CN114105348A - Device and method for treating benzo (a) pyrene in coking wastewater - Google Patents
Device and method for treating benzo (a) pyrene in coking wastewater Download PDFInfo
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Abstract
The invention discloses a device and a method for treating benzo (a) pyrene in coking wastewater. The device homogeneity adjusting device; the oil separation device is connected with the homogeneity adjusting device; the coagulating sedimentation device is connected with the oil separation device; the filtering device is connected with the coagulating sedimentation device; the first pH adjusting device is connected with the filtering device; with the fenton reactor that first pH adjusting device is connected, be provided with heterogeneous fenton catalysis module in the fenton reactor. The coking wastewater containing benzo (a) pyrene is treated in a heterogeneous Fenton oxidation device after being homogenized, oil-isolated, coagulating and precipitated and pH adjusted, and the treated effluent benzo (a) pyrene reaches the standard and can be partially recycled or sent to the next process unit. The method for treating coking wastewater containing benzo (a) pyrene can effectively ensure that the first pollutant benzo (a) pyrene at the discharge outlet of the device reaches the standard.
Description
Technical Field
The invention belongs to the technical field of chemical industry and environmental protection, and particularly relates to a device and a method for treating benzo (a) pyrene in coking wastewater.
Background
Delayed coking is one of the important means for heavy oil processing, and its advantages in heavy oil processing are becoming more and more apparent with the upgrading and deterioration of crude oil. However, the waste water of the coking industry contains a large amount of organic matters which are difficult to treat, and especially polycyclic aromatic hydrocarbon pollutants are not only difficult to degrade, but also are generally strong carcinogenic substances. The benzo (a) pyrene (BaP) belongs to the first pollutant strictly controlled by the state, is mainly generated by the high-temperature pyrolysis, cyclization and polymerization of carbonaceous substances such as coal, petroleum, firewood and the like, has strong carcinogenicity, and can directly threaten human health while causing serious environmental pollution. The benzo (a) pyrene has strict emission control standards in wastewater, and the emission standard of the benzo (a) pyrene is lower than 0.03 mu g/L in the 31570-2015 standard of the refining industry. Because the concentration of benzo (a) pyrene in wastewater is low, the standard discharge is difficult to realize by using the conventional method for treatment. With the national higher and higher environmental protection requirements, how to treat the coking wastewater containing benzo (a) pyrene becomes a problem to be solved urgently in the coking industry.
At present, the reports on the treatment technology of benzo (a) pyrene in wastewater are less, and the technology for treating coking wastewater containing benzo (a) pyrene is more lacking. CN200810155656.5 reports a method for deeply treating benzo (a) pyrene in a drinking water source by a biological membrane, which is characterized by fusing protoplasts of three parent strains of eukaryotic prokaryotic cells of white rot fungi, indigenous bacteria YZ and saccharomyces cerevisiae, constructing genetic engineering bacteria through gene recombination and integration, and introducing the genetic engineering bacteria into a columnar reactor filled with an activated carbon carrier to remove the benzo (a) pyrene in the drinking water source. However, the process aims at trace benzo (a) pyrene in drinking water, and industrial wastewater is difficult to treat. CN201410312754.0 reports a method for rapidly, efficiently and selectively degrading trace benzo (a) pyrene in water, after wastewater containing trace benzo (a) pyrene after conventional biochemical treatment is cut into water films by filler in an ozone catalytic oxidation reaction tank, the water films are contacted and dissolved with ozone or ozonized air flowing reversely, and the trace benzo (a) pyrene in the wastewater is selectively degraded. However, the technology only adopts ozone oxidation, the consumption of the oxidant is large, and the cost is high. CN201610734933.2 reports an advanced treatment process for petrochemical wastewater, which is characterized in that a composite treatment agent is prepared from modified starch, silicon carbonate, aluminum hydroxide, polymeric ferric sulfate, polyaluminium silicate sulfate, calcite powder, egg white powder, sodium hypochlorite, polymeric aluminum calcium chloride, sodium hydroxide caustic soda flakes, glacial acetic acid, 3-oxo-1-cyclopentanecarboxylic acid, potassium ethoxide, pilocarpine and a coagulant aid, and the composite treatment agent is matched with corresponding water treatment processes such as adsorption, treatment with a treatment agent, anaerobic treatment, photocatalytic oxidation, sodium hypochlorite oxidation, aeration, electric flocculation, electric air flotation and the like, so that COD, oil content, benzo (a) pyrene content and chroma of the treated wastewater are all remarkably reduced, and the requirements of environmental protection and standard reaching can be met. However, the process is complex, a lot of auxiliary agents are added into the wastewater, the cost is high, and the subsequent sewage and sludge treatment is difficult.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a device and a method for treating benzo (a) pyrene in coking wastewater. Firstly, after the coking wastewater containing benzo (a) pyrene is homogenized, subjected to oil removal, subjected to coagulating sedimentation and subjected to pH adjustment, the coking wastewater enters a heterogeneous Fenton oxidation device for treatment, the treated effluent benzo (a) pyrene reaches the standard, and part of the effluent is recycled or sent to the next process unit. The method for treating coking wastewater containing benzo (a) pyrene can effectively ensure that the first pollutant benzo (a) pyrene at the discharge outlet of the device reaches the standard.
According to a first method aspect, the invention provides a device for treating benzo (a) pyrene in coking wastewater, which comprises:
a homogeneity adjusting device;
the oil separation device is connected with the homogeneity adjusting device;
the coagulating sedimentation device is connected with the oil separation device;
the filtering device is connected with the coagulating sedimentation device;
the first pH adjusting device is connected with the filtering device;
with the fenton reactor that first pH adjusting device is connected, be provided with heterogeneous fenton catalysis module in the fenton reactor.
According to some embodiments of the present invention, the homogenization treatment device is used for performing homogenization treatment on the coking wastewater to obtain homogenized coking wastewater.
According to some embodiments of the invention, the oil separation device is used for carrying out oil separation treatment on the homogenized coking wastewater to remove scum and oil substances in the wastewater.
According to some embodiments of the invention, the coagulating sedimentation device is used for coagulating sedimentation treatment of the wastewater after oil separation treatment to obtain coagulated wastewater and sludge sediment, and the precipitated sludge is collected at the bottom of the coagulating sedimentation tank and discharged from a sludge discharge port for waste residue collection.
According to some embodiments of the invention, the filtration device is used to further remove suspended matter from the coagulated wastewater.
According to some embodiments of the invention, the filter device is a Y-filter.
According to some embodiments of the invention, the first pH adjusting device is used to adjust the pH of the filtered incoming water.
According to some embodiments of the invention, the fenton reactor is used for performing a fenton catalytic oxidation reaction of wastewater after pH adjustment.
According to some embodiments of the invention, the fenton reactor comprises an effluent zone, a reaction zone provided with a heterogeneous fenton catalytic module and an influent zone.
According to some embodiments of the invention, a distribution plate is disposed between the reaction zone and the water inlet zone.
According to some embodiments of the invention, the distribution plate is selected from a grid distribution plate or a strip distribution plate.
According to some embodiments of the invention, the water outlet zone is provided with a first water outlet and a circulating water outlet, the water inlet zone is provided with a water inlet, and the circulating water outlet and the water inlet are connected through a pipeline.
According to some embodiments of the invention, the heterogeneous fenton catalytic module comprises a heterogeneous fenton catalyst.
According to some embodiments of the invention, one or more swash plates are provided in the oil barrier.
According to some embodiments of the invention, the inclined plate is at an angle of 30 to 45 degrees to the horizontal.
According to some embodiments of the invention, the apparatus further comprises a second pH adjusting device connected to the fenton reactor.
According to some embodiments of the invention, the second pH adjusting device is used for pH adjustment of the fenton reaction effluent.
In some embodiments of the present invention, the apparatus includes a homogenizing tank, an oil separation tank, a coagulating sedimentation tank, a filter, a first pH adjusting tank, a fenton reactor, a circulating pump, and a second pH adjusting tank, which are connected in sequence.
According to some embodiments of the invention, the homogenizing pool 1 is connected with the inlet of the homogenizing pool lifting pump 2 through a pipeline, the outlet of the homogenizing tank lift pump 2 is connected with the inlet 4 of the oil separation tank through a pipeline, the outlet 5 of the oil separation tank is connected with the inlet 9 of the coagulating sedimentation tank through a pipeline, the outlet 17 of the coagulating sedimentation tank is connected with a Y-shaped filter 18 through a pipeline, the outlet water of the Y-shaped filter 18 is connected with an inlet 22 of a pH adjusting tank through a pipeline, an outlet 23 of the pH adjusting tank is mixed with circulating water and then is connected with an inlet 25 at the bottom of the Fenton reactor through a pipeline, the circulating water outlet 29 of the Fenton reactor is connected with the inlet of a circulating pump 30, the outlet of the circulating pump 30 is connected with the outlet of a metering pump 32 of H2O2 through a pipeline, the outlet 31 of the Fenton reactor is connected with the inlet 37 of the pH adjusting tank through a pipeline, and the outlet 38 of the pH adjusting tank is connected with the inlet 40 of the effluent sedimentation tank through a pipeline.
According to a second aspect, the method for treating benzo (a) pyrene in coking wastewater provided by the invention adopts the device of the first aspect, and comprises the following steps:
s1, introducing the coking wastewater into a homogenizing adjusting device for homogenizing adjustment to obtain first effluent;
s2, introducing the first effluent obtained in the step S1 into an oil separation device for oil separation treatment to obtain second effluent;
s3, introducing the second effluent obtained in the step S2 into a coagulating sedimentation device for coagulating sedimentation treatment to obtain third effluent after coagulating sedimentation treatment;
s4, introducing the third effluent obtained in the step S3 into a filtering device for filtering treatment to obtain fourth effluent after filtering treatment;
s5, introducing the fourth effluent obtained in the step S4 into a first pH adjusting device for pH adjustment to obtain an acidic fifth effluent;
and S6, introducing the fifth effluent obtained in the step S5 into a Fenton reactor for catalytic oxidation reaction to obtain reacted sixth effluent.
According to some embodiments of the invention, in S2, the residence time of the first effluent in the oil separator is 10-80min, such as 15min, 25min, 30min, 40min, 50min, 65min, 70min and any value in between.
According to some embodiments of the invention, in S2, the residence time of the first effluent in the oil separator is 20-60 min.
According to some embodiments of the invention, the oil content in the second effluent is less than 3mg/L in S2.
According to some embodiments of the invention, in S3, the second effluent is introduced into a coagulating sedimentation device to be mixed with a coagulating sedimentation agent for coagulating sedimentation, and the wastewater after coagulating sedimentation is separated to obtain a third effluent.
According to some embodiments of the invention, the coagulating sedimentation agent comprises a flocculating agent and a coagulant.
According to some embodiments of the invention, the flocculant is selected from one or more of polymers of iron.
According to some embodiments of the invention, the flocculant is selected from the group consisting of Polymeric Ferric Sulfate (PFS).
According to some embodiments of the invention, the coagulant aid is selected from one or more of polyacrylamide coagulant aids.
According to some embodiments of the invention, the coagulant aid is selected from Polyacrylamide (PAM).
According to some embodiments of the present invention, the flocculant is present in an amount of 50 to 150mg/L, such as 55mg/L, 65mg/L, 70mg/L, 80mg/L, 90mg/L, 95mg/L, 110mg/L, 120mg/L, 130mg/L and any value therebetween, based on the volume of the coking wastewater.
According to some embodiments of the invention, the flocculant is used in an amount of 60 to 100mg/L based on the volume of the coking wastewater.
According to some embodiments of the present invention, the coagulant aid is used in an amount of 1 to 15mg/L, such as 2mg/L, 3.5mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L, 8mg/L, 9mg/L, 11mg/L, 12mg/L, 13mg/L and any value therebetween, based on the volume of the coking wastewater.
According to some embodiments of the present invention, the coagulant aid is used in an amount of 3 to 10mg/L based on the volume of the coking wastewater.
According to some embodiments of the invention, in S5, the pH of the fourth effluent is adjusted with a mineral acid.
According to some embodiments of the invention, the pH of the acidic fifth effluent in S5 is 2-4.5.
According to some embodiments of the invention, in S5, the inorganic acid is selected from one or more of hydrochloric acid, sulfuric acid, and nitric acid.
In some preferred embodiments of the present invention, the acid used to adjust the pH of the fourth effluent is preferably H2SO4H at a concentration of preferably 10%2SO4。
According to some embodiments of the invention, in S6, the fifth effluent is subjected to a catalytic oxidation reaction with an oxidant in the presence of a heterogeneous fenton catalyst.
According to some embodiments of the invention, the heterogeneous fenton catalyst has a volume fill ratio within the fenton reactor of 50-90%, such as 55%, 60%, 65%, 70%, 75%, 80%, 85% and any value in between.
According to some embodiments of the present invention, the oxidizing agent is used in an amount of 0.5 to 6g/L, such as 1.0g/L, 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L, 3.5g/L, 4.0g/L, 4.5g/L, 5.0g/L, 5.5g/L, and any value therebetween, based on the volume of the coking wastewater.
According to some embodiments of the invention, the residence time of the fifth effluent in the fenton reactor is between 0.5 and 2h, such as 0.6h, 0.8h, 1.0h, 1.2h, 1.4h, 1.6h, 1.8h and any value in between.
According to some embodiments of the invention, the heterogeneous fenton catalyst comprises a carrier and an active component supported on the carrier.
According to some embodiments of the invention, the support is selected from activated carbon.
According to some embodiments of the invention, the active component is selected from Fe and/or Cu.
According to some embodiments of the invention, the loading of the active component is 5-20 wt% of the support, such as 7 wt%, 9 wt%, 11 wt%, 12 wt%, 15 wt%, 17 wt%, 19 wt%, and any value therebetween.
According to the invention, a heterogeneous Fenton catalyst is adopted, the catalyst can be separated from a reaction system and recycled, macroporous biological activated carbon is preferably selected as a carrier, and the spent carrier activated carbon can be sent to a coking device for combustion treatment without secondary pollution.
According to some embodiments of the invention, the oxidant is selected from 27.5% hydrogen peroxide.
In some preferred embodiments of the present invention, the oxidizing agent is hydrogen peroxide, and preferably, the mass fraction of the hydrogen peroxide is 27.5%.
According to some embodiments of the present invention, a part of the sixth effluent obtained in S6 is passed into the second pH adjusting device for pH adjustment to obtain a treated effluent, and the remaining part of the sixth effluent is recycled as a circulating water to the fenton reactor for continuing the catalytic oxidation reaction.
According to some embodiments of the present invention, the circulating water and the fifth effluent and/or the oxidant are mixed and introduced into the water inlet zone of the fenton reactor, and enter the reaction zone after being distributed by the distribution plate to perform the catalytic oxidation reaction.
In the invention, a part of the sixth effluent is taken as circulating water and circulated to the Fenton reactor for continuous catalytic oxidation reaction, so that organic substances of benzo (a) pyrene can be better degraded and decomposed thoroughly. In the invention, the bottom of the Fenton reactor is provided with a grid plate water distribution area (the grid plate means that the water distribution area of the water distribution plate is in a grid strip shape), a catalyst carrier is arranged in the oxidation reaction area, and the catalyst catalyzes H2O2Decompose to generate high-activity hydroxyl free radical (OH), effectively degrade organic matters, avoid instantaneously generating a large amount of OH, and improve H2O2The utilization ratio of (2).
According to some embodiments of the present invention, the pH of the sixth effluent passed into the second pH adjusting device is adjusted with a basic solution, preferably to a slightly alkaline pH, e.g. 7-9.
According to some embodiments of the invention, the lye is preferably a NaOH solution.
According to some preferred embodiments of the invention, the method comprises the following specific steps:
firstly, feeding the coking wastewater into a homogenizing and adjusting tank for homogenizing and adjusting;
secondly, the homogenized coking wastewater is introduced into an oil separation tank to remove scum and oil substances in the wastewater, and after oil separation treatment, the oil content in the wastewater is less than 3mg/L, so that the adverse effect of tar substances on a subsequent oxidation unit is eliminated;
thirdly, introducing the wastewater subjected to the oil separation treatment into a coagulation sedimentation tank, adding a flocculating agent and a coagulant aid to mix with the wastewater, and coagulating to generate alum flocs and alum floc sediment under the action of a stirring paddle;
fourthly, filtering supernatant after coagulating sedimentation, then feeding the filtered supernatant into a pH adjusting tank I, adding acid into the pH adjusting tank I to adjust the pH value, mixing the supernatant with circulating water, then feeding the mixture into a Fenton reactor to be treated, discharging a part of effluent after the concentration of benzo (a) pyrene reaches the standard, and discharging most of circulating water and H2O2Mixing and refluxing to the reactor;
and fifthly, the effluent of the Fenton reactor enters a pH adjusting tank II, alkali is added into the pH adjusting tank II to adjust the pH value, the effluent enters an effluent tank, and part of the effluent is recycled or enters the next process unit.
According to some embodiments of the invention, the coking wastewater has a benzo (a) pyrene concentration of 0.03 to 90 μ g/L.
The invention has the following beneficial effects:
(1) the invention adopts the oil separation tank to pretreat the coking wastewater, can effectively remove heavy oil and missible oil in the wastewater at low cost, and is beneficial to subsequent operation units.
(2) The invention adopts the coagulating sedimentation treatment, removes most suspended matters and partial dissolved pollutants in the coking wastewater through the high-efficiency coagulating sedimentation pretreatment, reduces the consumption of chemical agents in the subsequent oxidation process, reduces the treatment cost, and simultaneously effectively improves the treatment effect.
(3) Heterogeneous Fenton catalyst is arranged in an oxidation reaction zone of the Fenton device, the catalyst can be separated from a reaction system and recycled, macroporous biological activated carbon is preferably selected as a carrier, and the spent carrier activated carbon can be sent to a coking device for combustion treatment without secondary pollution.
(4) Heterogeneous Fenton catalyst for catalyzing H2O2Decompose to generate high-activity hydroxyl free radical (OH), effectively degrade organic matters, avoid instantaneously generating a large amount of OH, and improve H2O2The utilization ratio of (2).
(5) The method can degrade benzo (a) pyrene organic matters at normal temperature and normal pressure, is thorough in decomposition, and has high application value; the reactor has the advantages of simplified structure, small occupied area and capability of reducing the production and manufacturing cost and the use and operation cost.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention:
in fig. 1, 1 is a homogenizing tank, 2 is a homogenizing tank lift pump, 3 is an oil separating tank, 4 is an oil separating tank inlet, 5 is an oil separating tank outlet, 6 is a coagulating agent tank, 7 is an agent metering pump, 8 is a coagulating sedimentation tank, 9 is a coagulating sedimentation tank inlet, 10 is a coagulating zone, 11 is a hollow rotating shaft, 12 is a stirring blade, 13 is a partition plate, 14 is a sedimentation zone, 15 is a sludge discharge port, 16 is an overflow weir, 17 is a coagulating sedimentation tank outlet, 18 is a Y-shaped filter, 19 is an acid liquid tank, 20 is an acid liquid metering pump, 21 is a pH adjusting tank one, 22 is a pH adjusting tank one inlet, 23 is a pH adjusting tank one outlet, 24 is a fenton reactor, 25 is a fenton reactor inlet, 26 is a distribution plate, 27 is a catalyst carrier, 28 is a water outlet zone, 29 is a circulating water outlet, 30 is a circulating pump, 31 is a fenton reactor outlet, and 32 is H2O2Metering pump, 33 is H2O2The tank 34 is an alkali liquor tank, 35 is an alkali liquor metering pump, 36 is a pH adjusting tank II, 37 is an inlet of the pH adjusting tank II, 38 is an outlet of the pH adjusting tank II, 39 is a water outlet tank, 40 is an inlet of the water outlet tank, 41 is an outlet of the water outlet tank, and 42 is a sludge discharge port of the water outlet tank.
Detailed Description
The invention provides a device for treating benzo (a) pyrene in coking wastewater, which comprises a homogenizing tank 1, an oil separation tank 3, a coagulating sedimentation tank 8, a filter 18, a pH adjusting tank I21, a Fenton reactor 24, a circulating pump 30 and a pH adjusting tank II 36 which are connected in sequence. The device comprises a homogenizing tank 1, a homogenizing tank lifting pump 2, an oil separation tank inlet 4, an oil separation tank outlet 5, a coagulating sedimentation tank inlet 9, a coagulating sedimentation tank outlet 17, a Y-type filter 18, a pH adjusting tank inlet 22, a pH adjusting tank outlet 23, a circulating water outlet 29, a circulating pump 30 and an H outlet, wherein the homogenizing tank 1 is connected with the homogenizing tank lifting pump 2 through a pipeline, the homogenizing tank lifting pump 2 outlet is connected with the oil separation tank inlet 4 through a pipeline, the oil separation tank outlet 5 is connected with the coagulating sedimentation tank inlet 9 through a pipeline, the coagulating sedimentation tank outlet 17 is connected with the Y-type filter 18 through a pipeline, the Y-type filter 18 outlet is connected with the pH adjusting tank inlet 22 through a pipeline, the pH adjusting tank outlet 23 is connected with the circulating water through a pipeline after being mixed with the circulating water and then is connected with the Fenton reactor bottom inlet 25, the Fenton reactor circulating water outlet 29 is connected with the circulating pump 30, and the circulating pump 30 outlet is connected with the H inlet2O2The outlet of the metering pump 32 is connected with the outlet of the Fenton reactor 31 through a pipeline, the outlet of the Fenton reactor 31 is connected with the inlet 37 of the pH adjusting tank through a pipeline, and the outlet 38 of the pH adjusting tank is connected with the inlet 40 of the effluent sedimentation tank through a pipeline.
The invention provides a treatment method for treating benzo (a) pyrene in coking wastewater, which is shown in the attached figure 1:
(1): feeding the coking wastewater into a homogenizing and adjusting tank 1 for homogenizing and adjusting;
(2): the homogenized coking wastewater is sent to an oil separation tank 3 through a homogenizing tank lifting pump 2 to remove scum and oil substances in the wastewater, after oil separation treatment, the oil content in the wastewater is less than 3mg/L, and the adverse effect of tar substances on a subsequent oxidation unit is eliminated;
(3): sending the water discharged from the oil separation tank 3 to a coagulating sedimentation tank 8, adding a flocculating agent and a coagulant aid to mix with the wastewater, coagulating to generate alum floc under the action of a stirring blade, discharging the alum floc precipitate from a sludge discharge port, and removing most of benzo (a) pyrene attached to suspended matters;
(4): discharging supernatant after coagulating sedimentation in the coagulating sedimentation tank 8 through an overflow weir 16, filtering effluent again through a Y-shaped filter 18, then feeding the effluent into a pH adjusting tank I21, adding acid into the pH adjusting tank I to adjust the pH value, mixing the effluent with circulating water, and then feeding the mixture into a Fenton reactor 24 for treatment, wherein the concentration of benzo (a) pyrene in the effluent reaches the standard, discharging a part of the effluent, and most of the circulating water and H2O2Mixing and refluxing to the reactor;
(5): and the effluent of the Fenton reactor enters a pH adjusting tank II, alkali is added into the pH adjusting tank II to adjust the pH value, the effluent enters an effluent tank, and part of the effluent is recycled or enters the next process unit.
A large amount of iron mud is generated in the traditional homogeneous Fenton reaction, the concentration of iron ions in effluent can exceed the standard, a catalyst cannot be recycled, and the treatment cost is high. The bottom of the Fenton reactor is provided with a grid plate water distribution area, a catalyst carrier is arranged in the oxidation reaction area, and the catalyst catalyzes H2O2Decompose to generate high-activity hydroxyl free radical (OH), effectively degrade organic matters, avoid instantaneously generating a large amount of OH, and improve H2O2The utilization ratio of (2). Heterogeneous catalysisThe catalyst can be separated from the reaction system and recycled, the carrier is preferably macroporous biological activated carbon, and the spent carrier activated carbon after use can be sent to a coking device for combustion treatment without secondary pollution.
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the invention in any way.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1: the concentration of benzo (a) pyrene in a discharge outlet of a coking device of a certain refinery is 80 mug/L, the benzo (a) pyrene is treated by adopting the process flow of the invention, the benzo (a) pyrene is treated by heterogeneous Fenton catalytic oxidation after oil removal and flocculation sedimentation, the retention time of an oil separation tank is 40min, the dosage of PFS is added according to 90mg of wastewater per liter, the dosage of PAM is added according to 10mg of wastewater per liter, the pH of inlet water is adjusted to 3.5, the retention time of the wastewater in a Fenton oxidation device is 1H, H is added2O2The dosage of the catalyst is added according to 2g per liter of wastewater, the volume filling rate of the heterogeneous Fenton catalyst in the Fenton reactor is 70%, the heterogeneous catalyst is active carbon particles loaded with Fe, the load amount of Fe is 10 wt% of the active carbon, and the pH value of effluent is adjusted to be 7.5. The concentration of the benzo (a) pyrene in the effluent after treatment is 0.03 mu g/L.
Comparative example 1: the concentration of benzo (a) pyrene in certain coking wastewater is 80 mug/L. Using no coagulation device, unlike example 1, the heterogeneous Fenton residence time was increased by 30%, H2O2The dosage is increased by 25 percent, and the removal rate of benzo (a) pyrene is reduced by 20 percent.
Example 2: the concentration of benzo (a) pyrene in a discharge port of a coking device in a certain refinery is 5 mug/L, the benzo (a) pyrene is treated by adopting the process flow of the invention, the benzo (a) pyrene is treated by heterogeneous Fenton catalytic oxidation after oil removal and flocculation sedimentation, the retention time of an oil separation tank is 30min, the dosage of PFS is added according to 70mg of wastewater per liter, the dosage of PAM is added according to 5mg of wastewater per liter, the pH of inlet water is adjusted to 4.5, and the wastewater is subjected to Fenton oxygen oxidationThe residence time in the apparatus is 1H, H2O2The dosage of the catalyst is added according to 0.5g per liter of wastewater, the volume filling rate of the heterogeneous Fenton catalyst in the Fenton reactor is 70%, the heterogeneous catalyst is activated carbon particles loaded with Cu, the loading amount of the Cu is 10 wt% of the activated carbon, and the pH value of effluent is adjusted to be 8. The concentration of the benzo (a) pyrene in the effluent after treatment is 0.02 mu g/L.
Comparative example 2: the concentration of benzo (a) pyrene in certain coking wastewater is taken as 5 mu g/L. Different from the embodiment 2, the heterogeneous catalyst is Cu-loaded alumina particles, and the treated alumina particles which are out of service are dangerous wastes, so that secondary pollution is formed.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. An apparatus for treating benzo (a) pyrene in coking wastewater, comprising:
a homogeneity adjusting device;
the oil separation device is connected with the homogeneity adjusting device;
the coagulating sedimentation device is connected with the oil separation device;
the filtering device is connected with the coagulating sedimentation device;
the first pH adjusting device is connected with the filtering device;
with the fenton reactor that first pH adjusting device is connected, be provided with heterogeneous fenton catalysis module in the fenton reactor.
2. The device according to claim 1, wherein the Fenton reactor comprises an outlet area, a reaction area provided with the heterogeneous Fenton catalytic module and an inlet area, preferably a distribution plate is arranged between the reaction area and the inlet area, preferably the distribution plate is selected from a grid-shaped distribution plate or a strip-shaped distribution plate, and/or the outlet area is provided with a first water outlet and a circulating water outlet, the inlet area is provided with a water inlet, and the circulating water outlet and the water inlet are connected through a pipeline;
and/or the heterogeneous fenton catalytic module comprises a heterogeneous fenton catalyst.
3. The device according to claim 1 or 2, characterized in that one or more inclined plates are arranged in the oil separator, preferably the inclined plates are at an angle of 30-45 degrees to the horizontal;
and/or the apparatus further comprises a second pH adjusting means connected to the fenton reactor.
4. A method for treating benzo (a) pyrene in coking wastewater by using the apparatus of any one of claims 1 to 3, comprising the steps of:
s1, introducing the coking wastewater into a homogenizing adjusting device for homogenizing adjustment to obtain first effluent;
s2, introducing the first effluent obtained in the step S1 into an oil separation device for oil separation treatment to obtain second effluent;
s3, introducing the second effluent obtained in the step S2 into a coagulating sedimentation device for coagulating sedimentation treatment to obtain third effluent after coagulating sedimentation treatment;
s4, introducing the third effluent obtained in the step S3 into a filtering device for filtering treatment to obtain fourth effluent after filtering treatment;
s5, introducing the fourth effluent obtained in the step S4 into a first pH adjusting device for pH adjustment to obtain an acidic fifth effluent;
and S6, introducing the fifth effluent obtained in the step S5 into a Fenton reactor for catalytic oxidation reaction to obtain reacted sixth effluent.
5. The method according to claim 4, characterized in that in S2, the residence time of the first effluent in the oil separator is 10-80min, preferably 20-60 min; and/or the oil content in the second effluent is less than 3 mg/L.
6. The method according to claim 4 or 5, wherein in S3, the second effluent is introduced into a coagulating sedimentation device to be mixed with a coagulating sedimentation agent for coagulating sedimentation, and a third effluent is obtained after the wastewater after coagulating sedimentation is separated;
preferably, the coagulator flocculant and coagulant, more preferably the flocculant is selected from one or more of iron polymers, preferably from polymeric ferric sulphate, and/or the coagulant aid is selected from one or more of polyacrylamide coagulant aids, preferably from polyacrylamide;
most preferably, the dosage of the flocculating agent is 50-150mg/L, preferably 60-100mg/L and/or the dosage of the coagulant aid is 1-15mg/L, preferably 3-10mg/L based on the volume of the coking wastewater;
and/or in S5, adjusting the pH of the fourth effluent with a mineral acid, preferably the pH of the acidic fifth effluent is 2-4.5, more preferably the mineral acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid.
7. The method according to any one of claims 4 to 6, wherein in S6, the fifth effluent is subjected to a catalytic oxidation reaction with an oxidant in the presence of a heterogeneous Fenton catalyst;
preferably, the heterogeneous Fenton catalyst has a volume filling ratio in the Fenton reactor of 50 to 90%,
and/or the dosage of the oxidant is 0.5-6 g/L;
and/or the residence time of the fifth effluent in the Fenton reactor is 0.5-2 h.
8. The method according to any one of claims 4 to 7, wherein the heterogeneous Fenton catalyst comprises a carrier and an active component supported on the carrier,
preferably, the carrier is selected from activated carbon, and/or the active components are selected from Fe and/or Cu, and the loading amount of the active components accounts for 5-20 wt% of the carrier;
and/or the oxidant is 27.5% hydrogen peroxide.
9. The method according to any one of claims 4 to 8, wherein a part of the sixth effluent obtained in S6 is introduced into a second pH adjusting device for pH adjustment to obtain treated effluent, and the rest of the sixth effluent is recycled as circulating water to a Fenton reactor for continuous catalytic oxidation reaction;
preferably, the circulating water is mixed with the fifth effluent and/or the oxidant, then introduced into the water inlet area of the fenton reactor, and then enters the reaction area after being distributed by the distribution plate to perform catalytic oxidation reaction.
10. The method according to any one of claims 4 to 9, wherein the coking wastewater has a benzo (a) pyrene concentration of 0.03 to 90 μ g/L.
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