that the temperature stability of the fixed bed catalyst bed layer can be ensured at the same time as pumping to the upper end of the inside of the first reaction chamber 220 and the second reaction chamber 222, respectively. At this time, the water flow is uniformly dispersed in various reaction branch tubes 232 from the insertion port 2260 at the bottom end of the homogenizing disk 226, and the waste water reacts with the ruthenium-based catalyst in the reaction branch tube 232 to reduce the water flow. The water after the reaction enters the heat exchanger 3, and after heat exchange and cooling, it enters the filler absorption column 4, and the water in the filler absorption column 4 absorbs the ammonia after the reaction to become ammonia water, which is collected and collected. Gas containing carbon dioxide enters the gasometer and is stored, and the treated water enters the primary water storage tank 5 and is stored.
S4: The heat in the heat exchanger 3 can be recovered and recharged into the fixed bed reactor 2, and the water quality detector 52 can be recharged.
Is used to detect whether or not the treated water quality meets the standard, and if the standard is not met, water may be pumped up to the filler absorption tower 4 again by the water replenishment circulation pump 50.
When treating wastewater using the existing filler absorption tower 4

Example 2
This embodiment is almost the same as that of Example 1 except for the following points.
The filler absorption tower 4 includes an absorption shell 40 having an air inlet 400 at the bottom end and an air outlet 401 at the upper end, a spray member 41 distributed in the absorption shell 40 in order from top to bottom, a filler press member 42, and the filler absorption tower 4. The adjusting frame 420 and the absorbing shell 40, which include the filler layer 43, are symmetrically provided on the left and right sides of the absorbing shell 40, and a plurality of engaging circular holes 4200 are uniformly provided on the side wall from top to bottom. A press frame 421 provided inside and located at the upper end of the filler layer 43, and two arc-shaped buckle plates 422 provided on both the left and right sides of the outer wall of the absorption shell 40 and fixedly connected to the left and right sides of the press frame 421, respectively. A vertical limiting groove 402 is provided at the position of the two arcuate buckle plates 422 on the side wall of the absorption shell 40, and the arcuate buckle plate 422 is connected to the outer wall of the adjustment frame 420 via a slide sleeve 4220. , Slide sleeve 4
A fixing circular hole 4221 is provided on the 220, and the fixing circular hole 4221 is an engaging circular hole 42.
Connected to 00 via bolts
The height of the vertical limiting groove 402 is equal to the distance between the uppermost and lowermost engaging circular holes 4200, the height of the arcuate buckle plate 422 is larger than the height of the vertical limiting groove 402, and the arcuate buckle plate. A seal adhesion layer 4222 is provided on the inner wall of the 422.
The filler absorption tower 4 operates as follows:
By adjusting the height of the slide sleeve 4220 from the adjustment frame 420, the distance between the press frame 421 and the filler layer 43 is adjusted, and when the filler layer 43 needs to be replaced, the slide sleeve 4220 is adjusted on the adjustment frame 420. Move upward with, insert the bolt into the fixing circular hole 4221 and the engaging circular hole 4200 at the corresponding height to fix it, separate the press frame 421 and the filler layer 43, and then replace it to complete the replacement. Then, the slide sleeve 4220 is moved downward on the adjustment frame 420, and the bolt is inserted into the fixing circular hole 4221 and the engaging circular hole 4200 at the corresponding heights to fix the press frame 42.
Even when the filler layer 43 is pressed in step 1 and the airflow rising from under the filler absorption tower 4 is large, the press frame 421 does not shift.
Statistical analysis of the results of Examples 1 and 2 above revealed that the effects of different filler absorption towers 4 on the treatment effect of contaminants in wastewater were obtained, and the specifics are as follows.
Conclusion 1: When using a conventional commercially available filler absorption tower 4, if the airflow rising from under the filler absorption tower 4 is large, there is a problem that the internal filler is likely to be lost. Although the overall removal rate is only 46.23%, the filler absorption tower 4 of the present application has a press frame inside, and at the same time, the distance between the press frame and the filler layer can be adjusted, which greatly increases the possibility of filler loss. The overall removal rate of pollutants in wastewater is 59.6%.

Example 3
This embodiment is almost the same as that of Example 2 except for the following.
The catalyst arranged in each reaction branch tube 232 is a ruthenium-based catalyst, and the removal rate of the pyridine polycyclic compound in the wastewater is 76.58%.
Statistical analysis of the results of Examples 2 and 3 above revealed the effects of various catalysts on the treatment effect of the pyridine multicyclic compound, which is a major contaminant in wastewater, and the specific conclusions are as follows. Is.
Conclusion 2: With the same other equipment and parameters, the removal rate for the pyridine multicyclic compound, which is the main pollutant in the wastewater by the nickel catalyst, is 59.6%, and the main pollution in the wastewater by the ruthenium-based catalyst. The removal rate for the pyridine polycyclic compound, which is a product, is 76.
.. Since it is 58%, the effect when a ruthenium-based catalyst is used is higher.

Example 4
This embodiment is almost the same as that of Example 3 except for the following.
The heating temperature of the heating element 24 with respect to the fixed bed reactor 2 is 300 ° C., and the stabilization time is 30 mi.
It was n, and the removal rate of the pyridine polycyclic compound in the wastewater was 78.26%.

Example 5
This embodiment is almost the same as that of Example 4 except for the following.
The heating temperature of the heating element 24 with respect to the fixed bed reactor 2 is 320 ° C., and the stabilization time is 30 mi.
It was n, and the removal rate of the pyridine polycyclic compound in the wastewater was 80.12%.

Example 6
This embodiment is almost the same as that of Example 4 except for the following.
The heating temperature of the heating element 24 for the fixed bed reactor 2 is 350 ° C., and the stabilization time is 30 mi.
It was n, and the removal rate of the pyridine polycyclic compound in the wastewater was 89.36%.

Example 7
This embodiment is almost the same as that of Example 4 except for the following.
The heating temperature of the heating element 24 with respect to the fixed bed reactor 2 is 400 ° C., and the stabilization time is 30 mi.
It was n, and the removal rate of the pyridine polycyclic compound in the wastewater was 68.12%.
Statistical analysis of the results of Examples 4-7 above revealed the effects of different heating temperatures on the treatment effects of the pyridine multicyclic compounds, which are the major contaminants in wastewater, and the specific conclusions are as follows: It's a street.
Conclusion 3: If the heating temperature rises, with other equipment and related parameters constant,
The removal rate of the pyridine polycyclic compound, which is the main contaminant in the waste water, gradually increased, and when the heating temperature was 350 ° C., the removal rate reached the maximum, specifically 89.36%, and then. As the temperature was further increased, the removal rate of the pyridine polycyclic compound in the waste water gradually decreased, so that the heating temperature reached the maximum when the heating temperature was 350 ° C.

Example 8
This embodiment is almost the same as that of Example 6 except for the following.
After heating the fixed bed reactor 2, the stabilization time was 45 min, and the removal rate of the pyridine polycyclic compound in the wastewater was 90.13%.

Example 9
This embodiment is almost the same as that of Example 6 except for the following.
After heating the fixed bed reactor 2, the stabilization time was 50 min, and the removal rate of the pyridine polycyclic compound in the wastewater was 91.16%.

Example 10
This embodiment is almost the same as that of Example 6 except for the following.
After heating the fixed bed reactor 2, the stabilization time was 55 min, and the removal rate of the pyridine polycyclic compound in the wastewater was 93.26%.

Example 11
This embodiment is almost the same as that of Example 6 except for the following.
After heating the fixed bed reactor 2, the stabilization time was 60 min, and the removal rate of the pyridine polycyclic compound in the wastewater was 96.58%.

Example 12
This embodiment is almost the same as that of Example 6 except for the following.
After heating the fixed bed reactor 2, the stabilization time was 65 min, and the removal rate of the pyridine polycyclic compound in the wastewater was 86.95%.

Example 13
This embodiment is almost the same as that of Example 6 except for the following.
After heating the fixed bed reactor 2, the stabilization time was 70 min, and the removal rate of the pyridine polycyclic compound in the wastewater was 76.56%.
Statistical analysis of the results of Examples 8-13 above yielded the effects of various temperatures and times on the treatment effects of the pyridine multicyclic compounds, which are the major contaminants in wastewater, and the specific conclusions are: It is as follows.
Conclusion 4: With constant other equipment and related parameters, the removal rate of the major contaminants in the wastewater, the pyridine multicyclic compound, gradually increases with increasing stabilization time, with a stabilization time of 60 min. The removal rate of the pyridine polycyclic compound reached the maximum, specifically 96.5.
It is 8%, and when the stabilization time exceeds 60 min, the removal rate of the pyridine polycyclic compound gradually decreases, which means that the temperature continues to rise as the stabilization time becomes longer, and when the stabilization time exceeds the optimum heating temperature, the pyridine gradually decreases. Since the removal rate of the polycyclic compound is lowered, the optimum stability time is 60 min.

Test Example Under the temperature condition of 350 ° C., the wastewater treatment system of this example and the conventional wastewater treatment system were used to treat the same amount of wastewater of the pyridine organic matter, respectively, and the treatment time was 2 hours, and the pyridine organic matter was treated. The included wastewater detection index parameter table is shown in Table 1, and a comparison table of both wastewater treatment performances is shown in Table 2.
Table 1: Detection index parameter table of wastewater containing pyridine organic matter

Table 2: Comparison table of wastewater treatment performance between the system of this embodiment and the conventional technology system

As described above, when the wastewater containing the same pyridine organic matter is treated in the same time by using the wastewater treatment system of the present embodiment and the wastewater treatment system of the prior art at the same temperature, the effect of the present embodiment is the prior art. It can be seen that it is significantly better than the wastewater treatment effect of.

Claims (6)

Waste liquid storage tank (1) and
It is connected to the waste liquid storage tank (1), and a ruthenium catalyst or a nickel catalyst is fixed.
Fixed bed reactors have a (2),
A heat exchanger (3) connected to the fixed bed reactor (2) and having a circulation loop formed between the fixed bed reactors (2).
A filler absorption tower (4) that absorbs ammonia, which is connected to the heat exchanger (3) and to which the gasometer (60) is connected via the water-sealed tank (6).
It is equipped with a primary water storage tank (5) connected to the filler absorption tower (4) and provided with a water replenishment circulation pump (50) at the connection point.
A flow meter (20) is connected to the fixed bed reactor (2) and the waste liquid storage tank (1), respectively.
And a waste liquid pump (21) is provided, and the fixed bed reactor (2) has a first reaction chamber (220), a partition chamber (221) and a second reaction chamber (222) in this order from top to bottom. ), The reaction tube rack (23) provided in the first reaction chamber (220) and the second reaction chamber (222), respectively, and the partition chamber (221). Including the heating element (24) provided in the first
A wastewater inlet (223) and a discharge bubble (224) are provided on the side walls of the reaction chamber (220) and the second reaction chamber (222), respectively, and the first reaction chamber (220) is provided.
And an outlet (225) is provided at the bottom end of the second reaction chamber (222), and the reaction tube rack (23) has an upper connection plate (230), a lower connection plate (231), and the upper connection plate (23).
It is located between the lower connection plate (231) and the upper and lower ends, respectively, of the upper connection plate (23).
0) and a plurality of reaction branch pipes (232) provided through the lower connecting plate (231), and a plurality of guide plates (2320) are provided along the vertical direction in each of the reaction branch pipes (232). The spiral heat insulating jacket 1 (2321) and the spiral heat insulating jacket 2 (2322) are provided from the inside to the outside of the reaction branch tube (232) so as to cross each other, and the spiral heat insulating jacket 1 (2321) is provided. ) And the spiral heat insulating jacket 2 (2322), a spiral heat insulating heating chamber (2323) is configured, and the heating elements (24) are connected through the bottom end of each spiral heat insulating heating chamber (2323). Being done
The primary water storage tank (5) supplies water to the water-sealed tank (6), and the primary water storage tank (5)
Liquid level meter (51) is provided, et al is on,
A catalyst is placed in each reaction branch tube (232), and the catalyst is a nickel catalyst or ruthenium.
It ’s a catalyst,
The filler absorption tower (4) is provided with an air inlet (400) at the bottom end and an air outlet (4) at the upper end.
The absorption shell (40) provided with 01) is divided into the absorption shells (40) in order from top to bottom.
Clothed spray member (41), filler press member (42) and filler layer (43)
The filler press member (42) is symmetrical on the left and right sides of the absorption shell (40).
An adjustment flap that is arranged and uniformly provided with a plurality of engaging circular holes (4200) on the side wall from top to bottom.
Located in the ram (420), absorption shell (40) and at the top of the filler layer (43)
Press frame (421), each provided on the left and right sides of the outer wall of the absorption shell (40)
Two arc-shaped bars fixedly connected to the left and right sides of the press frame (421), respectively.
A side wall of the absorption shell (40), including a tackle plate (422), with two arcs.
A vertical limiting groove (402) is provided at the position of the buckle plate (422), and the arc shape is described.
Buckle plate (422) is adjustable frame (4220) via slide sleeve (4220)
A circular hole for fixing (4220) connected to the outer wall of 420) and on the slide sleeve (4220).
4221) is provided, and the fixing circular hole (4221) is provided with an engaging circular hole (4200).
Connected via Lut ,
A wastewater treatment system for pyridine polycyclic compounds. A homogenizing disk (226) is provided at the bottom end of the wastewater inlet (223) corresponding to the second reaction chamber (222) of the first reaction chamber (220), and the homogenizing disk (226) is provided. At the bottom end, there is a one-to-one correspondence with the reaction branch tube (232) (2260).
) Is provided, the upper end of each reaction branch tube (232) extends outward through the upper connection plate (230), and the insertion port (2260) is the upper end of the corresponding reaction branch tube (232). The wastewater treatment system for a pyridine polycyclic compound according to claim 1, wherein the wastewater is inserted into an outer wall. Access ports (227) are provided on the side walls of the first reaction chamber (220), the partition chamber (221) and the second reaction chamber (222), respectively, and a ruthenium group is provided in each reaction branch tube (232). The wastewater treatment system for a pyridine polycyclic compound according to claim 1, wherein a catalyst is arranged. A horizontal filter (10) is provided in the waste liquid storage tank (1), and a waste liquid storage tank (1) is provided.
A sludge discharge port (11) is provided at the center of the bottom end of 1), the bottom end of the wastewater storage tank (1) has an arcuate structure, and the bottom end is in the circumferential direction of the sludge discharge port (11). The wastewater treatment system for a pyridine polycyclic compound according to claim 1, wherein a plurality of sludge guide grooves (110) distributed along the sludge guide grooves (110) are provided. The height of the vertical limiting groove (402) is equal to the distance between the uppermost and lowermost engaging circular holes (4200), and the height of the arcuate buckle plate (422) is that of the vertical limiting groove (402). wastewater treatment system of pyridine a heterocyclic compound according to claim 1, higher than that, the sealing adhesive layer (4222) is provided on the inner wall of the arc-shaped buckle plate (422), it is characterized. S1: When the wastewater flows into the wastewater storage tank (1), the solid impurities in the wastewater are filtered by the horizontal filter (10) and then temporarily stored in the wastewater storage tank (1).
S2: The heating element (24) is started, and the fixed bed reactor (2) is heated by the heating element (24). At this time, heat passes through the bottom end of each spiral heat insulating heating chamber (2323) and is inside the fixed bed reactor (2). And spreads upward in a spiral along the spiral heat insulating heating chamber (2323).
The spiral heat insulating jacket 2 (2322) is arranged away from the reaction branch tube (232), and heat is indirectly transferred to the reaction branch tube (232) via the spiral heat insulating jacket 2 (2322) to enter the inside thereof. It can be heated, and the heat directly contacts the side wall of the reaction branch tube (232) and the reaction branch tube (
A step to avoid causing local charring of the catalyst in 232) and affecting its catalytic performance.
S3: When the temperature of the fixed bed reactor (2) within reached 350 ℃, 30~60min stabilize, waste pumping start the pump (21), waste liquid pumped waste water effluent storage using a pump (21) through the tank (1) from two wastewater inlet (223), at first the <br/> and pumped into the interior of the upper end of the reaction chamber (220) and a second reaction chamber (222), respectively, fixed bed The pumping amount is controlled by the flow meter (20) so that the temperature stability of the catalyst bed layer can be ensured, and at this time, the water flow varies from the insertion port (2260) at the bottom end of the uniformized disk (226). The wastewater is uniformly dispersed in the reaction branch tube (232), the wastewater reacts with the ruthenium-based catalyst in the reaction branch tube (232), and the water after the reduction reaction enters the heat exchanger (3) to exchange heat and heat. After cooling, it enters the filler absorption tower (4), and the water in the filler absorption tower (4) absorbs the reacted ammonia and becomes ammonia water, which is collected, and the gas containing methane and carbon dioxide enters the gasometer and is stored. The step in which the treated water enters and is stored in the primary water storage tank (5),
S4: Whether the heat in the heat exchanger (3) can be recovered and re-injected into the fixed bed reactor (2), and the water quality after treatment meets the standard by using the water quality detector (52). The invention according to any one of claims 1 to 5, comprising: The process of treating waste water containing pyridine polycyclic compounds using the system of.

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