CN111675423A - Treatment method and system for nicotinic acid medical intermediate wastewater - Google Patents
Treatment method and system for nicotinic acid medical intermediate wastewater Download PDFInfo
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Abstract
The invention discloses a method and a system for treating nicotinic acid medical intermediate wastewater. The method comprises the following steps: (1) carrying out primary oxidation reaction treatment on a mixture consisting of wastewater and an oxidant under the condition of not using a catalyst to obtain a first product; (2) and carrying out secondary oxidation reaction treatment on the first product under the condition of using a catalyst to obtain a second product. The system comprises a wet oxidation reaction system, a spraying system, an evaporation desalting system and an aerobic biochemical reaction system. In the invention, in the mixture in the first-stage reactor, the components which are easily oxidized in the wastewater firstly undergo oxidation reaction, and then enter the second-stage reactor for catalytic reaction, so that the use efficiency and COD conversion rate of the catalyst can be obviously improved. And after the primary oxidation reaction, the temperature of the obtained first product is increased compared with that of the mixture, so that the rate of the secondary oxidation reaction can be increased.
Description
Technical Field
The invention relates to the technical field of wet oxidation water treatment, in particular to a method and a system for treating nicotinic acid medical intermediate wastewater.
Background
Water pollution is a main problem which needs to be solved at present in China, and industrial organic wastewater produced in factories is one of main sources of water pollution. Especially, the industrial wastewater generated in the production process of the medical intermediate has complex components, large biotoxicity, high COD, high salinity and high chroma, and is very difficult to treat. The main treatment methods at present are: the biological method, the extraction method, the incineration method, the Fenton method and the ozone method have the problems of high investment cost, secondary pollution, low treatment efficiency and the like.
The production process of the nicotinic acid medical intermediate has various raw materials and complex process, so the discharged wastewater has complex components, high COD (chemical oxygen demand), contains a large amount of organic matters, contains various cyclic compounds such as pyridine and the like, has poor biodegradability, has high salinity of 5-12 percent, has dark color, cannot be directly or diluted for biochemical oxidation treatment, and is one of the wastewater with great treatment difficulty in the current industrial organic wastewater. At present, the production factory adopts a method of direct evaporation and biochemical oxidation treatment of evaporation condensate. However, this method has serious problems: the viscosity of the waste water is high, the boiling point of the MVR evaporator is greatly increased, and the evaporation capacity is seriously reduced; the waste water blocks the heat exchange tube for multi-effect evaporation, and the discharging is difficult; inorganic salt in the wastewater is difficult to crystallize, a large amount of mixed hazardous waste substances of sticky organic matters and inorganic salt are formed, and the treatment cost is high; the evaporation condensate has high COD and poor biodegradability.
Disclosure of Invention
The invention aims to provide a wet oxidation reaction unit for water treatment and a wet oxidation reaction system for water treatment, so as to solve the technical problems of high investment cost, secondary pollution generation, low treatment efficiency and the like in wastewater treatment in the prior art.
The second purpose of the invention is to provide a method and a system for treating nicotinic acid medical intermediate wastewater, so as to solve the technical problems of poor evaporation crystallization effect, high condensate COD and poor biodegradability existing in the prior art in the treatment of nicotinic acid medical intermediates.
In order to achieve the above object, according to one aspect of the present invention, there are provided a wet oxidation reaction unit for water treatment and a wet oxidation reaction system for water treatment. The technical scheme is as follows:
a wet oxidation reaction unit for water treatment comprising
The primary reactor is used for carrying out primary oxidation reaction on a mixture consisting of waste water and an oxidant;
the secondary reactor is used for carrying out secondary oxidation reaction on the first product output by the primary reactor;
wherein, a catalyst packing layer is only arranged in the secondary reactor.
Further, a first mixer is arranged in the primary reactor; the first mixer is an atomizing distributor connected with the mixture inlet.
Furthermore, a circulating pump is arranged outside the primary reactor, and part of liquid at the upper part in the primary reactor is used as circulating liquid to flow into the primary reactor again from the lower part of the primary reactor.
Further, a partition plate is arranged at the upper part in the primary reactor, and the partition plate is connected with the inner wall of the primary reactor so as to form a buffer tank for accommodating the circulating liquid and preventing gas from flowing out through the circulating pump; and a circulating liquid outlet connected with the circulating pump is formed in the side wall of the primary reactor at the lower part of the buffer tank.
Further, the partition plate comprises a rectangular plate arranged along the axial direction of the primary reactor and an arc-shaped plate connecting the bottom of the rectangular plate and the inner wall of the primary reactor.
Further, the distance between the top of the rectangular plate and the top of the primary reactor is 10-20 cm.
Further, a liquid distributor is arranged in the primary reactor; the liquid distributor is connected with the circulating liquid inlet.
Furthermore, an oxidant inlet is also arranged on the secondary reactor.
Further, a second mixer is arranged in the secondary reactor; the second mixer is an atomizing distributor connected to the oxidant inlet.
Further, the first product inlet is arranged on the secondary reactor shell between the second mixer and the catalyst filler layer.
The wet oxidation reaction system for water treatment comprises a wet oxidation reaction unit and a heat exchange unit;
the wet oxidation reaction unit comprises a primary reactor and a secondary reactor, wherein the primary reactor is used for enabling a mixture consisting of wastewater and an oxidant to perform primary oxidation reaction and outputting a first product, and the secondary reactor is used for enabling the first product to perform secondary oxidation reaction and outputting a second product; wherein, a catalyst packing layer is only arranged in the secondary reactor;
and the heat exchange unit is used for heating and regulating the mixture and cooling and regulating the second product.
The heat exchange unit comprises a first heat exchanger, a second heat exchanger and a third heat exchanger which are sequentially connected and used for heating and adjusting the mixture, wherein the heat medium of the first heat exchanger and the heat medium of the second heat exchanger are the second product, and the heat medium of the third heat exchanger is heat conduction oil; the heat exchange unit also comprises a fourth heat exchanger for further cooling and adjusting a second product which sequentially passes through the second heat exchanger and the first heat exchanger, and a cooling medium of the fourth heat exchanger is cooling water.
Further, the device also comprises a pretreatment unit for pretreating the wastewater, wherein the pretreatment unit at least comprises a pH adjusting tank and a filtering device.
Furthermore, the filter device is a filter with the interception rate of particulate matters with the granularity of more than or equal to 30 mu m of more than or equal to 97 percent; a raw water pump is arranged in front of the filtering device; a plunger pump is arranged behind the filter device.
Further, the system also comprises an air supplementing unit used for supplementing the oxidant to the wastewater and the first product, wherein the air supplementing unit comprises an air compressor.
Further, still include the pressure regulating unit that adjusts the pressure of the second result after the cooling regulation, pressure regulating unit is including locating the pressure regulating valve on the pipeline.
Further, the device also comprises a post-treatment unit for post-treating the second product after temperature reduction adjustment, wherein the post-treatment unit at least comprises a gas-liquid separation device; gas obtained by the separation of the gas-liquid separation device enters a spraying system; the liquid obtained by the separation of the gas-liquid separation device enters an evaporation desalting system and an aerobic biochemical reaction system.
Further, the spraying system comprises an acid washing tower and a caustic washing tower which are connected in sequence.
Further, the evaporation desalination system comprises an MVR evaporator, a single-effect evaporator and a crystallizer which are sequentially connected.
Further, an intermediate tank is arranged between the gas-liquid separation device and the evaporation desalination system.
In order to achieve the aim, the invention also provides a method and a system for treating the wastewater of the nicotinic acid medical intermediate. The technical scheme is as follows:
the treatment method of the nicotinic acid medical intermediate wastewater comprises the following steps:
(1) carrying out primary oxidation reaction treatment on a mixture consisting of wastewater and an oxidant under the condition of not using a catalyst to obtain a first product;
(2) and carrying out secondary oxidation reaction treatment on the first product under the condition of using a catalyst to obtain a second product.
Further, the method comprises the steps of pretreating the wastewater before primary oxidation reaction treatment, wherein the pretreatment comprises pH adjustment, filtration and oxidant injection; the method also comprises the step of heating and adjusting the mixture after pretreatment; the method also comprises the step of cooling and adjusting the second product; and further performing gas-liquid separation treatment on the second product after temperature reduction adjustment.
Further, the filtering is to enable the wastewater after pH adjustment to pass through a filter with the interception rate of particulate matters with the particle size of more than or equal to 30 mu m of more than or equal to 97 percent; when the oxidant is air, the flow of the wastewater in the mixture output by the wastewater pretreatment is 3-9 m3The air flow is 200-650 Nm3H; the pressure of the mixture is 5-10 MPa; the temperature of the mixture after temperature rise adjustment is 220-230 ℃; the temperature of the second product after temperature reduction adjustment is 40-90 ℃; and (3) washing the gas obtained by gas-liquid separation treatment, discharging, and carrying out evaporative crystallization desalination treatment and aerobic biochemical reaction treatment on the liquid obtained by gas-liquid separation treatment.
Further, the primary oxidation reaction treatment is carried out in a primary reactor, the mixture enters from the lower part of the primary reactor, and a first product obtained by the reaction flows out from the upper part of the primary reactor; and a circulating pump for enabling part of liquid at the upper part in the primary reactor to flow into the primary reactor from the lower part of the primary reactor again as circulating liquid is arranged outside the primary reactor.
Further, a first mixer is arranged in the primary reactor; and a buffer tank which is used for accommodating the circulating liquid and preventing gas from flowing out through a circulating pump is arranged in the primary reactor.
Further, in the primary reactor, the reaction pressure is 6-7.5 MPa, and the space velocity of the mixture is 0.5-1.0 h-1The liquid circulation rate is 100-400%.
And further, the secondary oxidation reaction treatment is carried out in a secondary reactor, a catalyst filler layer is arranged in the secondary reactor, the first product enters from the lower part of the secondary reactor and then passes through the catalyst filler layer, and the second product obtained by the reaction flows out from the upper part of the secondary reactor.
Further, a second mixer is also arranged in the secondary reactor; and supplementing an oxidant into the secondary reactor.
Further, in the secondary reactor, the reaction pressure is 6-7 MPa, and the space velocity of the first product is 0.5-1.0 h-1When the oxidant is air, the air flow is 100-200 Nm3The filling amount of the catalyst in the catalyst filling layer is 0.5-1.5 times of the volume flow of the first product per hour; the catalyst is a metal-supported catalyst.
The system for treating the nicotinic acid medical intermediate wastewater comprises a wet oxidation reaction system, a spraying system, an evaporation desalting system and an aerobic biochemical reaction system; the wet oxidation reaction system comprises a wet oxidation reaction unit, wherein the wet oxidation reaction unit comprises a primary reactor and a secondary reactor, the primary reactor is used for enabling a mixture consisting of waste water and an oxidant to perform primary oxidation reaction and outputting a first product, and the secondary reactor is used for enabling the first product to perform secondary oxidation reaction and outputting a second product; wherein, a catalyst packing layer is only arranged in the secondary reactor.
In the invention, in the mixture in the first-stage reactor, the easily oxidized components in the wastewater firstly undergo oxidation reaction and then enter the second-stage reactor for catalytic reaction, so that the use efficiency and COD conversion rate of the catalyst can be obviously improved. And after the primary oxidation reaction, the temperature of the obtained first product is increased compared with that of the mixture, so that the rate of the secondary oxidation reaction can be increased. By verification, the COD of the second product water obtained by the treatment of the system and the method disclosed by the invention is removed by more than 80% compared with the COD in the wastewater, which shows that the COD and the viscosity of the second product obtained after the two-stage oxidation reaction are obviously reduced, the heat exchange tube of an evaporator is not easily blocked by the second product water, the salt can be removed to the maximum extent through the evaporation and crystallization operation, and the subsequent biodegradability is improved. The circulating pump is arranged outside the primary reactor, so that the liquid in the primary reactor can be forcibly circulated, not only is gas-liquid mixing and mass transfer enhanced, but also the primary oxidation reaction time can be obviously prolonged, and the oxidation effect is improved. The system and the method are particularly suitable for treating the medical intermediate wastewater, particularly the nicotinic acid medical intermediate wastewater, and have the advantages of low energy consumption, low investment cost, no secondary pollution and high treatment efficiency.
The invention is further described with reference to the following figures and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
FIG. 1 is a schematic view of a wet oxidation reaction system for water treatment and a system for treating waste water of nicotinic acid pharmaceutical intermediates according to the present invention.
FIG. 2 is a schematic diagram of a primary reactor in a wet oxidation reaction unit according to the present invention.
Fig. 3 is a sectional view taken along line a-a in fig. 2.
FIG. 4 is a schematic diagram of a secondary reactor in a wet oxidation reaction unit of the present invention.
The relevant references in the above figures are:
100-wet oxidation reaction system, 101-liquid outlet, 102-lifting lug, 110-first-stage reactor, 111-circulating pump, 112-mixture inlet, 113-first product outlet, 114-first mixer, 115-liquid distributor, 116-circulating liquid inlet, 117-circulating liquid outlet, 118-clapboard, 210-second-stage reactor, 211-first product inlet, 212-second product outlet, 213-catalyst packing layer, 214-oxidant inlet, 215-second mixer, 216-supporting plate, 217-pressing plate, 310-first heat exchanger, 320-second heat exchanger, 330-third heat exchanger, 340-fourth heat exchanger, 410-pH regulating tank, 420-raw water pump, 430-filtering device, 440-plunger pump, 510-air compressor, 520-pressure regulating valve, 530-gas-liquid separation device, 540-intermediate tank, 600-spraying system, 610-acid cleaning tower, 620-alkaline cleaning tower, 700-evaporation desalting system, 710-MVR evaporator, 720-single-effect evaporator, 730-crystallizer and 800-aerobic biochemical reaction system.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions.
As shown in fig. 1, a wet oxidation reaction system for water treatment includes: the device comprises a pretreatment unit, a wet oxidation reaction unit, a heat exchange unit, a gas supplementing unit, a pressure adjusting unit and a post-treatment unit. Wherein the content of the first and second substances,
the pretreatment unit comprises a pH adjusting tank 410, a raw water pump 420, a filtering device 430 and a plunger pump 440 which are connected in sequence.
The wet oxidation reaction unit includes a primary reactor 110 for performing a primary oxidation reaction on a mixture of wastewater and an oxidizer and outputting a first product, and a secondary reactor 210 for performing a secondary oxidation reaction on the first product and outputting a second product.
The heat exchange unit is used for heating and regulating the mixture and cooling and regulating the second product; firstly, the heat exchange unit comprises a first heat exchanger 310, a second heat exchanger 320 and a third heat exchanger 330 which are connected in sequence and used for heating and regulating a mixture, wherein heat media of the first heat exchanger 310 and the second heat exchanger 320 are the second product, and heat media of the third heat exchanger 330 are heat conduction oil; secondly, the heat exchange unit further comprises a fourth heat exchanger 340 for further cooling and adjusting a second product passing through the second heat exchanger 320 and the first heat exchanger 310 in sequence, and a cooling medium of the fourth heat exchanger 340 is cooling water. When the reactor is started, the mixture is preheated through the third heat exchanger 330, and enters the first-stage reactor 110 to perform exothermic reaction after the mixture reaches the reaction condition temperature; in the reaction stage, the third heat exchanger 330 stops heating, and at this time, the heat of the second product is utilized to realize efficient heat exchange between the mixture and the second product in the first heat exchanger 310 and the second heat exchanger 320; the remaining heat of the second product after heat exchange with the mixture is recovered in fourth heat exchanger 340.
The air supply unit is used for supplying an oxidant to the wastewater and the first product; the oxidant is air, the air supply unit comprises an air compressor 510, a part of the compressed air compressed by the air compressor 510 is mixed with the wastewater and then enters the heat exchange unit, and a part of the compressed air enters the secondary reactor 210.
The pressure adjusting unit is used for adjusting the pressure of the second product after temperature reduction adjustment; the pressure regulating unit includes a pressure regulating valve 520 provided on the pipeline.
The post-processing unit is used for performing post-processing on the second product after temperature reduction adjustment; the post-treatment unit includes a gas-liquid separation device 530; the gas obtained by the separation of the gas-liquid separation device 530 enters a spraying system 600; the liquid separated by the gas-liquid separation device 530 enters the evaporation desalination system 700 and the aerobic biochemical reaction system 800. The spray system 600 includes an acid wash tower 610 and a caustic wash tower 620 connected in series. The evaporation desalination system 700 comprises an MVR evaporator 710, a single-effect evaporator 720 and a crystallizer 730 which are connected in sequence. An intermediate tank 540 is provided between the gas-liquid separation device 530 and the evaporation and desalination system 700.
As shown in fig. 2, a first mixer 114 is disposed in the primary reactor 110, and the first mixer 114 is an atomizing distributor connected to the mixture inlet 112. The first-stage reactor 110 is externally provided with a circulating pump 111 which makes part of the liquid in the upper part of the first-stage reactor 110 as circulating liquid flow into the first-stage reactor 110 again from the lower part of the first-stage reactor 110. A partition plate 118 is arranged at the upper part in the primary reactor 110, and the partition plate 118 is connected with the inner wall of the primary reactor 110 so as to form a buffer tank for accommodating the circulating liquid and preventing gas from flowing out through the circulating pump 111; a circulating liquid outlet 117 connected with the circulating pump 111 is arranged on the side wall of the primary reactor 110 at the lower part of the buffer tank. As shown in fig. 2 to 3, the partition 118 includes a rectangular plate disposed along the axial direction of the primary reactor 110 and an arc-shaped plate connecting the bottom of the rectangular plate and the inner wall of the primary reactor 110, and the distance between the top of the rectangular plate and the top of the primary reactor 110 is 15 cm. The first-stage reactor 110 is provided with a liquid distributor 115 connected to a circulating liquid inlet 116.
As shown in fig. 4, a first product inlet 211, an oxidant inlet 214, a second mixer 215 and a catalyst packing layer 213 are provided in the secondary reactor 210; the second mixer 215 is an atomizing distributor connected to the oxidant inlet 214; the first product inlet 211 is located on the shell of the secondary reactor 210 between the second mixer 215 and the layer of catalyst packing 213. The catalyst packing layer 213 has a lower support plate 216, an upper press plate 217, and a catalyst located between the support plate 216 and the press plate 217.
Lifting lugs 102 are arranged on the shells of the primary reactor 110 and the secondary reactor 210, and liquid discharge ports 101 are arranged at the bottoms of the primary reactor and the secondary reactor.
In the first-stage reactor 110, the easily reactive substances in the high-temperature wastewater are oxidized by the oxidant and converted into a first product with lower concentration of COD. In the secondary reactor 210, the organic matter difficult to be oxidized in the first product is oxidized and decomposed into small molecular carboxylic acid and CO by the oxidant under the action of the catalyst2And H2And O, further reducing COD in the wastewater, and converting organic nitrogen into nitrogen by catalytic oxidation, thereby realizing degradation of organic matters in the wastewater. Chemical Oxygen demand (cod) is the amount of reducing substances to be oxidized in a water sample measured by a chemical method, the reducing substances are generally organic substances, and the oxidizing agent used for measuring the chemical Oxygen demand is generally potassium permanganate or potassium dichromate.
An example of the application of the wet oxidation reaction system 100 is the treatment of waste water containing nicotinic acid pharmaceutical intermediates. The COD of the nicotinic acid medical intermediate wastewater is 35000mg/L, and the treatment process comprises the following steps:
(1) pretreatment: the pH of the wastewater is adjusted to 6 in the pH adjusting tank 410 with sodium hydroxide, and then pressurized to 0.3MPa (gauge pressure) by the raw water pump 420, filtered by the filter 430, and pressurized to 7.0MPa by the plunger pump 440. The filtering device 430 is a filter with the interception rate of particulate matters with the granularity of more than or equal to 30 mu m of more than or equal to 97 percent. Air as an oxidant is pressurized to 7.0MPa by the air compressor 510 and then mixed with wastewater conveyed by the plunger pump 440 in the pipeline mixer to obtain a mixture, and the mixture is conveyed to the heat exchange unit. The flow of wastewater in the mixture was 5m3Flow rate of air 400 Nm/h3/h。
(2) Heat exchange: the mixture sequentially passes through the first heat exchanger 310, the second heat exchanger 320 and the third heat exchanger 330, the temperature rises to 230 ℃, and then enters the first-stage reactor 110 from the mixture inlet 112 at the bottom of the first-stage reactor 110 to start the oxidation reaction.
(3) Wet oxidation reaction
A. The mixture is subjected to primary oxidation reaction in a primary reactor 110; the mixture enters from the lower part of a primary reactor 110, the reaction pressure in the primary reactor 110 is 6.5MPa, and the space velocity of the mixture is 0.8h-1The flow rate of the circulation pump 111 is 15m3The liquid circulation rate is 300 percent. The mixture reaches the first product outlet 113 at the top of the first stage reactor 110 and exits the reactor to produce a first product that rises in temperature to about 245 ℃.
B. The first product and the make-up air undergo a secondary oxidation reaction in the secondary reactor 210; the first product and air enter from a first product inlet 211 at the bottom of the secondary reactor 210 with an air flow of 150Nm3H is used as the reference value. In the secondary reactor 210, the reaction pressure was 6.3MPa, and the space velocity of the first product was 0.8h-1. The catalyst in the catalyst filler layer 213 is a metal-loaded catalyst, the active component of the catalyst is a Ru/Pt catalyst, the carrier is activated carbon, and the loading amount of the catalyst is 0.8 times of the volume flow of the first product per hour. The first product reaches the top of the secondary reactor 210 and exits the reactor at a second product outlet 212, resulting in a second product that has a temperature that rises to about 262 ℃.
(4) Heat exchange: the second product is cooled to 45 ℃ after passing through the second heat exchanger 320, the first heat exchanger 310 and the fourth heat exchanger 340 in sequence. The second product after temperature reduction enters a gas-liquid separation device 530 after being decompressed by a pressure regulating valve 520.
(5) Gas-liquid separation: the liquid obtained by gas-liquid separation comes out from the bottom of the gas-liquid separation device 530, the COD thereof is 5320mg/L, and the removal rate of the COD compared with the waste water is 84.8%. The liquid is sent to an evaporation desalination system 700 and an aerobic biochemical reaction system 800; the gas obtained by gas-liquid separation is sent to the spraying system 600 from the top of the gas-liquid separation device 530.
In the evaporation desalination system 700, the liquid is evaporated by the MVR evaporator 710 and the single-effect evaporator 720 and then crystallized in the crystallizer 730, so as to recover inorganic salts. And (3) sending the evaporated liquid from the evaporation desalting system 700 to an aerobic biochemical reaction system 800 for further aerobic biochemical reaction treatment, wherein the retention time of the evaporated liquid is 12 hours, the evaporated liquid is finally discharged after reaching the standard, and the COD (chemical oxygen demand) of the discharged water is lower than 40 mg/L. The "aerobic biochemical reaction treatment" refers to a treatment method in which aerobic microorganisms (including facultative microorganisms) are used to carry out biological metabolism in the presence of oxygen to degrade organic matters, so that the organic matters are stabilized and made harmless.
In the spray system 600, the gas is sprayed and washed by the acid washing tower 610 and the alkali washing tower 620 in sequence and then discharged to the atmosphere. Wherein, the acid cleaning tower 610 adopts dilute sulphuric acid as an absorbent, and the alkaline cleaning tower 620 adopts sodium hydroxide as an absorbent.
Therefore, the system for treating the waste water of the nicotinic acid medical intermediate is shown in figure 1 and comprises the following components: wet oxidation reaction system 100, spraying system 600, evaporation desalination system 700 and aerobic biochemical reaction system 800. The wet oxidation reaction system 100 includes the above pretreatment unit, wet oxidation reaction unit, heat exchange unit, gas supply unit, pressure regulation unit, and post-treatment unit.
The "wet oxidation" is a method of subjecting an organic substance suspended or dissolved in a liquid to a high-temperature high-pressure oxidation treatment in the presence of liquid-phase water.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (10)
1. The treatment method of the nicotinic acid medical intermediate wastewater comprises the following steps:
(1) carrying out primary oxidation reaction treatment on a mixture consisting of wastewater and an oxidant under the condition of not using a catalyst to obtain a first product;
(2) and carrying out secondary oxidation reaction treatment on the first product under the condition of using a catalyst to obtain a second product.
2. The method for treating nicotinic acid medical intermediate wastewater as claimed in claim 1, wherein the method comprises the following steps: the method also comprises the steps of pretreating the wastewater before the primary oxidation reaction treatment, wherein the pretreatment comprises pH regulation, filtration and oxidant injection; the method also comprises the step of heating and adjusting the mixture after pretreatment; the method also comprises the step of cooling and adjusting the second product; and further performing gas-liquid separation treatment on the second product after temperature reduction adjustment.
3. The method for treating nicotinic acid medical intermediate wastewater as claimed in claim 2, wherein the method comprises the following steps: the filtration is that the wastewater after pH adjustment passes through a filter with the interception rate of particulate matters with the granularity of more than or equal to 30 mu m of more than or equal to 97 percent; when the oxidant is air, the flow of the wastewater in the mixture output by the wastewater pretreatment is 3-9 m3The air flow is 200-650 Nm3H; the pressure of the mixture is 5-10 MPa; the temperature of the mixture after temperature rise adjustment is 220-230 ℃; the temperature of the second product after temperature reduction adjustment is 40-90 ℃; washing the gas obtained by gas-liquid separation treatment and then discharging; and carrying out evaporative crystallization desalting treatment and aerobic biochemical reaction treatment on the liquid obtained by the gas-liquid separation treatment.
4. The method for treating nicotinic acid medical intermediate wastewater as claimed in claim 1, wherein the method comprises the following steps: the primary oxidation reaction treatment is carried out in a primary reactor (110), the mixture enters from the lower part of the primary reactor (110), and a first product obtained by the reaction flows out from the upper part of the primary reactor (110); and a circulating pump (111) which is used for enabling part of liquid at the upper part in the primary reactor (110) to flow into the primary reactor (110) from the lower part of the primary reactor (110) again as circulating liquid is arranged outside the primary reactor (110).
5. The method for treating nicotinic acid medical intermediate wastewater as claimed in claim 4, wherein the method comprises the following steps: a first mixer (114) is arranged in the primary reactor (110); a buffer tank which contains the circulating liquid and prevents gas from flowing out through a circulating pump (111) is arranged in the primary reactor (110).
6. The method for treating nicotinic acid medical intermediate wastewater as claimed in claim 5, wherein the method comprises the following steps: in the primary reactor (110), the reaction pressure is 6-7.5 MPa, and the space velocity of the mixture is 0.5-1.0 h-1The liquid circulation rate is 100-400%.
7. The method for treating nicotinic acid medical intermediate wastewater as claimed in claim 1, wherein the method comprises the following steps: the secondary oxidation reaction treatment is carried out in a secondary reactor (210), a catalyst filler layer (213) is arranged in the secondary reactor (210), the first product enters from the lower part of the secondary reactor (210) and then passes through the catalyst filler layer (213), and the second product obtained by the reaction flows out from the upper part of the secondary reactor (210).
8. The method for treating nicotinic acid medical intermediate wastewater as claimed in claim 7, wherein the method comprises the following steps: a second mixer (215) is also arranged in the secondary reactor (210); further comprising replenishing an oxidant into the secondary reactor (210).
9. The method for treating nicotinic acid medical intermediate wastewater as claimed in claim 8, wherein the method comprises the following steps: in the secondary reactor (210), the reaction pressure is 6-7 MPa, and the space velocity of the first product is 0.5-1.0 h-1When the oxidant is air, the air flow is 100-200 Nm3The filling amount of the catalyst in the catalyst filling layer (213) is 0.5-1.5 times of the volume flow of the first product per hour; the catalyst is a metal-supported catalyst.
10. Nicotinic acid class medical intermediate waste water's processing system, its characterized in that: comprises a wet oxidation reaction system (100), a spraying system (600), an evaporation desalination system (700) and an aerobic biochemical reaction system (800); wherein the wet oxidation reaction system (100) comprises a wet oxidation reaction unit, the wet oxidation reaction unit comprises a primary reactor (110) for carrying out primary oxidation reaction on a mixture consisting of waste water and an oxidant and outputting a first product, and a secondary reactor (210) for carrying out secondary oxidation reaction on the first product and outputting a second product; wherein, a catalyst filling layer (213) is arranged only in the secondary reactor (210).
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