CN112679006A - Treatment device and treatment method for acrylonitrile-containing wastewater - Google Patents
Treatment device and treatment method for acrylonitrile-containing wastewater Download PDFInfo
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- CN112679006A CN112679006A CN201910989182.2A CN201910989182A CN112679006A CN 112679006 A CN112679006 A CN 112679006A CN 201910989182 A CN201910989182 A CN 201910989182A CN 112679006 A CN112679006 A CN 112679006A
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Abstract
The invention relates to the field of sewage treatment, and discloses a treatment device and a treatment method for acrylonitrile-containing wastewater, wherein the treatment device comprises: the device comprises a pretreatment unit and a vacuum ultraviolet light catalytic reaction unit, wherein the pretreatment unit is used for filtering acrylonitrile-containing wastewater to be treated to obtain filtrate; the vacuum ultraviolet light catalytic reaction unit is communicated with the pretreatment unit and is used for carrying out vacuum ultraviolet light catalytic reaction on the filtrate to obtain reacted effluent; the vacuum ultraviolet light catalytic reaction unit can irradiate vacuum ultraviolet waves smaller than or equal to 200nm and short-wavelength ultraviolet waves larger than 200nm at the same time. The device and the method for treating the acrylonitrile wastewater can realize the efficient removal of the highly toxic acrylonitrile.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a treatment device and a treatment method for acrylonitrile-containing wastewater.
Background
Acrylonitrile is an important organic chemical raw material, is mainly applied to the fields of synthetic fibers, synthetic plastics and synthetic rubber, and polymers and derivatives thereof are also widely applied to the industries of daily necessities and building materials. The currently common acrylonitrile production process is a propylene ammoxidation method, and acrylonitrile is prepared by taking propylene, ammonia and oxygen in air as raw materials.
Acrylonitrile is a highly toxic substance, and a trace amount of soluble acrylonitrile in a water body causes potential triple-cause toxicity. The acrylonitrile-containing wastewater discharged in the acrylonitrile production process has a remarkable inhibiting effect on microorganisms, and the untreated acrylonitrile wastewater enters a sewage plant to cause serious impact on a biochemical treatment unit. Therefore, the acrylonitrile-containing wastewater needs to be pretreated to reduce the concentration of acrylonitrile, reduce the biotoxicity of the wastewater and improve the biodegradability of the wastewater.
The common pretreatment process of the acrylonitrile-containing wastewater comprises coagulation, adsorption, electrochemistry, advanced oxidation, biochemistry and the combination of the processes, but the existing process has low treatment efficiency and is difficult to stably and efficiently remove acrylonitrile in the wastewater, so that the effluent causes serious impact on a rear-end biochemical system.
Therefore, the development of a novel high-efficiency acrylonitrile-containing wastewater treatment process and the exploration of a method for improving the removal rate and the biodegradability of acrylonitrile in wastewater have important practical significance and application value for the stable operation of a sewage plant.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a treatment device and a treatment method for acrylonitrile-containing wastewater, which can realize the efficient removal of acrylonitrile in the wastewater.
The inventor of the invention finds that the high-efficiency vacuum ultraviolet catalytic oxidation technology has good treatment effect on the waste water containing the acrylonitrile which is difficult to treat and has high toxicity. The vacuum ultraviolet light can simultaneously irradiate vacuum ultraviolet waves with the wavelength less than or equal to 200nm and short-wavelength ultraviolet waves with the wavelength more than 200 nm. Preferably, the catalyst is selectively used for the catalytic reaction of the ultraviolet light while the vacuum ultraviolet light is irradiated, on one hand, the vacuum ultraviolet wave band (less than or equal to 200nm) can realize that a large amount of hydroxyl free radicals OH are generated by irradiating water, and the using amount of the catalyst can be greatly reduced; on the other hand, the coupling of the short wavelength ultraviolet band (more than 200nm) and different catalysts can form a homogeneous photocatalytic reaction system and/or a heterogeneous photocatalytic reaction system, and the combined action of the two can realize the high-efficiency removal of the highly toxic acrylonitrile in the wastewater, thus being a green advanced oxidation advanced treatment process.
According to a preferred embodiment of the invention, the high-toxicity acrylonitrile in the wastewater can be removed more efficiently by adopting a high-efficiency vacuum ultraviolet light catalytic reaction process and combining a semiconductor photocatalyst based on a molecular sieve as a porous carrier and/or combining an active metal and/or non-metal heterogeneous catalyst based on the molecular sieve as the porous carrier.
In order to achieve the above object, an aspect of the present invention provides an apparatus for treating acrylonitrile-containing wastewater, wherein the apparatus comprises: the device comprises a pretreatment unit and a vacuum ultraviolet light catalytic reaction unit;
the pretreatment unit is used for filtering acrylonitrile-containing wastewater to be treated to obtain filtrate;
the vacuum ultraviolet light catalytic reaction unit is communicated with the pretreatment unit and is used for carrying out vacuum ultraviolet light catalytic reaction on the filtrate to obtain reacted effluent; the vacuum ultraviolet light catalytic reaction unit can irradiate vacuum ultraviolet waves smaller than or equal to 200nm and short-wavelength ultraviolet waves larger than 200nm at the same time.
Preferably, the wavelength of the vacuum ultraviolet wave is 185nm, and the wavelength of the short wavelength ultraviolet wave is 254 nm.
The second aspect of the present invention provides a method for treating acrylonitrile-containing wastewater, wherein the method comprises:
a pretreatment step: filtering the acrylonitrile-containing wastewater to be treated to obtain filtrate;
vacuum ultraviolet light catalytic reaction: carrying out vacuum ultraviolet light catalytic reaction on the filtrate under the irradiation of vacuum ultraviolet light to obtain reacted effluent; the vacuum ultraviolet light has both vacuum ultraviolet waves less than or equal to 200nm and short wavelength ultraviolet waves greater than 200 nm.
Preferably, the wavelength of the vacuum ultraviolet wave is 185nm, and the wavelength of the short wavelength ultraviolet wave is 254 nm.
The third aspect of the present invention provides a method for treating acrylonitrile-containing wastewater, wherein the method is performed in the treatment apparatus of the present invention, and the method comprises:
a pretreatment step: the method comprises the following steps of (1) filtering acrylonitrile-containing wastewater to be treated in a pretreatment unit to obtain filtrate;
vacuum ultraviolet light catalytic reaction: the filtrate enters a vacuum ultraviolet light catalytic reaction unit, and is subjected to vacuum ultraviolet light catalytic reaction under the irradiation of vacuum ultraviolet light to obtain reacted effluent; the vacuum ultraviolet light has both vacuum ultraviolet waves less than or equal to 200nm and short wavelength ultraviolet waves greater than 200 nm.
Preferably, the wavelength of the vacuum ultraviolet wave is 185nm, and the wavelength of the short wavelength ultraviolet wave is 254 nm.
The technical scheme of the invention has the following advantages:
the treatment device and the treatment method for acrylonitrile-containing wastewater can realize the efficient removal of acrylonitrile in the wastewater, and have the characteristics of short process flow, small occupied area, easy operation and the like.
The acrylonitrile-containing wastewater treatment device and the acrylonitrile-containing wastewater treatment method fully utilize the dual-waveband characteristics of the vacuum ultraviolet light source, and can be combined with a homogeneous catalyst and a heterogeneous catalyst to improve the yield of free radicals under the optimal condition.
The treatment device and the treatment method for the acrylonitrile-containing wastewater can selectively realize homogeneous catalysis and/or heterogeneous catalysis reaction under vacuum ultraviolet irradiation, and have the characteristics of easily controlled reaction conditions, high treatment efficiency, energy conservation and the like.
According to a specific embodiment of the invention, the method for treating the acrylonitrile-containing wastewater uses the molecular sieve loaded with the semiconductor material and/or the molecular sieve loaded with the metal and/or the nonmetal active component as the heterogeneous catalyst, has good adsorption characteristics and optical characteristics, and can remove the high-toxicity acrylonitrile in the wastewater more efficiently under the irradiation of the two-waveband vacuum ultraviolet light.
Drawings
FIG. 1 is a view for explaining a preferred embodiment of the method for treating acrylonitrile-containing wastewater according to the present invention.
FIG. 2 is a view for explaining a method for treating acrylonitrile-containing wastewater according to the present invention.
Description of the reference numerals
1: a water inlet pool 2: stirrer
3: and (4) a water inlet pump: first-stage sand filtering unit
5: 6, quartz sand: back flush outlet
7: secondary medium-efficiency filtering unit 8: PP cotton filter element
9: homogeneous catalyst mixing zone 10: automatic feeding device for homogeneous catalyst
11: heterogeneous catalyst feeding device 12: reaction cylinder of vacuum ultraviolet device
13: vacuum ultraviolet light source 14: aeration plate
15: air inlet 16: heterogeneous molecular sieve catalysts
17: the guide shell 18: hollow membrane module
19: and (3) water outlet pump 20: monitoring pool
4-1: a sand filtration unit vent valve 7-1: middle-effect filtering unit emptying valve
12-1: vacuum ultraviolet light catalytic unit atmospheric valve
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, the apparatus for treating acrylonitrile-containing wastewater comprises: a pretreatment unit and a vacuum ultraviolet light catalytic reaction unit, wherein,
the pretreatment unit is used for filtering acrylonitrile-containing wastewater to be treated to obtain filtrate;
the vacuum ultraviolet light catalytic reaction unit is communicated with the pretreatment unit and is used for carrying out vacuum ultraviolet light catalytic reaction on the filtrate to obtain reacted effluent; the vacuum ultraviolet light catalytic reaction unit can irradiate vacuum ultraviolet waves smaller than or equal to 200nm and short-wavelength ultraviolet waves larger than 200nm at the same time.
According to the present invention, it is preferable that the wavelength of vacuum ultraviolet waves is 185nm and the wavelength of short wavelength ultraviolet waves (UVC) is 254 nm.
According to the invention, the pretreatment unit is used for filtering the acrylonitrile-containing wastewater to remove particle suspended matters, thereby reducing the turbidity of the acrylonitrile-containing wastewater. The pretreatment unit may be any of various pretreatment devices known in the art capable of achieving the above-described object.
Preferably, as shown in fig. 1, the pretreatment unit comprises a primary sand filtration unit 4 and a secondary medium-efficiency filtration unit 7 which are communicated in sequence. The primary sand filtration unit 4 comprises a primary water inlet, a primary water outlet, a primary sand filtration unit emptying valve 4-1 and a back flush water outlet 6, the primary water inlet is used for introducing acrylonitrile-containing wastewater to be treated into the primary sand filtration unit 4, and the primary sand filtration unit emptying valve 4-1 is used for opening and emptying gas in the primary sand filtration unit 4 or closing to stop the emptying of the gas. The backwash water discharge opening 6 is used to open to introduce backwash water to backwash the primary sand filtration unit 4 and discharge contaminants or to close the backwash water discharge opening 6 to stop discharge of contaminants (normally, when the primary sand filtration unit 4 is operating, the backwash water discharge opening 6 is closed). The secondary medium-efficiency filtering unit 7 comprises a secondary water inlet, a secondary water outlet and a secondary medium-efficiency filtering unit emptying valve 7-1, the primary water outlet is communicated with the secondary water inlet through a pipeline, and the secondary water outlet is communicated with the vacuum ultraviolet light catalytic reaction unit through a filtrate water outlet pipeline. The secondary medium-effect filtering unit emptying valve 7-1 is used for opening and emptying the gas in the secondary medium-effect filtering unit 7 or closing to stop the emptying of the gas. In order to further improve the catalytic efficiency, the energy utilization efficiency and the light penetration performance of the vacuum ultraviolet light catalytic reaction unit, the two-stage filtering unit of the first-stage sand filtering unit and the second-stage medium-efficiency filtering unit is combined with the vacuum ultraviolet light catalytic reaction unit, suspended matters in wastewater are effectively removed through second-stage filtering, the turbidity of the wastewater is greatly reduced, and the catalytic efficiency of the vacuum ultraviolet light catalytic reaction unit is further improved.
According to the invention, as shown in fig. 1, the processing device further comprises: a catalyst adding unit, wherein the catalyst adding unit comprises: the homogeneous catalyst feeding unit comprises: the device comprises a homogeneous catalyst automatic feeding device 10 and a homogeneous catalyst mixing zone 9 which are communicated with each other, wherein the homogeneous catalyst automatic feeding device 10 is used for feeding a homogeneous catalyst into the homogeneous catalyst mixing zone 9. The homogeneous catalyst mixing area 9 is arranged on a pipeline communicated between the pretreatment unit and the vacuum ultraviolet light catalytic reaction unit, preferably, the homogeneous catalyst adding unit is arranged on a pipeline communicated between the secondary middle-effect filtering unit 7 and the vacuum ultraviolet light catalytic reaction unit, and the secondary water outlet is communicated with the water inlet of the vacuum ultraviolet light catalytic reaction unit through the homogeneous catalyst mixing area 9 on the filtrate water outlet pipeline.
According to the present invention, the homogeneous catalyst mixing zone 9 is used for mixing the filtrate obtained after filtration by the pretreatment unit with the homogeneous catalyst, and therefore, the homogeneous catalyst mixing zone 9 may be a part of the filtrate outlet pipe and also be tubular. Preferably, in consideration of the pressure when the homogeneous catalyst is added to the homogeneous catalyst mixing zone 9 by the homogeneous catalyst automatic adding device 10 and the requirement of uniform mixing, the pipe diameter of the homogeneous catalyst mixing zone 9 is larger than the pipe diameter of the filtrate water outlet pipeline, and more preferably, the pipe inner diameter of the homogeneous catalyst mixing zone 9 is 1.5-2 times of the pipe inner diameter of the filtrate water outlet pipeline.
According to the water quality and the treatment difficulty of the acrylonitrile-containing wastewater, the homogeneous catalyst can be selectively added or not added, and if required, the homogeneous catalyst can be added into the filtrate through the homogeneous catalyst adding unit. Further, when the treatment efficiency and the acrylonitrile removal rate need to be improved, a heterogeneous catalyst can be selectively added, for example, the heterogeneous catalyst can be independently added, or the homogeneous catalyst and the heterogeneous catalyst can be simultaneously added, so that the treatment device and the treatment method for the acrylonitrile-containing wastewater can selectively realize the ultraviolet catalytic reaction of homogeneous catalysis and/or heterogeneous catalysis under vacuum ultraviolet irradiation. Preferably, as shown in fig. 1, the catalyst adding unit further comprises: and the automatic heterogeneous catalyst adding device 11 is communicated with the vacuum ultraviolet light catalytic reaction unit.
According to the present invention, as shown in fig. 1, the vacuum ultraviolet photocatalytic reaction unit includes: a vacuum ultraviolet device reaction cylinder 12 with sealed top and bottom, a vacuum ultraviolet light source 13 arranged in the vacuum ultraviolet device reaction cylinder 12, a water inlet arranged at the lower part of the vacuum ultraviolet device reaction cylinder 12, a water outlet arranged at the top of the vacuum ultraviolet device reaction cylinder 12 and a vacuum ultraviolet light catalysis unit emptying valve 12-1. A filtrate water outlet of the pretreatment unit, preferably a secondary water outlet of the secondary middle-effect filtration unit 7 is communicated with a water inlet of the vacuum ultraviolet device reaction cylinder 12 through a pipeline. The vacuum ultraviolet light source 13 is used for irradiating the filtrate to perform vacuum ultraviolet light catalytic reaction.
According to the invention, the high-efficiency vacuum ultraviolet light source has two wave band wavelengths, namely a vacuum ultraviolet light wave band less than or equal to 200nm and a short wavelength ultraviolet light wave band more than 200 nm. The vacuum ultraviolet device reaction cylinder 12 can be connected in series in one stage or multiple stages, so as to better realize the catalytic reaction of the wastewater according to the concentration of acrylonitrile in the wastewater and the wastewater treatment requirement. The reaction cylinder of the vacuum ultraviolet device is generally made of stainless steel.
According to a preferred embodiment of the present invention, the processing device further comprises an opening disposed at the top, and a sleeve disposed in the vacuum ultraviolet device reaction cylinder 12, wherein the bottom end of the sleeve is closed, and the peripheral side wall of the upper end of the sleeve is fixedly connected with the opening disposed at the top. In order to protect the vacuum ultraviolet light source 13 from directly contacting the acrylonitrile-containing wastewater and enable the acrylonitrile-containing wastewater to normally irradiate, the vacuum ultraviolet light source 13 generally needs to be arranged in a sleeve, the bottom end of the sleeve is closed, the upper end of the sleeve is open, and the peripheral side wall of the upper end of the sleeve is fixedly connected with the open hole arranged at the top so as to fix the upper end of the sleeve with the top, so that the vacuum ultraviolet light source 13 can be conveniently placed, fixed and taken out. Furthermore, the bottom end of the sleeve may be free, i.e. not fixed. The number of the top openings and the number of the vacuum ultraviolet light sources 13 are matched with the number of the sleeves, and the number of the top openings and the number of the vacuum ultraviolet light sources 13 can be one or more. The sleeve can be made of various materials which can resist water corrosion and do not influence the normal irradiation of the vacuum ultraviolet light source, and is preferably made of quartz material.
According to the present invention, the outer circumferential sidewall of the upper end of the sleeve may be fixed to the vacuum ultraviolet device reaction cylinder 12 by a conventional method, for example, one or more of screw coupling, bolt coupling, and bonding using an adhesive, depending on the materials of the sleeve and the top of the vacuum ultraviolet device reaction cylinder 12.
Preferably, in order to further ensure the vacuum ultraviolet light catalytic reaction effect, the vacuum ultraviolet device reaction cylinder 12 is a cylinder, and the number of the vacuum ultraviolet light sources 13 is such that the treatment capacity of the acrylonitrile-containing wastewater treatment device can be satisfied, for example, the number of the vacuum ultraviolet light sources 13 can be 1-10, and preferably, the vacuum ultraviolet light sources 13 are plural and distributed along the circumferential direction of the vacuum ultraviolet device reaction cylinder 12. More preferably, the vacuum ultraviolet light sources 13 are uniformly distributed along the circumferential direction of the vacuum ultraviolet device reaction cylinder 12 by 4-8. The vertical distance between the inner wall of the reaction cylinder 12 of the vacuum ultraviolet device and the vacuum ultraviolet light source 13 (namely, a vacuum ultraviolet lamp) is 5-10mm, and the distance between the adjacent vacuum ultraviolet light sources 13 (namely, vacuum ultraviolet lamps) is 10-20 mm. As described above, when more than two, for example, 4 vacuum ultraviolet light sources are required to be disposed in the vacuum ultraviolet device reaction cylinder 12, correspondingly, 4 sleeves are provided, and correspondingly, 4 openings are provided at the top, and the outer peripheral side wall of the upper end of each sleeve is fixedly connected to the opening provided at the top. Preferably, the vacuum ultraviolet light source 13 is a straight tube vacuum ultraviolet lamp. More preferably, the sleeve and the vacuum ultraviolet light source are of an integral structure, that is, the position of the vacuum ultraviolet light source is fixed when the sleeve is fixed in the top opening.
According to the present invention, the periphery of the top of the vacuum ultraviolet device reaction cylinder 12 is hermetically connected to the top of the vacuum ultraviolet device reaction cylinder 12, and the bottom of the vacuum ultraviolet device reaction cylinder 12 and the cylinder are preferably of an integral structure. The sealing connection mode can be selected according to the materials of the vacuum ultraviolet device reaction cylinder 12 and the top, such as one or more of welding, screw connection, bonding, snap connection and clamping groove connection. Preferably, the vacuum ultraviolet device reaction cylinder 12 is of an integral structure with the top, the cylinder and the bottom.
According to the wastewater oxidation device of the present invention, the top, the barrel and the bottom of the vacuum ultraviolet device reaction barrel 12 can be made of various materials resistant to wastewater corrosion, for example, one or more of a metal material and a non-metal material can be adopted, the metal material can be stainless steel, the non-metal material can be one or more of an inorganic material and an organic material, for example, one or more of a ceramic material, a glass material and a polymer material (such as organic glass) can be included but not limited.
According to the invention, a guide cylinder 17 is arranged in a space surrounded by a plurality of vacuum ultraviolet light sources 13 distributed along the circumferential direction of the vacuum ultraviolet device reaction cylinder 12 and along the height direction of the vacuum ultraviolet device reaction cylinder 12, the guide cylinder 17 is used for guiding acrylonitrile-containing wastewater to enter from the lower part and flow out from the upper part, and the heterogeneous catalyst is in a uniform and fluidized state in the vacuum ultraviolet device reaction cylinder 12. In a further preferred case, in order to facilitate the extraction of the effluent after the reaction, the guide cylinder 17 is disposed along the axial direction of the reaction cylinder 12 of the vacuum ultraviolet device.
The guide shell 17 may be of a construction known in the art according to the present invention. Preferably, specifically, in order to facilitate better diversion and further improve the wastewater treatment effect, the upper part of the diversion cylinder 17 is a cylindrical cylinder, the lower part of the diversion cylinder is a bell-mouth-shaped cylinder with gradually enlarged diameter, one end of a small-diameter opening of the lower bell-mouth-shaped cylinder is fixedly connected with the lower end of the cylindrical cylinder, more preferably, the diameter-height ratio of the upper cylindrical cylinder is 0.8-1:1, and the ratio of the height of the lower bell-mouth-shaped cylinder to the height of the upper cylindrical cylinder is 0.6-0.8: 1; the total height of the guide cylinder (17) is 45-55% of the vertical distance from the top of the reaction cylinder body (12) of the vacuum ultraviolet device to the bottom of the reaction cylinder body, and the vertical distance from one end of the large-diameter opening of the horn-mouth-shaped cylinder at the lower part of the guide cylinder (17) to the bottom of the reaction cylinder body (12) of the vacuum ultraviolet device is 15-20% of the vertical distance from the top of the reaction cylinder body (12) of the vacuum ultraviolet device to the bottom of the reaction cylinder body. The guide cylinder 17 may be fixed in a manner conventional in the art, for example, the guide cylinder 17 may be directly fixed to the top of the vacuum ultraviolet device reaction cylinder 12 by a connecting rod, or the guide cylinder 17 may be fixedly connected to a hollow portion of a fixed ring net (the hollow portion of the fixed ring net has the same diameter as the outer diameter of the upper cylindrical cylinder of the guide cylinder 17) by arranging the fixed ring net along the radial direction of the vacuum ultraviolet device reaction cylinder 12. The guide cylinder 17 can be made of various materials which can resist the corrosion of waste water and do not influence the normal irradiation of the vacuum ultraviolet light source, and is preferably made of quartz material.
According to the present invention, preferably, the wastewater treatment apparatus further comprises: a hollow membrane module 18 disposed above the draft tube 17. The hollow membrane module 18 is used for filtering the effluent after the reaction and leading the effluent out of the vacuum ultraviolet device reaction cylinder 12 through a water outlet, for example, the treated effluent can be subjected to solid-liquid separation with a heterogeneous catalyst through the hollow membrane module 18, and other particle suspended impurities in the treated wastewater can be further filtered. Further preferably, in order to facilitate the discharge of the effluent after the reaction, the hollow membrane module 18, the guide cylinder 17 and the water outlet of the vacuum ultraviolet device reaction cylinder 12 are all arranged along the axial direction of the vacuum ultraviolet device reaction cylinder 12. In order to facilitate the separation of the heterogeneous catalyst in a fluidized state, the hollow membrane module 18 is disposed above the guide cylinder 17 and spaced from the guide cylinder 17, preferably by 10-15% of the vertical distance from the top of the reaction cylinder 12 to the bottom of the reaction cylinder in the vacuum ultraviolet device.
According to the present invention, the hollow membrane module 18 may be of a construction known in the art. Preferably, the hollow membrane module 18 is a hollow fiber membrane and/or a hollow ceramic membrane. The hollow membrane module 18 may be fixed in a manner conventional in the art, for example, the upper end of the hollow membrane module 18 may be fixedly connected to the top of the vacuum ultraviolet device reaction cylinder 12.
According to the present invention, the wastewater treatment apparatus further comprises: an aeration disc 14 arranged at the bottom in the vacuum ultraviolet device reaction cylinder 12 and an air inlet 15 arranged at the bottom of the vacuum ultraviolet device reaction cylinder 12. The material of the aeration disc 14 is usually titanium alloy, and the porosity of the aeration disc 14 is 30-50%, preferably 45-50% from the viewpoint of better realizing the efficient treatment of the wastewater containing acrylonitrile; the pore diameter is 1-20 μm, preferably 8-15 μm. The gas inlet 15 is used for introducing aeration gas, the aeration gas enters the wastewater after being distributed through the aeration disc 14, the gas for aeration can be oxidizing gas, such as at least one selected from ozone, air and oxygen, and the oxidizing gas can be further combined with a catalyst to perform catalytic oxidation under vacuum ultraviolet irradiation, so that the high-efficiency catalytic oxidation and removal of acrylonitrile in the wastewater are realized. The gas used for aeration may also be an inert gas, for example, typically nitrogen. The aeration tray 14 is disposed such that the guide cylinder 17 is positioned above the aeration tray 14 from the viewpoint of facilitating the guide of the wastewater by the guide cylinder 17.
According to the present invention, as shown in fig. 1, the apparatus for treating acrylonitrile-containing wastewater further comprises: a water inlet unit and/or a water outlet unit; the water inlet unit is communicated with the pretreatment unit, preferably the primary sand filtration unit 4, and is used for collecting, homogenizing and stirring the acrylonitrile-containing wastewater to be treated, and the acrylonitrile-containing wastewater enters the pretreatment unit, preferably the primary sand filtration unit 4, through a water outlet pipeline; the water outlet unit is communicated with the vacuum ultraviolet light catalytic reaction unit and is used for collecting and monitoring the water outlet after reaction.
According to the invention, as shown in fig. 1, the water inlet unit comprises a water inlet tank 1, the water inlet tank 1 is provided with a water inlet pipeline and a water outlet pipeline, and the water outlet pipeline is provided with a water inlet pump 3 for controlling the flow of the acrylonitrile-containing wastewater; a stirrer 2 is arranged in the water inlet tank 1 and used for stirring the wastewater.
According to the invention, as shown in fig. 1, the effluent unit comprises an effluent monitoring tank 20; the effluent monitoring pool 20 is communicated with a water outlet of the vacuum ultraviolet light catalytic reaction unit through a water discharge pipeline and is used for collecting and monitoring effluent after reaction; and the water discharge pipeline is also provided with a water discharge pump 19 for opening a water discharge port of the vacuum ultraviolet light catalytic reaction unit to introduce the reacted water into a water discharge monitoring pool 20 or closing the water discharge port of the vacuum ultraviolet light catalytic reaction unit to stop the discharge of the reacted water.
The operation of the apparatus for treating acrylonitrile-containing wastewater according to the present invention will be described below with reference to FIG. 1:
the method comprises the steps of starting a water inlet pump 3 of a water inlet pipeline, starting an emptying valve 4-1 of a primary sand filtration unit 4, starting an emptying valve 7-1 of a secondary intermediate-efficiency filtration unit 7, starting an emptying valve 12-1 of a vacuum ultraviolet light catalysis unit, starting a water outlet pump 19, keeping the same flow rate of the water inlet pump 3 and the water outlet pump 19, respectively closing the emptying valve 4-1 of the primary sand filtration unit 4, the emptying valve 7-1 of the secondary intermediate-efficiency filtration unit 7 and the emptying valve 12-1 of the vacuum ultraviolet light catalysis unit during overflow, and filling the pipelines and the reactor with acrylonitrile-containing wastewater to be treated at the moment.
The method comprises the steps of enabling acrylonitrile-containing wastewater to be treated to enter a primary sand filtering unit 4 from a water inlet tank 1 of a water inlet unit through a water inlet tank water outlet pipeline for primary sand filtering, then entering a secondary middle-effect filtering unit 7 for secondary filtering to remove particle suspended substances so as to reduce turbidity of the wastewater, enabling obtained filter liquor to be introduced into a homogeneous catalyst mixing zone 9 through a filtrate water outlet pipeline, starting an automatic homogeneous catalyst feeding device 10, controlling feeding flow of a homogeneous catalyst, enabling the filter liquor and the homogeneous catalyst to be fully mixed in the homogeneous catalyst mixing zone 9, and then enabling the filter liquor and the homogeneous catalyst to enter a vacuum ultraviolet device reaction cylinder 12 of a vacuum ultraviolet catalytic reaction unit. Before and/or while starting the vacuum ultraviolet light source 13 to perform the vacuum ultraviolet light catalytic reaction, the heterogeneous catalyst is added by the heterogeneous catalyst automatic adding device 11. The vacuum ultraviolet light source 13 is started, the air inlet 15 connected with an external air source is started, the aeration disc 14 is in an aeration state, the guide cylinder 17 is used for guiding the wastewater containing acrylonitrile to flow from the lower part to the upper part and flow out, and enables the heterogeneous catalyst to be in a uniform and fluidized state in the vacuum ultraviolet device reaction cylinder 12, the heterogeneous catalyst is adsorbed and treated by ultraviolet light catalysis in the vacuum ultraviolet device reaction cylinder 12, and the wastewater enters the water outlet monitoring pool 20 of the water outlet unit after being filtered by the hollow membrane component 18 after being subjected to one-stage or multi-stage (figure 1 is one stage) ultraviolet light catalysis reaction. The effluent of the effluent pump 19 is the treated acrylonitrile-containing wastewater. The acrylonitrile-containing wastewater is subjected to two-stage filtration, adsorption, ultraviolet light catalysis, filtration and other treatments in the whole process.
The second aspect of the present invention provides a method for treating acrylonitrile-containing wastewater, wherein the method comprises:
a pretreatment step: filtering the acrylonitrile-containing wastewater to be treated to obtain filtrate;
vacuum ultraviolet light catalytic reaction: carrying out vacuum ultraviolet light catalytic reaction on the filtrate under the irradiation of vacuum ultraviolet light to obtain reacted effluent; the vacuum ultraviolet light has both vacuum ultraviolet waves less than or equal to 200nm and short wavelength ultraviolet waves greater than 200 nm.
According to the invention, in the pretreatment step, it is sufficient to ensure that the acrylonitrile-containing wastewater to be treated is filtered to remove particle suspended matter and thereby reduce its turbidity. Preferably, according to an embodiment of the present invention, in order to further improve the photocatalytic efficiency, energy utilization efficiency, and light penetration performance of vacuum ultraviolet light catalysis, before performing vacuum ultraviolet light catalysis reaction, the acrylonitrile-containing wastewater to be treated is sequentially subjected to primary sand filtration and secondary intermediate-efficiency filtration, so as to effectively remove suspended matters in the acrylonitrile-containing wastewater, and greatly reduce turbidity of the wastewater, thereby further improving the catalytic reaction efficiency of the vacuum ultraviolet unit. Preferably, the turbidity of the filtrate obtained after the second filtration is less than 5 NTU. Further preferably, in order to meet the turbidity requirement of the filtrate, the first-stage sand filtration adopts quartz sand as a filter material, and the diameter of the filter material is 0.5-8mm, and more preferably 0.5-5 mm; the filling rate of the filter material is 60-85%, and the retention time of the first-stage sand filtration is 5-10 min. Further preferably, the middle-effect filtration is performed by using a PP cotton filter element, and the filtration pore size is 1-5 μm, more preferably 0.5-3 μm; the retention time of the secondary medium-effect filtration is 2-5 min.
According to the present invention, in the vacuum ultraviolet light catalytic reaction step, the wavelength of vacuum ultraviolet waves irradiated by the vacuum ultraviolet light is preferably 185nm, while the wavelength of short wavelength ultraviolet waves (UVC) irradiated is preferably 254 nm.
According to the invention, the irradiation of vacuum ultraviolet light and the homogeneous catalyst are coupled to form a homogeneous photocatalytic reaction system, so that the treatment effect of the acrylonitrile-containing wastewater can be further improved. The irradiation of vacuum ultraviolet light is coupled with a heterogeneous catalyst to form an adsorption-ultraviolet light catalytic reaction system, so that the removal rate and the treatment efficiency of the acrylonitrile-containing wastewater can be further improved.
Therefore, preferably, the treatment method further comprises a catalyst mixing step: the catalyst comprises a homogeneous catalyst and a heterogeneous catalyst, and the filtrate is selectively mixed with the homogeneous catalyst and/or the heterogeneous catalyst before and/or while the filtrate is subjected to vacuum ultraviolet light catalytic reaction under the irradiation of vacuum ultraviolet light. Further preferably, the filtrate is mixed with the catalyst in the following manner: the homogeneous catalyst is mixed with the filtrate in a continuous addition prior to the vacuum ultraviolet photocatalytic reaction, and the heterogeneous catalyst is mixed with the filtrate in a batch addition, more preferably a one-time addition, prior to and/or simultaneously with the vacuum ultraviolet photocatalytic reaction.
Specifically, the homogeneous catalyst may be various photocatalysts conventionally used in the art, and preferably, the homogeneous catalyst is selected from one or more of hydrogen peroxide, sodium persulfate, ferrous sulfate and sodium hypochlorite, and preferably, the homogeneous catalyst is used in the form of an aqueous solution, and may be appropriately selected from the amounts of the homogeneous catalyst added according to the concentration of acrylonitrile in the acrylonitrile-containing wastewater, and preferably, the amount of the homogeneous catalyst used in the form of an aqueous solution is 0.3 to 1.5L/h, so that the molar concentration ratio of the homogeneous catalyst to acrylonitrile in the wastewater is 0.2 to 0.8: 1. Specifically, it is more preferable to set the molar concentration ratio of hydrogen peroxide to acrylonitrile in the wastewater to 0.5 to 0.8:1, the molar concentration ratio of sodium persulfate to acrylonitrile in the wastewater to 0.2 to 0.5:1, the molar concentration ratio of ferrous sulfate to acrylonitrile in the wastewater to 0.5 to 0.8:1, and the molar concentration ratio of sodium hypochlorite to acrylonitrile in the wastewater to 0.3 to 0.5: 1. Wherein, the adding concentration of the hydrogen peroxide solution, namely the hydrogen peroxide solution, is generally 30 weight percent, the adding concentration of the sodium persulfate solution is generally 60-100g/L, the adding concentration of the ferrous sulfate solution is generally 0.1M, and the adding concentration of the sodium hypochlorite solution is generally 0.1M.
Specifically, the heterogeneous catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component is at least one of a semiconductor material, a metal in the VIII group of the periodic table, a nonmetal element in the IVA group of the periodic table and a nonmetal element in the VA group of the periodic table. The inventor of the invention finds that the heterogeneous catalyst obtained by loading at least one active component selected from semiconductor materials, metal elements in the VIII group of the periodic table, non-metal elements in the IVA group of the periodic table and non-metal elements in the VA group of the periodic table on a molecular sieve carrier is coupled with vacuum ultraviolet light to form an adsorption-ultraviolet light catalytic reaction system, so that the removal rate of acrylonitrile in wastewater can be greatly improved, COD and BOD in wastewater can be greatly reduced, and more preferably, COD and BOD in wastewater are greatly reducedFurthermore, the homogeneous catalyst is further coupled, so that the treatment effect of the wastewater can be further improved. Wherein the semiconductor material is preferably TiO2And/or ZnO, the metal active component is preferably Fe and/or Cu, the nonmetal active component is preferably C and/or N, the carrier is a molecular sieve, and the molecular sieve is ZSM-5 and/or OMS-2; the content of the semiconductor material is 5-20 wt% based on the total weight of the heterogeneous catalyst, and the total content of the metal element and the nonmetal element calculated by element is 1-5 wt%. According to a preferred embodiment of the invention, the heterogeneous catalyst is a supported TiO2The ZSM-5 molecular sieve, the ZnO loaded ZSM-5 molecular sieve and the TiO loaded2Based on the total weight of the heterogeneous catalyst, and at least one of OMS-2 molecular sieve(s) of (A) and OMS-2 molecular sieve(s) supporting ZnO, the TiO being based on the total weight of the heterogeneous catalyst2And the total content of ZnO is 3-8 wt%. The preparation method of the heterogeneous catalyst can be obtained by referring to the conventional preparation method in the field. For example, the catalyst can be prepared by a conventional wet impregnation method, or alternatively by a dry impregnation method (solid phase ion exchange). According to one embodiment of the invention, the preparation of the heterogeneous catalyst can be carried out according to the following steps: the molecular sieve (ZSM-5 and/or OMS-2) is impregnated with a solution containing a soluble compound of the active component, and the impregnated molecular sieve is dried and optionally calcined.
According to the invention, the heterogeneous catalyst is preferably used in an amount of 0.5g to 2g, based on 1L of acrylonitrile-containing waste water.
According to the present invention, in the vacuum ultraviolet photocatalytic reaction step, the reaction method comprises: carrying out vacuum ultraviolet light catalytic reaction on the filtrate; the power of a single vacuum ultraviolet light source is 20-150W, and preferably, the number of the vacuum ultraviolet light sources is 4-8; the residence time of the vacuum ultraviolet light catalytic reaction can be properly selected according to the concentration of acrylonitrile in the wastewater and the total power of the vacuum ultraviolet light source, and is preferably 30-90 min. Preferably, the filtrate is selectively mixed with a homogeneous catalyst and/or a heterogeneous catalyst, and more preferably, the filtrate is mixed with a homogeneous catalyst and a heterogeneous catalyst. Further preferably, the reaction is carried out under aeration conditions, and the gas used for aeration may be an oxidizing gas, for example, at least one selected from ozone, air and oxygen, and the oxidizing gas may be further combined with a catalyst to carry out catalytic oxidation under vacuum ultraviolet light irradiation, thereby realizing efficient catalytic oxidation and removal of acrylonitrile in the wastewater. The gas used for aeration may also be an inert gas, for example, typically nitrogen. The aeration rate can be properly selected according to the quality of the wastewater and the dosage of the heterogeneous catalyst, and preferably, the aeration rate is 50-200mL/min relative to 1L of the wastewater containing acrylonitrile.
According to the invention, the processing method further comprises: after the vacuum ultraviolet light catalytic reaction, the effluent water after the reaction is filtered, on one hand, heterogeneous catalysts can be separated, on the other hand, particle suspended matter impurities in the effluent water after the treatment can be further removed, the heterogeneous catalysts obtained through the separation can be recycled, and the effluent water after the treatment is led out through a water outlet of the vacuum ultraviolet catalytic reaction unit.
According to the present invention, preferably, the processing method further includes:
homogenizing: collecting, buffering and stirring before pretreating acrylonitrile-containing wastewater to be treated; and/or the presence of a gas in the gas,
a water drainage step: and collecting and monitoring the effluent after the reaction.
In a third aspect of the present invention, according to a specific embodiment, the method for treating acrylonitrile-containing wastewater is carried out in the treatment apparatus of the present invention.
The processing method comprises the following steps:
a pretreatment step: the method comprises the following steps of (1) filtering acrylonitrile-containing wastewater to be treated in a pretreatment unit to obtain filtrate;
vacuum ultraviolet light catalytic reaction: the filtrate enters a vacuum ultraviolet light catalytic reaction unit, and is subjected to vacuum ultraviolet light catalytic reaction under the irradiation of vacuum ultraviolet light to obtain reacted effluent; the vacuum ultraviolet light has vacuum ultraviolet waves less than or equal to 200nm and short-wavelength ultraviolet waves more than 200nm, preferably, the wavelength of the vacuum ultraviolet waves is 185nm, and the wavelength of the short-wavelength ultraviolet waves is 254 nm.
According to the invention, preferably, in the pretreatment step, the acrylonitrile-containing wastewater to be treated sequentially enters the primary sand filtration unit 4 through a water inlet pipeline for primary sand filtration and the secondary intermediate filtration unit 7 for secondary intermediate filtration to obtain a filtrate, so that the turbidity of the filtrate obtained after the secondary filtration is less than 5 NTU. More preferably, in order to meet the turbidity requirement of the filtrate, the first-stage sand filtration adopts quartz sand as a filter material, and the diameter of the filter material is 0.5-8mm, more preferably 0.5-5 mm; the filling rate of the filter material is 60-85%, and the retention time of the first-stage sand filtration is 5-10 min; the middle-effect filtration adopts a PP cotton filter element for filtration, and the filtration pore size is 1-5 μm, and more preferably 0.5-3 μm; the retention time of the secondary medium-effect filtration is 2-5 min.
According to the invention, in order to ensure the smooth operation of the filtering process, the primary sand filtering unit emptying valve 4-1 is opened and the back flush water outlet 6 is closed in the process of filtering the acrylonitrile-containing wastewater to be treated in the primary sand filtering unit 4 of the pretreatment unit, and the secondary middle-effect filtering unit emptying valve 7-1 is opened in the process of filtering the primary effluent led out from the primary sand filtering unit 4 in the secondary middle-effect filtering unit 7. And 4-1 of the first-stage sand filtration unit emptying valve and 7-1 of the second-stage medium-efficiency filtration unit emptying valve are respectively closed when water overflows.
According to the invention, the treatment process further comprises a catalyst mixing step: the catalyst comprises a homogeneous catalyst and a heterogeneous catalyst, the filtrate enters a vacuum ultraviolet light catalytic reaction unit, and the filtrate is selectively mixed with the homogeneous catalyst and/or the heterogeneous catalyst before and/or while the vacuum ultraviolet light catalytic reaction is carried out under the irradiation of vacuum ultraviolet light.
In the invention, preferably, the homogeneous catalyst adding unit and the heterogeneous catalyst adding device are respectively arranged, so that different types of catalysts can be selectively added according to the water quality and the treatment effect of the acrylonitrile-containing wastewater, for example, only the homogeneous catalyst can be added, and the homogeneous catalyst and the heterogeneous catalyst can be added simultaneously to further improve the treatment effect of the wastewater.
According to one embodiment of the present invention, the filtrate is mixed with the catalyst in a manner that: and (3) enabling the filtrate to enter a homogeneous catalyst mixing zone 9 of a catalyst adding unit through a filtrate water outlet pipeline to be mixed with a homogeneous catalyst which is added to the homogeneous catalyst mixing zone 9 through an automatic homogeneous catalyst adding device 10, wherein the homogeneous catalyst is mixed with the filtrate in a continuous adding mode. Further preferably, before and/or while the filtrate mixed with the homogeneous catalyst enters the vacuum ultraviolet device reaction cylinder 12 of the vacuum ultraviolet catalytic reaction unit, the heterogeneous catalyst is added into the vacuum ultraviolet device reaction cylinder 12, and more preferably, the heterogeneous catalyst is added into the vacuum ultraviolet device reaction cylinder 12 through the heterogeneous catalyst automatic adding device 11; the heterogeneous catalyst is added into the reaction cylinder 12 of the vacuum ultraviolet device in a batch mode, preferably in a one-time mode, and is mixed with the filtrate. The vacuum ultraviolet light catalytic reaction is carried out under the irradiation of the vacuum ultraviolet light, the irradiation of the vacuum ultraviolet light is coupled with the homogeneous catalyst to form a homogeneous photocatalytic reaction system, the irradiation of the vacuum ultraviolet light is coupled with the heterogeneous catalyst to form an adsorption-photocatalytic reaction system, and the high-efficiency removal of acrylonitrile in the acrylonitrile-containing wastewater can be further improved.
According to the present invention, the structures and parameters of the automatic homogeneous catalyst feeding device 10, the homogeneous catalyst mixing zone 9, the heterogeneous catalyst feeding device 11 and the vacuum ultraviolet device reaction cylinder 12, and the compositions, types and amounts of the homogeneous catalyst and the heterogeneous catalyst have been described above, and are not described herein again.
More preferably, in the vacuum ultraviolet photocatalytic reaction step, the reaction method comprises: and (3) introducing the filtrate into a reaction cylinder 12 of a vacuum ultraviolet device, and simultaneously starting a vacuum ultraviolet light source 13 to irradiate the acrylonitrile-containing wastewater to perform vacuum ultraviolet catalytic reaction. The power of a single vacuum ultraviolet light source is preferably 20-150W, and the number of the vacuum ultraviolet light sources is preferably 4-8; the residence time of the vacuum ultraviolet light catalytic reaction can be properly selected according to the concentration of acrylonitrile in the wastewater and the total power of the vacuum ultraviolet light source, and is preferably 30-90 min.
More preferably, a homogeneous catalyst and/or a heterogeneous catalyst is selectively mixed in the filtrate, and further preferably, a homogeneous catalyst and a heterogeneous catalyst are mixed in the filtrate.
Further preferably, the filtrate mixed with at least the heterogeneous catalyst enters the vacuum ultraviolet device reaction cylinder 12, enters from the lower part of the guide cylinder 17 and flows out from the upper part, and the heterogeneous catalyst is in a uniform and fluidized state in the vacuum ultraviolet device reaction cylinder 12, so that the heterogeneous catalyst is more fully contacted and mixed with the wastewater, and the wastewater treatment effect is further improved.
Further preferably, gas is introduced into the vacuum ultraviolet device reaction cylinder 12 through the gas inlet 15 and is aerated through the aeration disc 14 at the bottom of the vacuum ultraviolet device reaction cylinder 12. The aeration gas is preferably one or more selected from the group consisting of ozone, air, oxygen and nitrogen, and the aeration amount is 50 to 200mL/min based on 1L of acrylonitrile-containing wastewater.
According to the present invention, more preferably, the processing method further includes: after the vacuum ultraviolet light catalytic reaction, the effluent after the reaction is filtered by the hollow membrane component 18, and the effluent after the reaction is sent out of the vacuum ultraviolet device reaction cylinder 12 of the vacuum ultraviolet light catalytic reaction unit through the water outlet.
According to the invention, in order to ensure the smooth proceeding of the vacuum ultraviolet catalytic reaction, the vacuum ultraviolet catalytic unit emptying valve 12-1 is opened in the process of introducing the filtrate into the vacuum ultraviolet device reaction cylinder 12 of the vacuum ultraviolet catalytic reaction unit to carry out the vacuum ultraviolet catalytic reaction, and the vacuum ultraviolet catalytic unit emptying valve 12-1 is closed when overflowing.
According to the present invention, the structures and parameters of the aeration disc 14, the guide cylinder 17 and the hollow membrane module 18 have been described above and will not be described herein again.
According to the present invention, preferably, the processing method further includes:
homogenizing: before the acrylonitrile-containing wastewater to be treated enters the pretreatment unit, the acrylonitrile-containing wastewater is firstly put into a water inlet tank 1 of a water inlet unit for collection, buffering and stirring; and/or the presence of a gas in the gas,
a water drainage step: and the effluent after reaction enters an effluent monitoring pool 18 of the effluent unit for collection and monitoring.
According to the invention, the acrylonitrile-containing wastewater to be treated can be treated continuously or intermittently in the treatment device. When the treatment is carried out continuously, the water inlet speed of the acrylonitrile-containing wastewater to be treated is preferably 100-500mL/min, and the water inlet speed and the water outlet speed are the same.
The method of the invention can treat the acrylonitrile-containing wastewater with a wide concentration range, for example, the concentration of acrylonitrile in the wastewater can reach 50-500mg/L, the COD of the acrylonitrile-containing wastewater is generally 500-6000mg/L, and the BOD of the acrylonitrile-containing wastewater is generally 100-1000 mg/L.
The following examples are provided to illustrate the treatment effect of the method for treating acrylonitrile-containing wastewater of the present invention, and unless otherwise stated, the specific operations of the method for treating wastewater are as described above, and the following examples are not repeated.
Examples 1 to 6 were treated by using the acrylonitrile-containing wastewater treatment apparatus described in FIG. 1.
In the acrylonitrile-containing wastewater treatment device, a first-stage sand filtering unit is filled with 1mm quartz sand, the filling rate is 80%, and a second-stage middle-effect filtering unit is filtered by a 1-micrometer PP cotton filter element.
The vacuum ultraviolet device of the vacuum ultraviolet light catalytic reaction unit reacts the volume of the cylindrical barrel body by 35L, and the vertical distance from the top to the bottom of the barrel body is 500 mm. The vacuum ultraviolet light source is a straight tube vacuum ultraviolet lamp with an integrated structure, namely the straight tube vacuum ultraviolet lamp is arranged in a quartz sleeve, the radiation wavelength of the vacuum ultraviolet light source (straight tube lamp) is 185/254nm, the power of a single straight tube vacuum ultraviolet lamp is 20W, the length of a lamp tube is 430mm, and the diameter of the lamp tube is 21 mm. In examples 1 to 5, 8 lamps were provided, and 8 vacuum ultraviolet light sources were uniformly distributed along the circumferential direction of the vacuum ultraviolet device reaction cylinder, the vertical distance between the inner wall of the vacuum ultraviolet device reaction cylinder and the vacuum ultraviolet light source was 20mm, and the distance between adjacent vacuum ultraviolet light sources was 40 mm. In example 6, the number of the lamps is 4, the 4 vacuum ultraviolet light sources are uniformly distributed along the circumferential direction of the reaction cylinder of the vacuum ultraviolet device, the vertical distance between the inner wall of the reaction cylinder of the vacuum ultraviolet device and the vacuum ultraviolet light sources is 20mm, and the distance between adjacent vacuum ultraviolet light sources is 75 mm. In a space enclosed by vacuum ultraviolet light sources distributed along the circumferential direction of the reaction cylinder body of the vacuum ultraviolet device, a hollow membrane component and a quartz guide cylinder are arranged from top to bottom along the axial direction of the reaction cylinder body of the vacuum ultraviolet device, the diameter of a cylindrical cylinder body on the upper part of the quartz guide cylinder is 100mm, the height of the cylindrical cylinder body is 120mm, the lower part of the quartz guide cylinder is in a bell mouth shape with gradually increased diameter, the maximum diameter is 200mm, and the height of the bell mouth shape cylinder body on the lower part of the quartz guide cylinder is 100 mm. The hollow membrane component adopts a hollow plate-type ceramic membrane, the aperture is 0.1 mu m, and the porosity is 50 percent. The distance between the quartz guide cylinder and the hollow membrane component is 50mm (the interval is 10% of the vertical distance between the top of the reaction cylinder body 12 of the vacuum ultraviolet device and the bottom of the reaction cylinder body). An aeration disc is arranged at the bottom in the reaction cylinder body of the vacuum ultraviolet device, the quartz guide cylinder is positioned right above the aeration disc, the porosity of the aeration disc is 45 percent, and the aperture is 10 mu m.
In the following examples, the turbidity of the filtrate was measured by a turbidity meter of the HACH TL23 series.
Example 1
The water quality of the acrylonitrile-containing wastewater treated by the embodiment is as follows: the concentration of acrylonitrile is 100mg/L, COD is 1020mg/L, BOD is 195mg/L, and turbidity is 35 NTU.
The acrylonitrile-containing wastewater to be treated sequentially enters a first-stage sand filtration unit and a second-stage medium-efficiency filtration unit for second-stage filtration at a rate of 0.5L/min through a water outlet pipeline of a water inlet tank of a water inlet unit, a filtrate (turbidity 5NTU) is obtained from a filtrate outlet, the filtrate directly enters a reaction cylinder body of a vacuum ultraviolet catalytic device of a vacuum ultraviolet catalytic reaction unit through a filtrate water outlet pipeline, and neither homogeneous nor heterogeneous catalyst is added. Starting 8 vacuum ultraviolet light sources without starting an aeration device to perform vacuum ultraviolet catalytic reaction, collecting effluent after reaction by an effluent monitoring pool of an effluent unit after filtrate stays in a vacuum ultraviolet catalytic reaction cylinder for 70min, and measuring the effluent quality condition at an effluent pump flow rate of 500mL/min as follows: the concentration of acrylonitrile is 48.2mg/L, COD is 1002mg/L, BOD is 289mg/L, and turbidity is 2 NTU.
Example 2
The acrylonitrile-containing wastewater with the same water quality as that of example 1 was treated, except that the filtrate was mixed with 30 wt% aqueous hydrogen peroxide solution of the homogeneous catalyst added by the homogeneous catalyst automatic adding device in the homogeneous catalyst mixing zone through the filtrate outlet pipe, the molar concentration ratio of hydrogen peroxide to acrylonitrile was 0.5:1, and the inflow flow rate and the outflow flow rate of the acrylonitrile-containing wastewater to be treated were both 500 mL/min. The effluent quality was measured as follows: the concentration of acrylonitrile is 19.0mg/L, COD is 886mg/L, BOD is 301mg/L, and turbidity is 2 NTU.
Example 3
The method is characterized in that when the filtrate directly enters a reaction cylinder body of a vacuum ultraviolet catalytic device of a vacuum ultraviolet catalytic reaction unit through a filtrate outlet pipeline, heterogeneous molecular sieve catalyst is added into the reaction cylinder body of the vacuum ultraviolet catalytic device through a heterogeneous catalyst adding device, wherein the molecular sieve catalyst is loaded TiO2ZSM-5 molecular sieve (TiO)2Loading 5.0 wt%), the molecular sieve catalyst was added in an amount of 0.5g per 1L of wastewater, while the aeration apparatus was turned on to blow air, and the aeration amount was 100mL/min per 1L of wastewater. The water inlet flow rate and the water outlet flow rate of the acrylonitrile-containing wastewater to be treated are both 500 mL/min. The effluent quality was measured as follows: the concentration of acrylonitrile is 11.2mg/L, COD is 558mg/L, BOD is 208mg/L, and turbidity is 1 NTU.
Example 4
The acrylonitrile-containing wastewater with the same water quality as that of the acrylonitrile-containing wastewater in example 1 was treated, except that the filtrate was mixed with 30 wt% aqueous hydrogen peroxide solution of the homogeneous catalyst added by the homogeneous catalyst automatic adding device in the homogeneous catalyst mixing zone through the filtrate outlet pipe, the molar concentration ratio of hydrogen peroxide to acrylonitrile was 0.5:1, and at the same time, when the filtrate directly entered the reaction cylinder of the vacuum ultraviolet catalytic apparatus of the vacuum ultraviolet catalytic reaction unit through the filtrate outlet pipe, the filtrate passed through the non-filter outlet pipeThe homogeneous catalyst adding device adds heterogeneous molecular sieve catalyst into a reaction cylinder body of the vacuum ultraviolet catalytic device, wherein the molecular sieve catalyst is loaded TiO2ZSM-5 molecular sieve (TiO)2Loading 5.0 wt%), the molecular sieve catalyst was added in an amount of 0.5g per 1L of wastewater while the aeration apparatus was turned on to blow air, and the aeration amount was 100mL/min per 1L of wastewater. The water inlet flow rate and the water outlet flow rate of the acrylonitrile-containing wastewater to be treated are both 500 mL/min. The effluent quality was measured as follows: the concentration of acrylonitrile is 0mg/L, COD is 278mg/L, BOD is 111mg/L, and turbidity is 1 NTU.
Example 5
The acrylonitrile-containing wastewater with the same water quality as that of example 1 is treated by the same device and method as that of example 4, except that the inflow flow rate and the outflow flow rate of the acrylonitrile-containing wastewater to be treated are both 1.0L/min, and the effluent quality is determined as follows: the concentration of acrylonitrile is 5.6mg/L, COD is 405mg/L, BOD is 129mg/L, and turbidity is 2 NTU.
Example 6
Acrylonitrile-containing wastewater of the same quality as that of example 1 was treated by the same apparatus and method as in example 4, except that 4 vacuum ultraviolet light sources were turned on to perform vacuum ultraviolet catalytic reaction. The water inlet flow rate and the water outlet flow rate of the acrylonitrile-containing wastewater to be treated are both 500 mL/min. The effluent quality was measured as follows: acrylonitrile concentration 22.0mg/L, COD 767mg/L, BOD 269mg/L, turbidity 2 NTU.
Comparative example 1
Acrylonitrile-containing wastewater of the same quality as in example 1 was treated by the same apparatus and method as in example 2, except that the vacuum ultraviolet light source was turned off. The effluent quality was measured as follows: the concentration of acrylonitrile is 98.5mg/L, COD is 1018mg/L, BOD is 194mg/L, and turbidity is 2 NTU.
Comparative example 2
Acrylonitrile-containing wastewater of the same quality as in example 1 was treated by the same apparatus and method as in example 3, except that the vacuum ultraviolet light source was turned off. The effluent quality was measured as follows: acrylonitrile concentration 63.9mg/L, COD 705mg/L, BOD 136mg/L, turbidity 2 NTU.
Comparative example 3
Acrylonitrile-containing wastewater of the same quality as in example 1 was treated by the same apparatus and method as in example 4, except that the vacuum ultraviolet light source was turned off. The effluent quality was measured as follows: the concentration of acrylonitrile was 59.0mg/L, COD was 683mg/L, BOD was 132mg/L, and turbidity was 2 NTU.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (32)
1. An apparatus for treating acrylonitrile-containing wastewater, comprising: a pretreatment unit and a vacuum ultraviolet light catalytic reaction unit, wherein,
the pretreatment unit is used for filtering acrylonitrile-containing wastewater to be treated to obtain filtrate;
the vacuum ultraviolet light catalytic reaction unit is communicated with the pretreatment unit and is used for carrying out vacuum ultraviolet light catalytic reaction on the filtrate to obtain reacted effluent; the vacuum ultraviolet light catalytic reaction unit can simultaneously irradiate vacuum ultraviolet waves smaller than or equal to 200nm and short-wavelength ultraviolet waves larger than 200nm, and preferably the wavelength of the vacuum ultraviolet waves is 185nm and the wavelength of the short-wavelength ultraviolet waves is 254 nm.
2. The acrylonitrile-containing wastewater treatment device according to claim 1, wherein the pretreatment unit comprises a primary sand filtration unit (4) and a secondary medium-efficiency filtration unit (7) which are communicated in sequence;
the primary sand filtering unit (4) comprises a primary water inlet, a primary water outlet, a primary sand filtering unit emptying valve (4-1) and a backwashing water outlet (6);
the secondary medium-efficiency filtering unit (7) comprises a secondary water inlet, a secondary water outlet and a secondary medium-efficiency filtering unit emptying valve (7-1), the primary water outlet is communicated with the secondary water inlet through a pipeline, and the secondary water outlet is communicated with the vacuum ultraviolet light catalytic reaction unit through a filtrate water outlet pipeline.
3. The apparatus for treating acrylonitrile-containing wastewater according to claim 1 or 2, wherein the apparatus further comprises: a catalyst adding unit, wherein the catalyst adding unit comprises: the homogeneous catalyst feeding unit comprises: the device comprises a homogeneous catalyst automatic feeding device (10) and a homogeneous catalyst mixing zone (9) which are communicated with each other, wherein the homogeneous catalyst automatic feeding device (10) is used for feeding a homogeneous catalyst into the homogeneous catalyst mixing zone (9);
the homogeneous catalyst mixing area (9) is arranged on a pipeline communicated between the pretreatment unit and the vacuum ultraviolet light catalytic reaction unit, preferably, the homogeneous catalyst adding unit is arranged on a pipeline communicated between the secondary medium-efficiency filtering unit (7) and the vacuum ultraviolet light catalytic reaction unit, and the secondary water outlet is communicated with the water inlet of the vacuum ultraviolet light catalytic reaction unit through the homogeneous catalyst mixing area (9) on the filtrate water outlet pipeline.
4. The apparatus for treating acrylonitrile-containing wastewater as claimed in claim 3, wherein the homogeneous catalyst mixing zone (9) is tubular, the pipe diameter of the homogeneous catalyst mixing zone (9) is larger than that of the filtrate outlet pipe, preferably, the pipe inner diameter of the homogeneous catalyst mixing zone (9) is 1.5-2 times that of the filtrate outlet pipe.
5. The apparatus for treating acrylonitrile-containing wastewater according to claim 3, wherein the catalyst adding unit further comprises: the device for automatically adding the heterogeneous catalyst (11) is communicated with the vacuum ultraviolet light catalytic reaction unit.
6. The apparatus for treating acrylonitrile-containing wastewater as claimed in any one of claims 1 to 5, wherein the vacuum ultraviolet photocatalytic reaction unit comprises: the device comprises a vacuum ultraviolet device reaction cylinder (12) with sealed top and bottom, a vacuum ultraviolet light source (13) arranged in the vacuum ultraviolet device reaction cylinder (12), a water inlet arranged at the lower part of the vacuum ultraviolet device reaction cylinder (12), a water outlet arranged at the top of the vacuum ultraviolet device reaction cylinder (12) and a vacuum ultraviolet light catalytic unit emptying valve (12-1);
a filtrate water outlet of the pretreatment unit, preferably a secondary water outlet of a secondary medium-efficiency filtration unit (7), is communicated with a water inlet of a reaction cylinder (12) of the vacuum ultraviolet device through a pipeline; the vacuum ultraviolet light source (13) is used for irradiating the filtering liquid to carry out vacuum ultraviolet light catalytic reaction.
7. The processing device according to claim 6, wherein the processing device further comprises an opening arranged at the top and a sleeve arranged in the vacuum ultraviolet device reaction cylinder body (12), the vacuum ultraviolet light source (13) is arranged in the sleeve, the bottom end of the sleeve is closed, and the peripheral side wall of the upper end of the sleeve is fixedly connected with the opening arranged at the top;
preferably, the sleeve is a quartz sleeve;
further preferably, the sleeve and the vacuum ultraviolet light source (13) are of an integral structure.
8. The acrylonitrile-containing wastewater treatment device according to claim 6 or 7, wherein the vacuum ultraviolet device reaction cylinder (12) is a cylinder, the vacuum ultraviolet light sources (13) are multiple and distributed along the circumferential direction of the vacuum ultraviolet device reaction cylinder (12);
preferably, 4-8 vacuum ultraviolet light sources (13) are uniformly distributed along the circumferential direction of the vacuum ultraviolet device reaction cylinder (12), the vertical distance between the inner wall of the vacuum ultraviolet device reaction cylinder (12) and the vacuum ultraviolet light sources (13) is 5-10mm, and the distance between the adjacent vacuum ultraviolet light sources (13) is 10-20 mm.
9. The acrylonitrile-containing wastewater treatment device according to claim 8, wherein a guide cylinder (17) is arranged in a space surrounded by a plurality of vacuum ultraviolet light sources (13) distributed along the circumferential direction of the vacuum ultraviolet device reaction cylinder (12) and along the height direction of the vacuum ultraviolet device reaction cylinder (12), the guide cylinder (17) is used for guiding acrylonitrile-containing wastewater to enter from the lower part of the guide cylinder (17) and flow out from the upper part, and the heterogeneous catalyst is in a uniform and fluidized state in the vacuum ultraviolet device reaction cylinder (12).
10. The acrylonitrile-containing wastewater treatment device according to claim 9, wherein the guide cylinder (17) is arranged along the axial direction of the vacuum ultraviolet device reaction cylinder (12); the upper part of the guide shell (17) is a cylindrical shell, the lower part of the guide shell is a bell mouth-shaped shell with gradually enlarged diameter, one end of a small-diameter opening of the bell mouth-shaped shell at the lower part is fixedly connected with the lower end of the cylindrical shell, preferably, the diameter-height ratio of the upper cylindrical shell is 0.8-1:1, and the ratio of the height of the lower bell mouth-shaped shell to the height of the upper cylindrical shell is 0.6-0.8: 1; the total height of the guide cylinder (17) is 45-55% of the vertical distance from the top of the reaction cylinder body (12) of the vacuum ultraviolet device to the bottom of the reaction cylinder body, and the vertical distance from one end of the large-diameter opening of the horn-mouth-shaped cylinder at the lower part of the guide cylinder (17) to the bottom of the reaction cylinder body (12) of the vacuum ultraviolet device is 15-20% of the vertical distance from the top of the reaction cylinder body (12) of the vacuum ultraviolet device to the bottom of the reaction cylinder body.
11. The treatment apparatus according to claim 9 or 10, wherein the wastewater treatment apparatus further comprises: the hollow membrane component (18) is arranged above the guide flow cylinder (17), and the hollow membrane component (18) is used for filtering the effluent after reaction and leading the effluent after reaction out of the reaction cylinder body (12) of the vacuum ultraviolet device through a water outlet;
preferably, the water outlet of the vacuum ultraviolet device reaction cylinder (12), the hollow membrane module (18) and the guide cylinder (17) are all arranged along the axial direction of the vacuum ultraviolet device reaction cylinder (12), the hollow membrane module (18) and the guide cylinder (17) are arranged at intervals, and the intervals are 10-15% of the vertical distance from the top of the vacuum ultraviolet device reaction cylinder (12) to the bottom of the reaction cylinder;
more preferably, the hollow membrane module (18) is a hollow fiber membrane and/or a hollow ceramic membrane.
12. The apparatus for treating acrylonitrile-containing wastewater according to claim 9 or 10, wherein the apparatus for treating wastewater further comprises: an aeration disc (14) arranged at the bottom in the reaction cylinder body (12) of the vacuum ultraviolet device and an air inlet (15) arranged at the bottom of the reaction cylinder body (12) of the vacuum ultraviolet device, wherein the porosity of the aeration disc (14) is 30-50%, preferably 45-50%; the pore diameter is 1-20 μm, preferably 8-15 μm;
preferably, the guide cylinder (17) is positioned right above the aeration disc (14).
13. The apparatus for treating acrylonitrile-containing wastewater according to claim 1 or 2, wherein the apparatus for treating wastewater further comprises a water inlet unit and/or a water outlet unit;
the water inlet unit is communicated with the pretreatment unit, preferably the primary sand filtration unit (4), and is used for collecting, homogenizing and stirring the acrylonitrile-containing wastewater to be treated, and the acrylonitrile-containing wastewater enters the pretreatment unit, preferably the primary sand filtration unit (4), through a water outlet pipeline;
the water outlet unit is communicated with the vacuum ultraviolet light catalytic reaction unit and is used for collecting and monitoring the water outlet after reaction.
14. The apparatus for treating acrylonitrile-containing wastewater according to claim 13,
the water inlet unit comprises a water inlet pool (1);
the water inlet tank (1) is provided with a water inlet pipeline and a water outlet pipeline, and the water outlet pipeline is provided with a water inlet pump (3) for controlling the flow of the acrylonitrile-containing wastewater; a stirrer (2) is arranged in the water inlet tank (1) and is used for stirring the wastewater.
15. The apparatus for treating acrylonitrile-containing wastewater as claimed in claim 13, wherein said effluent unit comprises an effluent monitoring tank (20);
the water outlet monitoring pool (20) is communicated with a water outlet of the vacuum ultraviolet light catalytic reaction unit through a water outlet pipeline and is used for collecting and monitoring the outlet water after reaction;
and the water discharge pipeline is also provided with a water discharge pump (19) for opening a water discharge port of the vacuum ultraviolet light catalytic reaction unit to introduce the reacted water into a water discharge monitoring pool (20) or closing the water discharge port of the vacuum ultraviolet light catalytic reaction unit to stop the discharge of the reacted water.
16. A method for treating acrylonitrile-containing wastewater, which is characterized by comprising the following steps:
a pretreatment step: filtering the acrylonitrile-containing wastewater to be treated to obtain filtrate;
vacuum ultraviolet light catalytic reaction: carrying out vacuum ultraviolet light catalytic reaction on the filtrate under the irradiation of vacuum ultraviolet light to obtain reacted effluent; the vacuum ultraviolet light has vacuum ultraviolet waves less than or equal to 200nm and short-wavelength ultraviolet waves more than 200nm, preferably, the wavelength of the vacuum ultraviolet waves is 185nm, and the wavelength of the short-wavelength ultraviolet waves is 254 nm.
17. The treatment method according to claim 16, wherein in the pretreatment step, the acrylonitrile-containing wastewater to be treated is subjected to primary sand filtration and secondary intermediate-effect filtration in sequence, so that the turbidity of the filtrate obtained after the secondary filtration is less than 5 NTU;
preferably, the first-stage sand filtration adopts quartz sand as a filter material, and the diameter of the filter material is 0.5-8mm, more preferably 0.5-5 mm; the filling rate of the filter material is 60-85%, and the retention time of the first-stage sand filtration is 5-10 min;
preferably, the middle-effect filtration is performed by using a PP cotton filter element, and the filtration pore size is 1-5 μm, more preferably 0.5-3 μm; the retention time of the secondary medium-effect filtration is 2-5 min.
18. The process of claim 16, further comprising a catalyst mixing step: the catalyst comprises a homogeneous catalyst and a heterogeneous catalyst, and the filtrate is selectively mixed with the homogeneous catalyst and/or the heterogeneous catalyst before and/or while the filtrate is subjected to vacuum ultraviolet light catalytic reaction under the irradiation of vacuum ultraviolet light;
preferably, the filtrate is mixed with the catalyst in the following manner: the homogeneous catalyst is mixed with the filtrate in a continuous addition prior to the vacuum ultraviolet photocatalytic reaction, and the heterogeneous catalyst is mixed with the filtrate in a batch addition, more preferably a one-time addition, prior to and/or simultaneously with the vacuum ultraviolet photocatalytic reaction.
19. The treatment process according to claim 18, wherein the homogeneous catalyst is selected from one or more of hydrogen peroxide, sodium persulfate, ferrous sulfate and sodium hypochlorite, preferably the homogeneous catalyst is used in the form of an aqueous solution;
the molar concentration ratio of the homogeneous catalyst to acrylonitrile in the wastewater is 0.2-0.8: 1.
20. The process of claim 18, wherein the heterogeneous catalyst comprises a support and an active component supported on the support, wherein the active component is at least one of a semiconductor material, a metal of group VIII of the periodic Table, a non-metal of group IVA of the periodic Table, and a non-metal of group VA of the periodic Table, and wherein the semiconductor material is TiO2And/or ZnO, wherein the metal active component is Fe and/or Cu, the nonmetal active component is C and/or N, the carrier is a molecular sieve, and the molecular sieve is ZSM-5 and/or OMS-2; the content of the semiconductor material is 5-20 wt% based on the total weight of the heterogeneous catalyst; the total content of the metal element and the nonmetal element calculated by the elements is 1-5 wt% based on the total weight of the heterogeneous catalyst;
based on the amount of 1L of acrylonitrile-containing wastewater, the dosage of the heterogeneous catalyst is 0.5g-2g。
21. The process of any one of claims 16 and 18 to 20, wherein in the vacuum ultraviolet photocatalytic reaction step, the reaction method comprises: carrying out vacuum ultraviolet light catalytic reaction on the filtrate; the power of a single vacuum ultraviolet light source is 20-150W, and preferably, the number of the vacuum ultraviolet light sources is 4-8; the residence time of the vacuum ultraviolet light catalytic reaction is 30-90 min;
preferably, the filtrate is optionally mixed with a homogeneous catalyst and/or a heterogeneous catalyst, more preferably, the filtrate is mixed with a homogeneous catalyst and a heterogeneous catalyst;
further preferably, the reaction is carried out under aeration conditions, wherein the gas for aeration is selected from one or more of ozone, air, oxygen and nitrogen, and the aeration amount is 50 to 200mL/min based on 1L of the acrylonitrile-containing wastewater.
22. The processing method of claim 21, wherein the processing method further comprises: and filtering the effluent after the reaction after the vacuum ultraviolet light catalytic reaction.
23. The processing method according to any one of claims 16 to 22, wherein the processing method further comprises:
homogenizing: collecting, buffering and stirring before pretreating acrylonitrile-containing wastewater to be treated; and/or the presence of a gas in the gas,
a water drainage step: and collecting and monitoring the effluent after the reaction.
24. A method for treating acrylonitrile-containing wastewater, which is carried out in the treatment apparatus according to any one of claims 1 to 15, and which comprises:
a pretreatment step: the method comprises the following steps of (1) filtering acrylonitrile-containing wastewater to be treated in a pretreatment unit to obtain filtrate;
vacuum ultraviolet light catalytic reaction: the filtrate enters a vacuum ultraviolet light catalytic reaction unit, and is subjected to vacuum ultraviolet light catalytic reaction under the irradiation of vacuum ultraviolet light to obtain reacted effluent; the vacuum ultraviolet light has vacuum ultraviolet waves less than or equal to 200nm and short-wavelength ultraviolet waves more than 200nm, preferably, the wavelength of the vacuum ultraviolet waves is 185nm, and the wavelength of the short-wavelength ultraviolet waves is 254 nm.
25. The treatment method according to claim 24, wherein in the pretreatment step, the acrylonitrile-containing wastewater to be treated sequentially enters a primary sand filtration unit (4) for primary sand filtration and a secondary intermediate filtration unit (7) for secondary intermediate filtration to obtain a filtrate, so that the turbidity of the filtrate obtained after the secondary filtration is less than 5 NTU;
preferably, the first-stage sand filtration adopts quartz sand as a filter material, and the diameter of the filter material is 0.5-8mm, more preferably 0.5-5 mm; the filling rate of the filter material is 60-85%, and the retention time of the first-stage sand filtration is 5-10 min;
preferably, the middle-effect filtration is performed by using a PP cotton filter element, and the filtration pore size is 1-5 μm, more preferably 0.5-3 μm; the retention time of the secondary medium-effect filtration is 2-5 min.
26. The process of claim 24, further comprising a catalyst mixing step: the catalyst comprises a homogeneous catalyst and a heterogeneous catalyst, the filtrate enters a vacuum ultraviolet light catalytic reaction unit, and the filtrate is selectively mixed with the homogeneous catalyst and/or the heterogeneous catalyst before and/or while the vacuum ultraviolet light catalytic reaction is carried out under the irradiation of vacuum ultraviolet light;
preferably, the filtrate is mixed with the catalyst in the following manner: the filtrate enters a homogeneous catalyst mixing zone (9) of a catalyst adding unit through a filtrate water outlet pipeline and is mixed with a homogeneous catalyst added to the homogeneous catalyst mixing zone (9) through a homogeneous catalyst automatic adding device (10), and the homogeneous catalyst is mixed with the filtrate in a continuous adding mode;
preferably, before and/or at the same time when the filtrate mixed with the homogeneous catalyst enters a reaction cylinder (12) of a vacuum ultraviolet device of a vacuum ultraviolet catalytic reaction unit, the heterogeneous catalyst is added into the reaction cylinder (12) of the vacuum ultraviolet device, and more preferably, the heterogeneous catalyst is added into the reaction cylinder (12) of the vacuum ultraviolet device through an automatic heterogeneous catalyst adding device (11); the heterogeneous catalyst is added into a reaction cylinder (12) of the vacuum ultraviolet device in a batch mode, preferably in a one-time adding mode, and is mixed with the filtering liquid.
27. The treatment method according to claim 26, wherein the homogeneous catalyst is selected from one or more of hydrogen peroxide, sodium persulfate, ferrous sulfate and sodium hypochlorite, preferably the homogeneous catalyst is used in the form of an aqueous solution, and the dosage of the homogeneous catalyst used in the form of the aqueous solution is 0.3-1.5L/h, so that the molar concentration ratio of the homogeneous catalyst to acrylonitrile in the wastewater is 0.2-0.8: 1.
28. The process of claim 26, wherein the heterogeneous catalyst comprises a support and an active component supported on the support, wherein the active component is at least one of a semiconductor material, a metal of group VIII of the periodic Table of the elements, a non-metallic element of group IVA of the periodic Table of the elements, and a non-metallic element of group VA of the periodic Table of the elements, and wherein the semiconductor material is TiO2And/or ZnO, wherein the metal active component is Fe and/or Cu, the nonmetal active component is C and/or N, the carrier is a molecular sieve, and the molecular sieve is ZSM-5 and/or OMS-2; the content of the semiconductor material is 5-20 wt% based on the total weight of the heterogeneous catalyst; the total content of the metal element and the nonmetal element calculated by the elements is 1 to 5 weight percent based on the total weight of the heterogeneous catalyst;
based on the amount of 1L of acrylonitrile-containing wastewater, the dosage of the heterogeneous catalyst is 0.5g-2g。
29. The process of any one of claims 24 to 28, wherein in the vacuum uv-photocatalytic reaction step, the reaction method comprises: the filtrate enters a reaction cylinder (12) of a vacuum ultraviolet device, and simultaneously a vacuum ultraviolet light source (13) is started to irradiate the wastewater containing the acrylonitrile so as to carry out vacuum ultraviolet catalytic reaction; the power of a single vacuum ultraviolet light source is 20-150W, and the number of the vacuum ultraviolet light sources (13) is preferably 4-8; the residence time of the vacuum ultraviolet light catalytic reaction is 30-90 min;
preferably, the filtrate is optionally mixed with a homogeneous catalyst and/or a heterogeneous catalyst, more preferably, the filtrate is mixed with a homogeneous catalyst and a heterogeneous catalyst;
further preferably, the filtrate at least mixed with the heterogeneous catalyst enters the reaction cylinder (12) of the vacuum ultraviolet device, enters from the lower part of the guide cylinder (17) and flows out from the upper part, and the heterogeneous catalyst is in a uniform and fluidized state in the reaction cylinder (12) of the vacuum ultraviolet device;
further preferably, gas is introduced into the vacuum ultraviolet device reaction cylinder (12) through the gas inlet (15) and is aerated through the aeration disc (14) at the bottom of the vacuum ultraviolet device reaction cylinder (12), the aerated gas is selected from one or more of ozone, air, oxygen and nitrogen, and the aeration rate is 50-200mL/min relative to 1L of acrylonitrile-containing wastewater.
30. The process of claim 29, wherein the process further comprises: after the vacuum ultraviolet light catalytic reaction, the effluent water after the reaction is filtered by a hollow membrane component (18) and is sent out of a vacuum ultraviolet device reaction cylinder body (12) of a vacuum ultraviolet light catalytic reaction unit through a water outlet.
31. The process of claim 24, wherein the process further comprises:
homogenizing: before the acrylonitrile-containing wastewater to be treated enters the pretreatment unit, the acrylonitrile-containing wastewater is firstly put into a water inlet pool (1) of a water inlet unit for collection, buffering and stirring; and/or the presence of a gas in the gas,
a water drainage step: and the effluent after reaction enters an effluent monitoring pool (18) of the effluent unit for collection and monitoring.
32. The treatment method as claimed in any one of claims 24 to 31, wherein the water inlet speed of the acrylonitrile-containing wastewater to be treated is 100-500mL/min, and the water inlet speed and the water outlet speed are the same.
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