CN203625104U - Device for deeply treating oil refining sewage through catalytic ozonation - Google Patents
Device for deeply treating oil refining sewage through catalytic ozonation Download PDFInfo
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- CN203625104U CN203625104U CN201320614190.7U CN201320614190U CN203625104U CN 203625104 U CN203625104 U CN 203625104U CN 201320614190 U CN201320614190 U CN 201320614190U CN 203625104 U CN203625104 U CN 203625104U
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Abstract
The utility model discloses a device for deeply treating oil refining sewage through catalytic ozonation, belonging to the technical field of oil refining sewage treatment. The device comprises a liquid oxygen storage tank, an ozone generator, an ozone compressor, a high-pressure catalytic ozonation tower and a normal-pressure catalytic ozonation tower which are communicated in sequence. Due to the gradient utilization of high-pressure ozone in the high-pressure catalytic ozonation tower and residual ozone in the normal-pressure catalytic ozonation tower, the aim of degrading low-concentration macromolecular organic pollutants is achieved, and the effluent is up to the first class A discharge standard of the national urban industrial wastewater discharge standard; the device is simple, easy to control and capable of solving the problems of high ozone tail gas yield, low ozone utilization ratio and low degradation efficiency of low-concentration persistent organic pollutants in oil refining sewage and reducing the waste and pollution of ozone. Meanwhile, the ozone tail gas treatment problem is solved, the sewage treatment cost and energy consumption are reduced, and the economical efficiency for applying an ozone catalytic ozonation technology is increased.
Description
Technical field
The utility model relates to Refinery Wastewater Treatment Technology field, particularly a kind of oil refining sewerage catalytic ozonation advanced treatment apparatus.
Background technology
COD in oil refining sewerage after biochemical treatment (chemical oxygen demand chemical oxygen demand (COD)) scope is 80mg/L-120mg/L, TOC (total organic carbon total organic carbon) scope is 20mg/L-40mg/L, BOD5 < 10mg/L (five-day BOD biochemical oxygen demand), does not meet the one-level A mark (COD the highest permission emission concentration 50mg/L) of country's " cities and towns industrial sewage emission standard " in (GB18918-2002).Research is found, in oil refining sewerage after biochemical treatment, remain the solubilised state organic pollutant of the lower concentration of dispersion, this type organic is mainly by the stronger petroleum acids of polarity, condensed-nuclei aromatics class, form containing O, N, S heterocycles etc., make its molecular structure complexity, biodegradability extreme difference, is difficult to degrade to reduce organic pollutant load by microorganism means.
Prior art adopts catalytic ozonation sewage water treatment method, by the synergy of ozone and heterogeneous catalyst, improve ozone decomposed and produce OH(hydroxyl radical free radical) and the efficiency of degradable organic pollutant, the organic waste water of the difficult degradations such as P-TOLUENE SULFO ACID 99's sodium waste water, percolate, conventional refinery water, coking chemical waste water, neopentyl glycol waste water is degraded.
Realizing in process of the present utility model, utility model people finds that prior art at least exists following problem:
Prior art adopts catalytic ozonation sewage water treatment method how under normal pressure, to carry out, for the oil refining sewerage that contains the too low Persistent organic pollutants of concentration, all lower by making ozone and decomposing mass-transfer efficiency between OH both and the contaminant molecule producing, cause the problem that ozone dosage is large, ozone tail gas generation is large, ozone utilization rate is low, and lower to the degradation efficiency of the too low Persistent organic pollutants of concentration in sewage; For a large amount of ozone tail gas that have neither part nor lot in contaminant degradation, also need to set up ozone tail gas aftertreatment technology and remove, reduce the economy of catalytic ozonation technology application.
Utility model content
In order to solve the problem that prior art ozone utilization rate is low, the utility model embodiment provides a kind of oil refining sewerage catalytic ozonation advanced treatment apparatus.Described technical scheme is as follows:
A kind of oil refining sewerage catalytic ozonation advanced treatment apparatus, described oil refining sewerage catalytic ozonation advanced treatment apparatus comprises the liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower that are communicated with in turn.
Particularly, described liquid oxygen storage tank, described ozonizer, described ozone compressor are communicated with described high-pressure ozone catalyzed oxidation tower in turn by ozone pipeline, and described high-pressure ozone catalyzed oxidation tower is also communicated with by sewer pipeline in turn with described normal pressure catalytic ozonation tower 9.
Particularly, described oil refining sewerage catalytic ozonation advanced treatment apparatus also comprises the high-pressure pump and the valve that are communicated with in turn, and described valve is connected with the water-in of described high-pressure ozone catalyzed oxidation tower by sewer pipeline.
Described oil refining sewerage catalytic ozonation pretreatment unit also comprises at least three valves, and described valve installation is at least one pipeline of described sewer pipeline, described ozone pipeline, for adjusting, water conservancy diversion, the voltage stabilizing of fluid.
Particularly, as preferably, described high-pressure ozone catalyzed oxidation tower comprises tower body, solid-phase catalyst bed, pressure safety valve, water-in, inlet mouth and water outlet, described pressure safety valve is arranged on described tower bodies top, described water-in is arranged on described tower body bottom, and described water-in is connected with described high-pressure pump outlet by sewer pipeline, described inlet mouth is arranged on described tower body bottom, and described inlet mouth is connected with described ozone compressor outlet by ozone pipeline, described water outlet is arranged on described tower body top, and described water outlet is for being discharged into described normal pressure catalytic ozonation tower by the water outlet of described high-pressure ozone catalyzed oxidation tower.
Particularly, as preferably, described normal pressure catalytic ozonation tower comprises tower body, solid-phase catalyst bed, water-in, reliever and water outlet, described water-in is arranged on described tower body bottom, and described water-in is connected with the water outlet of described high-pressure ozone catalyzed oxidation tower by sewer pipeline, described reliever is arranged on described tower body bottom, described reliever is connected with the water-in of described normal pressure catalytic ozonation tower, described water outlet is arranged on described tower body top, described water outlet is for overflowing the water outlet of described normal pressure catalytic ozonation tower.
Particularly, as preferably, the material of the material of described high-pressure ozone catalyzed oxidation tower, described normal pressure catalytic ozonation tower, described ozone compressor material, the material of sewer pipeline and the material of ozone pipeline are 316L stainless steel.
Particularly, the principle of work of described oil refining sewerage catalytic ozonation advanced treatment apparatus is: the oil refining sewerage after materialization, biochemical treatment is pumped into high-pressure ozone catalyzed oxidation tower, meanwhile, high-pressure ozone gas is passed into high-pressure ozone catalyzed oxidation tower, in described high-pressure ozone catalyzed oxidation tower, in water body, ozone carries out the 1st grade of degradation treatment to organic pollutant under the synergy of solid-phase catalyst; The water outlet of described high-pressure ozone catalyzed oxidation tower is injected to normal pressure catalytic ozonation tower, and in described normal pressure catalytic ozonation tower, in water body, residual ozone carries out the 2nd grade of degraded to organic pollutant under the synergy of solid-phase catalyst.
The beneficial effect that the technical scheme that the utility model embodiment provides is brought is:
The oil refining sewerage catalytic ozonation advanced treatment apparatus that the utility model embodiment provides, by the liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower that are communicated with in turn, adopting high pressure high-concentrated ozone degraded macromolecule contaminant is small molecules pollutent, normal pressure low concentration ozone degradation of small molecular pollutent; The object that has realized degraded lower concentration macromole organic pollutant, water outlet reaches the one-level A mark of country's " cities and towns industrial sewage emission standard ", and device is simple, easy to control.The cascade utilization of residual ozone in high-pressure ozone catalyzed oxidation tower inner high voltage ozone-normal pressure catalytic ozonation tower, solved that ozone tail gas generation is large, ozone utilization rate is low and oil refining sewerage in the low problem of Persistent organic pollutants degradation efficiency of lower concentration, waste and the pollution of ozone are reduced, avoided the processing problem of ozone tail gas simultaneously, reduce cost and the energy consumption of sewage disposal, increased the economy of catalytic ozonation technology application.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the utility model embodiment, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only embodiment more of the present utility model, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of the oil refining sewerage catalytic ozonation advanced treatment apparatus that provides of the utility model embodiment;
Wherein: 1 liquid oxygen storage tank,
2 reducing valve,
3 under meters,
4 ozonizers,
5 ozone compressors,
6 valves,
7 high-pressure pump,
8 high-pressure ozone catalyzed oxidation towers,
81 high-pressure ozone catalyzed oxidation tower inlet mouths,
82 high-pressure ozone catalyzed oxidation tower water-ins,
83 pressure safety valves,
84 high-pressure ozone catalyzed oxidation tower water outlets,
9 normal pressure catalytic ozonation towers,
91 normal pressure catalytic ozonation tower water-ins,
92 normal pressure catalytic ozonation tower relievers,
93 normal pressure catalytic ozonation tower water outlets,
10 tower bodies.
Embodiment
For making the purpose of this utility model, technical scheme and advantage clearer, below in conjunction with accompanying drawing 1, the utility model embodiment is described in further detail.
Embodiment mono-
As shown in Figure 1, the utility model embodiment provides a kind of catalytic ozonation advanced treatment apparatus, described device comprises the liquid oxygen storage tank 1, ozonizer 4, ozone compressor 5, high-pressure ozone catalyzed oxidation tower 8 and the normal pressure catalytic ozonation tower 9 that are communicated with in turn, described liquid oxygen storage tank 1, described ozonizer 4, described ozone compressor 5 are communicated with described high-pressure ozone catalyzed oxidation tower 8 in turn by ozone pipeline, and described high-pressure ozone catalyzed oxidation tower 8 is also communicated with by sewer pipeline in turn with described normal pressure catalytic ozonation tower 9.
The oil refining sewerage catalytic ozonation advanced treatment apparatus that the utility model embodiment provides, by the liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower that are communicated with in turn, adopting high pressure high-concentrated ozone degraded macromolecule contaminant is small molecules pollutent, normal pressure low concentration ozone degradation of small molecular pollutent; The object that has realized degraded lower concentration macromole organic pollutant, water outlet reaches the one-level A mark of country's " cities and towns industrial sewage emission standard ", and device is simple, easy to control.The cascade utilization of residual ozone in high-pressure ozone catalyzed oxidation tower inner high voltage ozone-normal pressure catalytic ozonation tower, solved that ozone tail gas generation is large, ozone utilization rate is low and oil refining sewerage in the low problem of Persistent organic pollutants degradation efficiency of lower concentration, waste and the pollution of ozone are reduced, avoided the processing problem of ozone tail gas simultaneously, reduce cost and the energy consumption of sewage disposal, increased the economy of catalytic ozonation technology application.
In specific operation process, first will pass into liquid oxygen storage tank 1 from the liquid oxygen of refinery's air separation plant, described liquid oxygen is entered to ozonizer 4 by reducing valve 2, under meter 3 in turn and produce ozone mixed gas, again described ozone mixed gas is pressurized to 0.3-0.5MPa through ozone compressor 5, and control by valve 6, described high pressure high-concentrated ozone is injected from high-pressure ozone catalyzed oxidation tower 8 bottom high-pressure ozone catalyzed oxidation tower inlet mouths 81; Meanwhile, under the control of high-pressure pump 7, valve 6, oil refining sewerage is injected from high-pressure ozone catalyzed oxidation tower 8 bottom high-pressure ozone catalyzed oxidation tower water-ins 82; Described high-pressure ozone and described oil refining sewerage be in the molten ozone water of the interior formation saturated mode of high-pressure ozone catalyzed oxidation tower 8, and under heterogeneous catalyst synergy, organic pollutant is carried out to the 1st grade of degraded, and the macromole organic pollutant in oil refining sewerage is fallen
Separate as small molecules pollutent.High-pressure ozone catalyzed oxidation tower 8 tops are provided with pressure safety valve 83, for controlling the pressure of high-pressure ozone catalyzed oxidation tower, make it within the scope of safety operation.The sewage that completes the 1st grade of degradation treatment in high-pressure ozone catalyzed oxidation tower 8 is extruded from high-pressure ozone catalyzed oxidation tower 8 top high-voltage catalytic ozonation tower water outlets 84, and control by the self-pressure of sewage and by valve 6, make the water outlet of high-pressure ozone catalyzed oxidation tower 8 enter described normal pressure catalytic ozonation tower 9 by normal pressure catalytic ozonation tower 9 bottom normal pressure catalytic ozonation tower water-ins 91, then discharge by the normal pressure catalytic ozonation tower reliever 92 being arranged in normal pressure catalytic ozonation tower 9 towers the mixture that remains ozone and sewage, in atmosphere-pressure catalytic oxidation tower 9, under solid-phase catalyst synergy, ozone residual in water body is proceeded the 2nd grade of degraded to organic pollutant.The sewage that completes the 2nd grade of degree of depth degradation treatment overflows from normal pressure catalytic ozonation tower 9 top normal pressure catalytic ozonation tower water outlets 93, completes the advanced treatment to oil refining sewerage step catalytic ozonation.The object that normal pressure catalytic ozonation tower reliever 92 is set at normal pressure catalytic ozonation tower bottom is that in making water body, residual ozone can fully contact with water body, improve reaction efficiency, simultaneously, the water body of discharging from high-pressure ozone catalyzed oxidation tower 8 is with certain pressure, through the release of reliever, can be passed into uniformly in normal pressure catalytic ozonation tower safer this water body with pressure.
Particularly, as shown in Figure 1, described oil refining sewerage step catalytic ozonation treatment unit also comprises in turn the reducing valve 2 that is communicated with and under meter 3 and the high-pressure pump 7 and the valve 6 that are communicated with in turn, the described reducing valve 2 being communicated with is in turn connected with described ozonizer 4 inlet line by ozone pipeline with under meter 3, and the described high-pressure pump 7 being communicated with is in turn connected with described high-pressure ozone catalyzed oxidation tower 8 bottom high-pressure ozone catalyzed oxidation tower water-ins 82 by sewer pipeline with valve 6.
As shown in Figure 1, described high-pressure ozone catalyzed oxidation tower 8 comprises tower body 10, pressure safety valve 83, solid-phase catalyst bed, high-pressure ozone catalyzed oxidation tower water-in 82, high-pressure ozone catalyzed oxidation tower inlet mouth 81 and high-pressure ozone catalyzed oxidation tower water outlet 84, described pressure safety valve 83 is arranged on described tower body 10 tops, described high-pressure ozone catalyzed oxidation tower water-in 82 is arranged on described tower body bottom, and described high-pressure ozone catalyzed oxidation tower water-in 82 is connected with described high-pressure pump 7 outlets by sewer pipeline, described high-pressure ozone catalyzed oxidation tower inlet mouth 81 is arranged on described tower body 10 bottoms, described high-pressure ozone catalyzed oxidation tower inlet mouth 81 is connected with described ozone compressor 5 outlets by ozone pipeline, described high-pressure ozone catalyzed oxidation tower water outlet 84 is arranged on described tower body 10 tops, described high-pressure ozone catalyzed oxidation tower water outlet 84 is for being discharged into the water outlet of described high-pressure ozone catalyzed oxidation tower in described normal pressure catalytic ozonation tower.
As shown in Figure 1, described normal pressure catalytic ozonation tower comprises tower body 10, solid-phase catalyst bed, normal pressure catalytic ozonation tower water-in 91, normal pressure catalytic ozonation tower reliever 92 and normal pressure catalytic ozonation tower water outlet 93, described normal pressure catalytic ozonation tower water-in 91 is arranged on described tower body 10 bottoms, and described normal pressure catalytic ozonation tower water-in 91 is connected with described high-pressure ozone catalyzed oxidation tower water outlet 84 by sewer pipeline, described normal pressure catalytic ozonation tower water outlet 93 is arranged on described tower body 10 tops, described normal pressure catalytic ozonation tower water outlet 93 is for overflowing the water outlet of described normal pressure catalytic ozonation tower 10, described normal pressure catalytic ozonation tower reliever 92 is arranged on described tower body 10 bottoms, described normal pressure catalytic ozonation tower reliever 92 is connected with the normal pressure catalytic ozonation tower water-in 91 of described normal pressure catalytic ozonation tower 10.
The buffer tank of described high-pressure ozone catalyzed oxidation tower 9 and internals thereof, described normal pressure catalytic ozonation tower 10 and internals thereof, described ozone compressor 5, and the material of described sewer pipeline, described ozone pipeline is 316L stainless steel.
Embodiment bis-
The field pilot-scale of the oil refining sewerage step catalytic ozonation advanced treatment apparatus that the utility model embodiment provides is carried out at Liaohe River petro-chemical corporation wastewater treatment field.Oil refining sewerage used is the oil removal of process two-stage, two-stage air supporting, acidication, circulating sludge method water outlet after treatment.Concrete operations flow process is as follows:
First will pass into liquid oxygen storage tank from the liquid oxygen of refinery's air separation plant, described liquid oxygen is entered to ozonizer by reducing valve, under meter in turn and produce ozone mixed gas, again by described ozone mixed gas through ozone compressor boost to 0.3-0.5MPa, and by valve control, described high pressure high-concentrated ozone is injected from high-pressure ozone catalyzed oxidation tower bottom ozone inlet mouth; Meanwhile, under the control of high-pressure pump, valve, by oil refining sewerage, inject from high-pressure ozone catalyzed oxidation tower bottom water-in; Described high-pressure ozone and described oil refining sewerage form the molten ozone water of saturated mode in high-pressure ozone catalyzed oxidation tower, and under heterogeneous catalyst synergy, organic pollutant is carried out to the 1st grade of degraded, is small molecules pollutent by the macromole organic pollutant degradation in oil refining sewerage.High-pressure ozone catalyzed oxidation top of tower is provided with pressure safety valve, for controlling the pressure of high-pressure ozone catalyzed oxidation tower, makes it within the scope of safety operation.The sewage that completes the 1st grade of degradation treatment in high-pressure ozone catalyzed oxidation tower is extruded from high-pressure ozone catalyzed oxidation top of tower water outlet, and by the self-pressure of sewage and by valve control, make the water outlet of high-pressure ozone catalyzed oxidation tower enter described normal pressure catalytic ozonation tower by normal pressure catalytic ozonation tower bottom water-in, then discharge by the reliever being arranged in normal pressure catalytic ozonation tower the mixture that remains ozone and sewage, in atmosphere-pressure catalytic oxidation tower, under solid-phase catalyst synergy, ozone residual in water body is proceeded the 2nd grade of degraded to organic pollutant.The sewage that completes the 2nd grade of degree of depth degradation treatment overflows from normal pressure catalytic ozonation top of tower water outlet, completes the advanced treatment to oil refining sewerage step catalytic ozonation.
In operating process, the working pressure of high-pressure ozone catalyzed oxidation tower is 0.3-0.5MPa(gauge pressure), hydraulic detention time is 15min-20min, ozone dosage is 20g-30g/t sewage.The hydraulic detention time of normal pressure catalytic ozonation tower is 20min-30min.
In operating process, solid catalysis agent carrier used is coal-based activated carbon, composite reactive component is the mass ratio of Mn, Fe, Cu be 1:0.8:1 Mn, Fe, Cu three's oxide compound, and the massfraction that the charge capacity of described composite reactive component accounts for described carrier quality is 1.5%-2.5%.
The mean pore size of described active carbon from coal is 3.0nm～5.0nm, and specific surface area is 1100m
2/ g～1200m
2/ g, pore volume is 0.6ml/g～0.8ml/g, ash content is that 5m%-6m%(m% is massfraction), mean diameter is 3mm-4mm, mean length is 15mm-20mm.
The effect of the device that the utility model embodiment provides to oil refining sewerage processing:
Influent COD cr scope is at 80mg/L-120mg/L, and TOC scope is between 20mg/L-40mg/L, and BOD5 scope is between 8mg-10mg/L; Normal pressure catalytic ozonation tower effluent quality is basicly stable, and CODcr scope is at 32mg/L-46mg/L, and TOC scope is between 12mg/L-18mg/L, and BOD5 scope is between 3mg-10mg/L; Meet (GB18918-2002) one-level A mark of country's " cities and towns industrial sewage emission standard ".
The utility model embodiment provides liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower of oil refining sewerage catalytic ozonation advanced treatment apparatus by being communicated with in turn, adopting high pressure high-concentrated ozone degraded macromolecule contaminant is small molecules pollutent, normal pressure low concentration ozone degradation of small molecular pollutent; Realized the object of degraded lower concentration macromole organic pollutant, water outlet reaches the one-level A mark of country's " cities and towns industrial sewage emission standard ", install simple to operate, easy to control, can large-scale industrial application.The cascade utilization of high-pressure ozone-normal pressure ozone, solved that ozone tail gas generation is large, ozone utilization rate is low and oil refining sewerage in the low problem of Persistent organic pollutants degradation efficiency of lower concentration, reduced waste and the pollution of ozone.Avoid the processing problem of ozone tail gas simultaneously, reduced cost and the energy consumption of sewage disposal, increased the economy of catalytic ozonation technology application.
Embodiment tri-
The field pilot-scale of the oil refining sewerage step catalytic ozonation advanced treatment apparatus that the utility model embodiment provides is carried out at Liaohe River petro-chemical corporation wastewater treatment field.Oil refining sewerage used is the oil removal of process two-stage, two-stage air supporting, acidication, circulating sludge method water outlet after treatment.Concrete operations flow process is as follows:
First will pass into liquid oxygen storage tank from the liquid oxygen of refinery's air separation plant, described liquid oxygen is entered to ozonizer by reducing valve, under meter in turn and produce ozone mixed gas, again by described ozone mixed gas through ozone compressor boost to 0.4MPa, and by valve control, described high pressure high-concentrated ozone is injected from high-pressure ozone catalyzed oxidation tower bottom ozone inlet mouth; Meanwhile, under the control of high-pressure pump, valve, by oil refining sewerage, inject from high-pressure ozone catalyzed oxidation tower bottom water-in; Described high-pressure ozone and described oil refining sewerage form the molten ozone water of saturated mode in high-pressure ozone catalyzed oxidation tower, and under heterogeneous catalyst synergy, organic pollutant is carried out to the 1st grade of degraded, is small molecules pollutent by the macromole organic pollutant degradation in oil refining sewerage.High-pressure ozone catalyzed oxidation top of tower is provided with pressure safety valve, for controlling the pressure of high-pressure ozone catalyzed oxidation tower, makes it within the scope of safety operation.The sewage that completes the 1st grade of degradation treatment in high-pressure ozone catalyzed oxidation tower is extruded from high-pressure ozone catalyzed oxidation top of tower water outlet, and by the self-pressure of sewage and by valve control, make the water outlet of high-pressure ozone catalyzed oxidation tower enter described normal pressure catalytic ozonation tower by normal pressure catalytic ozonation tower bottom water-in, then discharge by the reliever being arranged in normal pressure catalytic ozonation tower the mixture that remains ozone and sewage, in atmosphere-pressure catalytic oxidation tower, under solid-phase catalyst synergy, ozone residual in water body is proceeded the 2nd grade of degraded to organic pollutant.The sewage that completes the 2nd grade of degree of depth degradation treatment overflows from normal pressure catalytic ozonation top of tower water outlet, completes the advanced treatment to oil refining sewerage step catalytic ozonation.
Wherein, the working pressure of high-pressure ozone catalyzed oxidation tower is 0.3MPa(gauge pressure), hydraulic detention time is 18min, ozone dosage is 20g/t sewage.The hydraulic detention time of normal pressure catalytic ozonation tower is 30min.
In operating process, solid catalysis agent carrier used is coal-based activated carbon, composite reactive component is the mass ratio of Mn, Fe, Cu be 1:0.8:1 Mn, Fe, Cu three's oxide compound, and the massfraction that the charge capacity of described composite reactive component accounts for described carrier quality is 1.5%.
The mean pore size of described active carbon from coal is 5.0nm, and specific surface area is 1200m
2/ g, pore volume is 0.6ml/g, ash content is that 6m%(m% is massfraction), mean diameter is 3mm, mean length is 20mm.
The effect of the device that the utility model embodiment provides to oil refining sewerage processing:
Influent COD cr is 100mg/L, and TOC is 40mg/L, and BOD5 is 8mg; Normal pressure catalytic ozonation tower effluent quality is basicly stable, and CODcr is 46mg/L, and TOC is 18mg/L, and BOD5 is 3mg/L; Meet (GB18918-2002) one-level A mark of country's " cities and towns industrial sewage emission standard ".
The oil refining sewerage catalytic ozonation advanced treatment apparatus that the utility model embodiment provides is by the liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower that are communicated with in turn, adopting high pressure high-concentrated ozone degraded macromolecule contaminant is small molecules pollutent, normal pressure low concentration ozone degradation of small molecular pollutent; The object that has realized degraded lower concentration macromole organic pollutant, water outlet reaches the one-level A mark of country's " cities and towns industrial sewage emission standard ".Install simple to operate, easy to control, can large-scale industrial application.The cascade utilization of high-pressure ozone-normal pressure ozone, solved that ozone tail gas generation is large, ozone utilization rate is low and oil refining sewerage in the low problem of Persistent organic pollutants degradation efficiency of lower concentration, reduced waste and the pollution of ozone.Avoid the processing problem of ozone tail gas simultaneously, reduced cost and the energy consumption of sewage disposal, increased the economy of catalytic ozonation technology application.
Embodiment tetra-
The field pilot-scale of the oil refining sewerage step catalytic ozonation advanced treatment apparatus that the utility model embodiment provides is carried out at Liaohe River petro-chemical corporation wastewater treatment field.Oil refining sewerage used is the oil removal of process two-stage, two-stage air supporting, acidication, circulating sludge method water outlet after treatment.Concrete operations flow process is as follows:
First will pass into liquid oxygen storage tank from the liquid oxygen of refinery's air separation plant, described liquid oxygen is entered to ozonizer by reducing valve, under meter in turn and produce ozone mixed gas, again by described ozone mixed gas through ozone compressor boost to 0.3-0.5MPa, and by valve control, described high pressure high-concentrated ozone is injected from high-pressure ozone catalyzed oxidation tower bottom ozone inlet mouth; Meanwhile, under the control of high-pressure pump, valve, by oil refining sewerage, inject from high-pressure ozone catalyzed oxidation tower bottom water-in; Described high-pressure ozone and described oil refining sewerage form the molten ozone water of saturated mode in high-pressure ozone catalyzed oxidation tower, and under heterogeneous catalyst synergy, organic pollutant is carried out to the 1st grade of degraded, is small molecules pollutent by the macromole organic pollutant degradation in oil refining sewerage.High-pressure ozone catalyzed oxidation top of tower is provided with pressure safety valve, for controlling the pressure of high-pressure ozone catalyzed oxidation tower, makes it within the scope of safety operation.The sewage that completes the 1st grade of degradation treatment in high-pressure ozone catalyzed oxidation tower is extruded from high-pressure ozone catalyzed oxidation top of tower water outlet, and by the self-pressure of sewage and by valve control, make the water outlet of high-pressure ozone catalyzed oxidation tower enter described normal pressure catalytic ozonation tower by normal pressure catalytic ozonation tower bottom water-in, then discharge by the reliever being arranged in normal pressure catalytic ozonation tower the mixture that remains ozone and sewage, in atmosphere-pressure catalytic oxidation tower, under solid-phase catalyst synergy, ozone residual in water body is proceeded the 2nd grade of degraded to organic pollutant.The sewage that completes the 2nd grade of degree of depth degradation treatment overflows from normal pressure catalytic ozonation top of tower water outlet, completes the advanced treatment to oil refining sewerage step catalytic ozonation.
Wherein, the working pressure of high-pressure ozone catalyzed oxidation tower is 0.5MPa(gauge pressure), hydraulic detention time is 20min, ozone dosage is 30g/t sewage.The hydraulic detention time of normal pressure catalytic ozonation tower is 20min.
In operating process, solid catalysis agent carrier used is coal-based activated carbon, composite reactive component is the mass ratio of Mn, Fe, Cu be 1:0.8:1 Mn, Fe, Cu three's oxide compound, and the massfraction that the charge capacity of described composite reactive component accounts for described carrier quality is 2.5%.
The mean pore size of described active carbon from coal is 3.0nm, and specific surface area is 1100m
2/ g, pore volume is 0.8ml/g, ash content is that 5m%(m% is massfraction), mean diameter is 4mm, mean length is 15mm.
The effect of the device that the utility model embodiment provides to oil refining sewerage processing:
Influent COD cr is 80mg/L, and TOC is 20mg/L, and BOD5 is 10mg; Normal pressure catalytic ozonation tower effluent quality is basicly stable, and CODcr is 32mg/L, and TOC is 12mg/L, and BOD5 is 5mg/L; Meet (GB18918-2002) one-level A mark of country's " cities and towns industrial sewage emission standard ".
The oil refining sewerage catalytic ozonation advanced treatment apparatus that the utility model embodiment provides is by the liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower that are communicated with in turn, adopting high pressure high-concentrated ozone degraded macromolecule contaminant is small molecules pollutent, normal pressure low concentration ozone degradation of small molecular pollutent; The object that has realized degraded lower concentration macromole organic pollutant, water outlet reaches the one-level A mark of country's " cities and towns industrial sewage emission standard ".Install simple to operate, easy to control, can large-scale industrial application.The cascade utilization of high-pressure ozone-normal pressure ozone, solved that ozone tail gas generation is large, ozone utilization rate is low and oil refining sewerage in the low problem of Persistent organic pollutants degradation efficiency of lower concentration, reduced waste and the pollution of ozone.Avoid the processing problem of ozone tail gas simultaneously, reduced cost and the energy consumption of sewage disposal, increased the economy of catalytic ozonation technology application.
Embodiment five
The field pilot-scale of the oil refining sewerage step catalytic ozonation advanced treatment apparatus that the utility model embodiment provides is carried out at Liaohe River petro-chemical corporation wastewater treatment field.Oil refining sewerage used is the oil removal of process two-stage, two-stage air supporting, acidication, circulating sludge method water outlet after treatment.Concrete operations flow process is as follows:
First will pass into liquid oxygen storage tank from the liquid oxygen of refinery's air separation plant, described liquid oxygen is entered to ozonizer by reducing valve, under meter in turn and produce ozone mixed gas, again by described ozone mixed gas through ozone compressor boost to 0.3MPa, and by valve control, described high pressure high-concentrated ozone is injected from high-pressure ozone catalyzed oxidation tower bottom ozone inlet mouth; Meanwhile, under the control of high-pressure pump, valve, by oil refining sewerage, inject from high-pressure ozone catalyzed oxidation tower bottom water-in; Described high-pressure ozone and described oil refining sewerage form the molten ozone water of saturated mode in high-pressure ozone catalyzed oxidation tower, and under heterogeneous catalyst synergy, organic pollutant is carried out to the 1st grade of degraded, is small molecules pollutent by the macromole organic pollutant degradation in oil refining sewerage.High-pressure ozone catalyzed oxidation top of tower is provided with pressure safety valve, for controlling the pressure of high-pressure ozone catalyzed oxidation tower, makes it within the scope of safety operation.The sewage that completes the 1st grade of degradation treatment in high-pressure ozone catalyzed oxidation tower is extruded from high-pressure ozone catalyzed oxidation top of tower water outlet, and by the self-pressure of sewage and by valve control, make the water outlet of high-pressure ozone catalyzed oxidation tower enter described normal pressure catalytic ozonation tower by normal pressure catalytic ozonation tower bottom water-in, then discharge by the reliever being arranged in normal pressure catalytic ozonation tower the mixture that remains ozone and sewage, in atmosphere-pressure catalytic oxidation tower, under solid-phase catalyst synergy, ozone residual in water body is proceeded the 2nd grade of degraded to organic pollutant.The sewage that completes the 2nd grade of degree of depth degradation treatment overflows from normal pressure catalytic ozonation top of tower water outlet, completes the advanced treatment to oil refining sewerage step catalytic ozonation.
Wherein, the working pressure of high-pressure ozone catalyzed oxidation tower is 0.4MPa(gauge pressure), hydraulic detention time is 15min, ozone dosage is 25g/t sewage.The hydraulic detention time of normal pressure catalytic ozonation tower is 25min.
In operating process, solid catalysis agent carrier used is coal-based activated carbon, composite reactive component is the mass ratio of Mn, Fe, Cu be 1:0.8:1 Mn, Fe, Cu three's oxide compound, and the massfraction that the charge capacity of described composite reactive component accounts for described carrier quality is 2.0%.
The mean pore size of described active carbon from coal is 4nm, and specific surface area is 1150m
2/ g, pore volume is 0.7ml/g, ash content is that 5.5m%(m% is massfraction), mean diameter is 3.5mm, mean length is 17mm.
The effect of the device that the utility model embodiment provides to oil refining sewerage processing:
Influent COD cr is 90mg/L, and TOC is 30mg/L, and BOD5 is 9mg; Normal pressure catalytic ozonation tower effluent quality is basicly stable, and CODcr is 36mg/L, and TOC is 14mg/L, and BOD5 is 6mg/L; Meet (GB18918-2002) one-level A mark of country's " cities and towns industrial sewage emission standard ".
The oil refining sewerage catalytic ozonation advanced treatment apparatus that the utility model embodiment provides is by the liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower that are communicated with in turn, adopting high pressure high-concentrated ozone degraded macromolecule contaminant is small molecules pollutent, normal pressure low concentration ozone degradation of small molecular pollutent; The object that has realized degraded lower concentration macromole organic pollutant, water outlet reaches the one-level A mark of country's " cities and towns industrial sewage emission standard ".Install simple to operate, easy to control, can large-scale industrial application.The cascade utilization of high-pressure ozone-normal pressure ozone, solved that ozone tail gas generation is large, ozone utilization rate is low and oil refining sewerage in the low problem of Persistent organic pollutants degradation efficiency of lower concentration, reduced waste and the pollution of ozone.Avoid the processing problem of ozone tail gas simultaneously, reduced cost and the energy consumption of sewage disposal, increased the economy of catalytic ozonation technology application.
Embodiment six
The field pilot-scale of the oil refining sewerage step catalytic ozonation advanced treatment apparatus that the utility model embodiment provides is carried out at Liaohe River petro-chemical corporation wastewater treatment field.Oil refining sewerage used is the oil removal of process two-stage, two-stage air supporting, acidication, circulating sludge method water outlet after treatment.Concrete operations flow process is as follows:
First will pass into liquid oxygen storage tank from the liquid oxygen of refinery's air separation plant, described liquid oxygen is entered to ozonizer by reducing valve, under meter in turn and produce ozone mixed gas, again by described ozone mixed gas through ozone compressor boost to 0.5MPa, and by valve control, described high pressure high-concentrated ozone is injected from high-pressure ozone catalyzed oxidation tower bottom ozone inlet mouth; Meanwhile, under the control of high-pressure pump, valve, by oil refining sewerage, inject from high-pressure ozone catalyzed oxidation tower bottom water-in; Described high-pressure ozone and described oil refining sewerage form the molten ozone water of saturated mode in high-pressure ozone catalyzed oxidation tower, and under heterogeneous catalyst synergy, organic pollutant is carried out to the 1st grade of degraded, is small molecules pollutent by the macromole organic pollutant degradation in oil refining sewerage.High-pressure ozone catalyzed oxidation top of tower is provided with pressure safety valve, for controlling the pressure of high-pressure ozone catalyzed oxidation tower, makes it within the scope of safety operation.The sewage that completes the 1st grade of degradation treatment in high-pressure ozone catalyzed oxidation tower is extruded from high-pressure ozone catalyzed oxidation top of tower water outlet, and by the self-pressure of sewage and by valve control, make the water outlet of high-pressure ozone catalyzed oxidation tower enter described normal pressure catalytic ozonation tower by normal pressure catalytic ozonation tower bottom water-in, then discharge by the reliever being arranged in normal pressure catalytic ozonation tower the mixture that remains ozone and sewage, in atmosphere-pressure catalytic oxidation tower, under solid-phase catalyst synergy, ozone residual in water body is proceeded the 2nd grade of degraded to organic pollutant.The sewage that completes the 2nd grade of degree of depth degradation treatment overflows from normal pressure catalytic ozonation top of tower water outlet, completes the advanced treatment to oil refining sewerage step catalytic ozonation.
Wherein, the working pressure of high-pressure ozone catalyzed oxidation tower is 0.45MPa(gauge pressure), hydraulic detention time is 19min, ozone dosage is 27g/t sewage.The hydraulic detention time of normal pressure catalytic ozonation tower is 28min.
In operating process, solid catalysis agent carrier used is coal-based activated carbon, composite reactive component is the mass ratio of Mn, Fe, Cu be 1:0.8:1 Mn, Fe, Cu three's oxide compound, and the massfraction that the charge capacity of described composite reactive component accounts for described carrier quality is 2.3%.
The mean pore size of described active carbon from coal is 4.5nm, and specific surface area is 1180m
2/ g, pore volume is 0.75ml/g, ash content is that 5.9m%(m% is massfraction), mean diameter is 3.8mm, mean length is 18mm.
The effect of the device that the utility model embodiment provides to oil refining sewerage processing:
Influent COD cr is 120mg/L, and TOC is 35mg/L, BOD
5for 9mg; Normal pressure catalytic ozonation tower effluent quality is basicly stable, and CODcr is 40mg/L, and TOC is 16mg/L, BOD
5for 8mg/L; Meet (GB18918-2002) one-level A mark of country's " cities and towns industrial sewage emission standard ".
The oil refining sewerage catalytic ozonation advanced treatment apparatus that the utility model provides is by the liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower that are communicated with in turn, adopting high pressure high-concentrated ozone degraded macromolecule contaminant is small molecules pollutent, normal pressure low concentration ozone degradation of small molecular pollutent; Realized the object of degraded lower concentration macromole organic pollutant, water outlet reaches the one-level A mark of country's " cities and towns industrial sewage emission standard ", install simple to operate, easy to control, can large-scale industrial application.The cascade utilization of high-pressure ozone-normal pressure ozone, solved that ozone tail gas generation is large, ozone utilization rate is low and oil refining sewerage in the low problem of Persistent organic pollutants degradation efficiency of lower concentration, reduced waste and the pollution of ozone.Avoid the processing problem of ozone tail gas simultaneously, reduced cost and the energy consumption of sewage disposal, increased the economy of catalytic ozonation technology application.
Above-mentioned the utility model embodiment sequence number, just to describing, does not represent the quality of embodiment.
The foregoing is only preferred embodiment of the present utility model, not in order to limit the utility model, all within spirit of the present utility model and principle, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection domain of the present utility model.
Claims (7)
1. an oil refining sewerage catalytic ozonation advanced treatment apparatus, it is characterized in that, described oil refining sewerage catalytic ozonation advanced treatment apparatus comprises the liquid oxygen storage tank, ozonizer, ozone compressor, high-pressure ozone catalyzed oxidation tower and the normal pressure catalytic ozonation tower that are communicated with in turn.
2. oil refining sewerage catalytic ozonation advanced treatment apparatus according to claim 1, it is characterized in that, described liquid oxygen storage tank, described ozonizer, described ozone compressor are communicated with described high-pressure ozone catalyzed oxidation tower in turn by ozone pipeline, and described high-pressure ozone catalyzed oxidation tower is also communicated with by sewer pipeline in turn with described normal pressure catalytic ozonation tower.
3. oil refining sewerage catalytic ozonation advanced treatment apparatus according to claim 1, it is characterized in that, described oil refining sewerage catalytic ozonation advanced treatment apparatus also comprises the high-pressure pump and the valve that are communicated with in turn, and described valve is connected with the water-in of described high-pressure ozone catalyzed oxidation tower by sewer pipeline.
4. oil refining sewerage catalytic ozonation advanced treatment apparatus according to claim 3, it is characterized in that, described high-pressure ozone catalyzed oxidation tower comprises tower body, solid-phase catalyst bed, pressure safety valve, water-in, inlet mouth and water outlet, described pressure safety valve is arranged on described tower bodies top, described water-in is arranged on described tower body bottom, and described water-in is connected with described high-pressure pump outlet by sewer pipeline, described inlet mouth is arranged on described tower body bottom, and described inlet mouth is connected with described ozone compressor outlet by ozone pipeline, described water outlet is arranged on described tower body top, and described water outlet is for being discharged into described normal pressure catalytic ozonation tower by the water outlet of described high-pressure ozone catalyzed oxidation tower.
5. according to the oil refining sewerage catalytic ozonation advanced treatment apparatus described in claim 1-4 any one, it is characterized in that, described normal pressure catalytic ozonation tower comprises tower body, solid-phase catalyst bed, water-in, reliever and water outlet, described water-in is arranged on described tower body bottom, and described water-in is connected with the water outlet of described high-pressure ozone catalyzed oxidation tower by sewer pipeline, described reliever is arranged on described tower body bottom, described reliever is connected with the water-in of described normal pressure catalytic ozonation tower, described water outlet is arranged on described tower body top, described water outlet is for overflowing the water outlet of described normal pressure catalytic ozonation tower.
6. oil refining sewerage catalytic ozonation advanced treatment apparatus according to claim 2, it is characterized in that, the material of described high-pressure ozone catalyzed oxidation tower, the material of described normal pressure catalytic ozonation tower, described ozone compressor material, the material of sewer pipeline and the material of ozone pipeline are 316L stainless steel.
7. a kind of oil refining sewerage catalytic ozonation advanced treatment apparatus according to claim 2, it is characterized in that, described oil refining sewerage catalytic ozonation advanced treatment apparatus also comprises at least three valves, described valve installation is at least one pipeline of described sewer pipeline, described ozone pipeline, for adjusting, water conservancy diversion, the voltage stabilizing of fluid.
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| CN201320614190.7U CN203625104U (en) | 2013-09-30 | 2013-09-30 | Device for deeply treating oil refining sewage through catalytic ozonation |
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| CN201320614190.7U CN203625104U (en) | 2013-09-30 | 2013-09-30 | Device for deeply treating oil refining sewage through catalytic ozonation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528913A (en) * | 2015-01-09 | 2015-04-22 | 中国石油大学(北京) | Method and device for mineralizing low-concentration persistent organic pollutants in oil refining sewage |
| CN105692866A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Packing method of catalyst for processing high-acid heavy crude oil processing wastewater |
| CN105692865A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Method for processing high-acid heavy crude oil processing wastewater |
| CN105692864A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Method for processing wastewater |
-
2013
- 2013-09-30 CN CN201320614190.7U patent/CN203625104U/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105692866A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Packing method of catalyst for processing high-acid heavy crude oil processing wastewater |
| CN105692865A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Method for processing high-acid heavy crude oil processing wastewater |
| CN105692864A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Method for processing wastewater |
| CN105692866B (en) * | 2014-11-27 | 2018-07-13 | 中国海洋石油集团有限公司 | A kind of packing method of the catalyst of processing high-acid heavy crude oil processing waste water |
| CN105692865B (en) * | 2014-11-27 | 2018-09-07 | 中国海洋石油集团有限公司 | A method of processing high-acid heavy crude oil processing waste water |
| CN105692864B (en) * | 2014-11-27 | 2018-09-07 | 中国海洋石油集团有限公司 | A method of processing waste water |
| CN104528913A (en) * | 2015-01-09 | 2015-04-22 | 中国石油大学(北京) | Method and device for mineralizing low-concentration persistent organic pollutants in oil refining sewage |
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Effective date of registration: 20190605 Address after: 100007 Dongzhimen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNPC EAST CHINA DESIGN INSTITUTE CO.,LTD. Patentee after: CHINA NATIONAL PETROLEUM Corp. Co-patentee after: China University of Petroleum (Beijing) Address before: 100007 Dongzhimen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: CHINA PETROLEUM ENGINEERING & CONSTRUCTION Corp. Patentee before: CHINA NATIONAL PETROLEUM Corp. Co-patentee before: China University of Petroleum (Beijing) |
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