CN207016655U - The system that catalytic wet oxidation handles oil-containing dross - Google Patents
The system that catalytic wet oxidation handles oil-containing dross Download PDFInfo
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- CN207016655U CN207016655U CN201720835380.XU CN201720835380U CN207016655U CN 207016655 U CN207016655 U CN 207016655U CN 201720835380 U CN201720835380 U CN 201720835380U CN 207016655 U CN207016655 U CN 207016655U
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Abstract
The utility model discloses a kind of system of catalytic wet oxidation processing oil-containing dross.The system includes oil-containing dross process tank, oxidant holding vessel, water store tank and the high-pressure pump being sequentially connected, preheater, wet catalytic oxidation reactor, condenser and gas processer, oil-containing dross process tank, oxidant holding vessel and water store tank and is connected in parallel to the import of high-pressure pump.System of the present utility model can effectively degrade the petroleum hydrocarbon in oil-containing dross, and dehydrating effect is good, simple to operate, and cost is cheap, effectively solve sewage treatment plant and produce that scum silica frost amount is big, reluctant problem.
Description
Technical field
The utility model belongs to field of environment engineering, is related to a kind of innoxious system of oil-containing dross in petrochemical industry, tool
Body is related to a kind of system of catalytic wet oxidation processing oil-containing dross.
Background technology
The oil removal treatment of current domestic enterprise of petrochemical refining oil-polluted water typically uses oil removal, one-level flotation and secondary floatation
Technique.Preliminary water-oil separating is first passed through, oil-polluted water enters the oil separation tank in sewage farm, is separated out the sump oil on sewage top layer,
Sewage after oil removal removes floation tank, is flocculated in floation tank through flocculant, then pressurized dissolved air floatation, is formed and wadded a quilt with cotton in sewage surface
Solidifying body, oil-containing dross is formed after scrapper conveyor separates.Oil-containing dross is in the processing procedure of oil-polluted water, and air flotation cell produces
A kind of end discarded object.Oil-containing dross is the flocculation group of various particles, water and bubble formation, and in semi-solid state, viscosity is big,
Poor fluidity.Its main component is various chemical agents, various surfactants, flocculant, oil emulsion, dispersed oil, mink cell focus
Composition, fine sand and substantial amounts of secondary clay mineral, together, emulsification flocculation is serious, its settling property extreme difference for various coagulation of materials,
Dehydration is very difficult, and its moisture content is high.
The method of processing oil-containing dross typically has two kinds at present：First method is used after scum silica frost is flocculated in sewage farm
Centrifuge separating and dehydrating, scum silica frost are crushed again after becoming solid, mix oil or coal burns, but because its cost is too high, such a processing
Method is applied fewer and fewer；Second method is Jiao being routed directly to the scum silica frost that floation tank comes out in Refinery Coking device
Change tower and mix refining.The method for mixing refining mainly has two kinds：First, scum silica frost is made into coking tower quench oil；Second, using coking tower waste heat to floating
Slag carries out gasification separation.Second method is to enter scum silica frost from coking tower rising pouring in high-temperature coke cooling procedure, is given as small
Water cooling high-temperature coke；Using the high-temperature residual heat of coke by oil ingredient heating evaporation olefiant gas therein, escape into and connect from tower top
Touch cooling system；Solid impurity is then adsorbed in coke layer surface, and is entered Jiao Chi with high pressure decoking process and produced as coke
Product, so as to realize the purpose of closed environmental protection treatment scum silica frost.Scum silica frost processing cost has not only been saved using the method, will can also have been floated
Oil in slag is effectively recycled, and increases the yield of coke, and therefore, the processing method is by most refinery
Used.
However, with the increase year by year of oil plant crude runs, and crude quality tends in poor quality, heaviness, and it is dirty
Inorganic matter, organic species content of material in water are significantly increased, and scum silica frost amount also increases year by year caused by air flotation cell.It is same with this
When, the scum silica frost amount that coking plant is handled every year is limited, so causes most of scum silica frost not handle.Therefore, to prevent from floating
Problem of environmental pollution caused by slag is excessive, is badly in need of a kind of oil-containing dross minimizing and innoxious processing unit.
Utility model content
The technical problems to be solved in the utility model is overcome the deficiencies in the prior art, there is provided oil-containing in a kind of petrochemical industry
The innoxious system of scum silica frost, carry out advanced treating particular for poisonous and harmful elements such as oil-containing dross petrochina hydro carbons, processing is imitated
The system of rate height, high treating effect and catalytic wet oxidation applied widely processing oil-containing dross.
In order to solve the above technical problems, the utility model uses following technical scheme：
A kind of system of catalytic wet oxidation processing oil-containing dross, the system include oil-containing dross process tank, oxidant
Holding vessel, water storage tank and the high-pressure pump being sequentially connected, preheater, wet catalytic oxidation reactor, condenser and gas treatment
Device, the oil-containing dross process tank, oxidant holding vessel and water storage tank are connected in parallel to the import of the high-pressure pump.
In the system of above-mentioned catalytic wet oxidation processing oil-containing dross, it is preferred that the wet catalytic oxidation reactor
Provided with the pilot outlet with ft connection, the condenser is provided with the pilot outlet with ft connection.
In the system of above-mentioned catalytic wet oxidation processing oil-containing dross, it is preferred that the wet catalytic oxidation reactor
Interior be provided with is used to adjust the heater of reaction temperature, charging aperture and use for explosion-proof safety valve, for conveying catalyst
In the agitator of stirring reaction solution.
System of the present utility model is by oil-containing dross, water, catalyst and persulfate in wet catalytic oxidation reactor
Reaction, produce strong oxidative free radical poisonous to the petroleum hydrocarbon in oil-containing dross, benzene homologues, anthracene, pyrene etc., mutagenesis, carcinogenic substance
Matter carries out advanced treating, makes its fully degraded, transforms into CO2、N2Deng harmless components, so as to reach degraded oil-containing dross
Purpose.The utility model can effectively degrade the petroleum hydrocarbon in oil-containing dross, and handle later solid product base
This is not aqueous, and dehydrating effect is good；Processing procedure is simple, and cost is cheap, and investment and operating cost are low, application easy to spread；Effectively
Solution sewage treatment plant produce scum silica frost amount it is big, it is difficult to the problem of processing.
Compared with prior art, the utility model has the advantage of：
1st, the catalytic wet oxidation system that the utility model uses has that oxidation rate is fast, treatment effeciency is high, the scope of application
It is the advantages that wide, easy to spread, and processing procedure is simple, cost is cheap, and investment and operating cost are low, effectively solve sewage disposal
It is big that factory produces scum silica frost amount, it is difficult to the problem of processing, protects environment.
2nd, the utility model provides a kind of processing system of oil-containing dross, closed high temperature (correspondingly generating high pressure)
Under the conditions of, over cure acid free radical and hydroxyl radical free radical degraded oil-containing dross are produced by activation of catalyst persulfate, effectively
Reduce harm of the oil-containing dross to environment.
3rd, system of the present utility model can be carried out abundant by specific connected mode to the petroleum hydrocarbon of oil-containing dross
Degraded, it is degraded to and endangers small, tractable gas phase, solid phase and liquid product, reach innoxious purpose.
Brief description of the drawings
Fig. 1 is the system schematic of catalytic wet oxidation processing oil-containing dross in the utility model embodiment 1.
Fig. 2 be the utility model embodiment 1 application example in differential responses temperature on oil-containing dross oil content influence
Graph of relation.
Fig. 3 be the utility model embodiment 1 application example in the differential responses time on oil-containing dross oil content influence
Graph of relation.
Fig. 4 is matching somebody with somebody for different ferrous sulfate and sodium peroxydisulfate to compare oil-containing in the application example of the utility model embodiment 1
The graph of relation that scum silica frost oil content influences.
Fig. 5 be the utility model embodiment 1 application example in different sodium peroxydisulfate additions to oil-containing dross oil content
The graph of relation of influence.
Marginal data：
1st, oil-containing dross process tank；2nd, oxidant holding vessel；3rd, water storage tank；4th, high-pressure pump；5th, preheater；6th, catalytic wet
Oxidation reactor；7th, condenser；8th, gas processer.
Embodiment
The utility model is further described below in conjunction with Figure of description and specific preferred embodiment, but not because
This and limit the scope of protection of the utility model.
Material and instrument employed in following examples are commercially available.
Embodiment 1：
A kind of system of catalytic wet oxidation processing oil-containing dross of the present utility model, as shown in figure 1, the catalytic wet oxygen
Changing the system of processing oil-containing dross includes oil-containing dross process tank 1, oxidant holding vessel 2, water storage tank 3, high-pressure pump 4, preheater
5th, wet catalytic oxidation reactor 6, condenser 7 and gas processer 8.Oil-containing dross process tank 1, oxidant holding vessel 2 and water
Storage tank 3 is connected in parallel to the import of high-pressure pump 4, at high-pressure pump 4, preheater 5, wet catalytic oxidation reactor 6, condenser 7 and gas
Reason device 8 is sequentially connected, i.e. the outlet of high-pressure pump 4 is connected to the import of preheater 5, and the outlet of preheater 5 is connected to catalytic wet
The import of oxidation reactor 6, the outlet (upper outlet) of wet catalytic oxidation reactor 6 are connected to the import of condenser 7, condenser
7 outlet (upper outlet) is connected to gas processer 8.
In the present embodiment, wet catalytic oxidation reactor 6 is additionally provided with the pilot outlet with ft connection, the pilot outlet
(lower to export) is externally connected.
In the present embodiment, condenser 7 is additionally provided with the pilot outlet with ft connection, and pilot outlet (lower to export) is connected to outer
Portion's treatment tank.
It is provided with the present embodiment, in wet catalytic oxidation reactor 6 and is used to adjust the heater of reaction temperature, for preventing
Quick-fried safety valve, the charging aperture for conveying catalyst and the agitator for stirring reaction solution, heater, safety valve and
Charging aperture omits show in Fig. 1.
The single part used in the system of above-mentioned the present embodiment is commercially available, but the design method of the system was not met
Report.
For the system of the catalytic wet oxidation processing oil-containing dross of above-mentioned the present embodiment when handling oil-containing dross, its work is former
Reason is as follows：
Oil-containing dross, oxidant (persulfate) and water are respectively from oil-containing dross process tank 1, oxidant holding vessel 2, water storage
Tank 3 is released, and in the duct after full and uniform mixing, is passed through preheater 5 by high-pressure pump 4, after preheated device 5 preheats, is heated
Oil-containing dross entrance to assigned temperature is filled with the wet catalytic oxidation reactor 6 of catalyst, carries out oxidative decomposition, warp
After spending certain reaction time, the gas-phase product obtained after processing is led at extraneous gas by condenser 7, condensed gas
Reason device 8 is discharged after handling, and condensed liquid (predominantly water and soluble hydrocarbons) is led to by the pilot outlet of condenser 7
To outside sewage disposal system, the solid product after processing leads to outside by the pilot outlet of wet catalytic oxidation reactor 6
Further recycling after processing.
In the present embodiment, wet catalytic oxidation reactor 6 is high-temperature high-pressure reaction kettle, and the function of preheater 5 is by oil-containing
The mixture of scum silica frost and oxidant and water is heated to react required temperature, then passes in reactor, at the reaction temperatures instead
Should, it is also required to set in reactor and keeps reaction temperature.
The system of catalytic wet persulfate oxidation processing oil-containing dross of the present utility model can be effectively to containing oil float
The poisonous, mutagenesis such as slag petrochina hydro carbons, benzene homologues, anthracene, pyrene, carcinogen carry out advanced treating, have oxidation rate fast, locate
The advantages that effect is good, applied widely is managed, it is big can effectively to solve sewage treatment plant's generation scum silica frost amount, it is difficult to the problem of processing.Through
After oil-containing dross processing system of the present utility model processing, in oil-containing dross oil content be reduced to 39.92% by 92.63%~
16.75%, significant effect.
A kind of system that oil-containing dross is handled using above-mentioned catalytic wet oxidation of the present utility model handles oil-containing dross
Application example, comprise the following steps：Oil-containing dross is mixed with water, catalyst and persulfate are then added, in airtight condition
Lower stirring reaction, reaction temperature be 150 DEG C~440 DEG C, the reaction time be 5min~75min, after reaction, obtain gas-phase product with
Solid product, gained gas-phase product is condensed, soluble gas-phase product is changed into liquid product, complete to oil-containing dross
Processing.
In the present embodiment, following preferable process conditions can be used to be implemented：
The catalyst and the mass ratio of persulfate added is 1: 1~30, and the dosage of persulfate is 0.75g/g oil-containings
Scum silica frost~1.08g/g oil-containing dross, reaction temperature are 220 DEG C~340 DEG C, and the reaction time is 15min~55min.
Catalyst is iron powder, containing ferrous molysite or containing ferric molysite, as ferrous ion, ferric iron from
One of son, Zero-valent Iron, preferred catalyst are ferrous sulfate, ferric sulfate or ferroso-ferric oxide, but not limited to this.
The preferred sodium peroxydisulfate of persulfate, potassium peroxydisulfate or ammonium persulfate, but not limited to this.
The mass ratio of oil-containing dross and water is 1: 1~5.
The speed of stirring is 30rps~90rps.In course of reaction, can control mixing speed is steady state value, preferably 60rps.
This method can the closed progress in high-temperature high-pressure reaction kettle, when reaction temperature is at 150 DEG C~440 DEG C, reaction pressure
Power is corresponding in the range of 1MPa~35MPa.
In the present embodiment, reacted gasification product is collected into liquid product by condenser pipe, and collect reacted solid
Phase product, by detection, the oil content of solid product is greatly reduced.Soluble gas-phase product is the petroleum hydrocarbon of oil-containing dross
Some soluble hydrocarbons in the gas phase are remained after class degraded, and remaining gas-phase product is CO2、SO2Deng and part it is insoluble
Petroleum hydrocarbon, remaining gas-phase product can further work-up recyclings.
It is proportioning in the application example on reaction temperature, reaction time, ferrous sulfate and sodium peroxydisulfate, over cure below
The research of the influence of sour sodium dosage.
A kind of method of catalytic wet oxidation processing oil-containing dross, comprises the following steps：Oil-containing dross is mixed with water, contained
The mass ratio of oil float slag and water is 1: 4, then adds ferrous sulfate and sodium peroxydisulfate, stirs and heated in confined conditions
Reaction, agitator speed 60rps, gas-phase product and solid product is obtained after reaction, gained gas-phase product is condensed, made
Soluble gas-phase product is changed into liquid product, completes the processing to oil-containing dross.
Influence on reaction temperature：
This group experiment is using reaction temperature as variable, reaction time 15min, and the dosage of ferrous sulfate and sodium peroxydisulfate is equal
For 0.25g/g oil-containing dross, i.e. the mass ratio of ferrous sulfate and sodium peroxydisulfate is 1: 1.Experimental result is shown in Table 1.
Influence of the reaction temperature of table 1 to oil-containing dross oil content
| Reaction temperature (DEG C) | 220 | 250 | 280 | 310 | 340 |
| Oil content (%) | 60.67 | 50.02 | 43.81 | 39.92 | 39.89 |
With the rise of reaction temperature, ferrous sulfate excites SO caused by persulfate4 -It is more and more with OH, it is right
The petroleum hydrocarbon degradation effect of oil-containing dross is significantly improved.As shown in Figure 2.When temperature reaches 310 DEG C, reach most
Good effect, oil content is reduced to 39.92% in oil-containing dross, the unobvious of oil content change thereafter, so optimum temperature is 310
℃。
It is the influence on the reaction time below：
Using the reaction time as variable, reaction temperature is 310 DEG C for this group experiment, and the dosage of ferrous sulfate and sodium peroxydisulfate is equal
For 0.25g/g oil-containing dross, i.e. the mass ratio of ferrous sulfate and sodium peroxydisulfate is 1: 1.Experimental result is shown in Table 2.
Influence of the reaction time of table 2 to oil-containing dross oil content
| Reaction time (min) | 15 | 25 | 35 | 45 | 55 |
| Oil content (%) | 39.92 | 38.72 | 37.85 | 35.55 | 35.51 |
From the figure 3, it may be seen that with the extension in reaction time, the petroleum hydrocarbon in oil-containing dross is further degraded, when anti-
When extending to 45min between seasonable, the oil content of oily sludge is reduced to 35.55%, and what oil content almost change without thereafter,
So Best Times are 45min.
It is the influence of the proportioning on ferrous sulfate and sodium peroxydisulfate below：
This group experiment is using the proportioning of ferrous sulfate and sodium peroxydisulfate as variable, and reaction temperature is 310 DEG C, and the reaction time is
45min.Experimental result is shown in Table 3.
Table 3 is with ferrous sulfate and sodium peroxydisulfate with the influence for comparing oil-containing dross oil content
As shown in Figure 4, with the increase of ferrous sulfate and the proportioning of sodium peroxydisulfate, oil content in oil-containing dross is under first
The trend risen after drop, when proportioning increases to 1: 5, oil content have decreased to minimum in the oil-containing dross after processing, be
33.22%, this shows that the optimum proportioning of ferrous sulfate and sodium peroxydisulfate is 1: 5.
It is the influence on sodium peroxydisulfate dosage below：
This group experiment is using the dosage of sodium peroxydisulfate as variable, and reaction temperature is 310 DEG C, reaction time 45min, sulfuric acid
Ferrous and sodium peroxydisulfate proportioning is 1: 5.Experimental result is shown in Table 4.
Influence of the sodium peroxydisulfate dosage of table 4 to oil-containing dross oil content
Influence of the sodium peroxydisulfate dosage to oil-containing dross petrochina hydrocarbon content is as shown in Figure 5.As shown in Figure 5, most
Under optimal conditions, the petroleum hydrocarbon content in oil-containing dross constantly declines with the increase of sodium peroxydisulfate dosage, when adding
When amount reaches 1g/g oil-containing dross, oil content, which declines, to tend towards stability, economically, it can be deduced that sodium peroxydisulfate optimum dosage
For 1g/g oil-containing dross.
It is described above, only it is preferred embodiment of the present utility model, not the utility model is made any formal
Limitation.Although the utility model is disclosed as above with preferred embodiment, but is not limited to the utility model.It is any ripe
Those skilled in the art is known, in the case where not departing from Spirit Essence of the present utility model and technical scheme, all using upper
The methods and technical content for stating announcement makes many possible changes and modifications to technical solutions of the utility model, or is revised as
With the equivalent embodiment of change.Therefore, every content without departing from technical solutions of the utility model, according to skill of the present utility model
It is new to still fall within this practicality to any simple modification, equivalent substitution, equivalence changes and modification made for any of the above embodiments for art essence
In the range of the protection of type technical scheme.
Claims (3)
1. a kind of system of catalytic wet oxidation processing oil-containing dross, it is characterised in that the system includes oil-containing dross processing
Tank (1), oxidant holding vessel (2), water storage tank (3) and the high-pressure pump (4) being sequentially connected, preheater (5), catalytic wet oxidation
Reactor (6), condenser (7) and gas processer (8), the oil-containing dross process tank (1), oxidant holding vessel (2) and water
Storage tank (3) is connected in parallel to the import of the high-pressure pump (4).
2. the system of catalytic wet oxidation processing oil-containing dross according to claim 1, it is characterised in that the wet type is urged
Oxidation device (6) is provided with the pilot outlet with ft connection, and the condenser (7) is provided with to go out with the auxiliary of ft connection
Mouthful.
3. the system of catalytic wet oxidation processing oil-containing dross according to claim 1 or 2, it is characterised in that described wet
Provided with the heater for adjusting reaction temperature, for explosion-proof safety valve, for conveying in formula catalyst oxidation reactor (6)
The charging aperture of catalyst and the agitator for stirring reaction solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216011A (en) * | 2017-07-11 | 2017-09-29 | 湖南大学 | Catalytic wet oxidation handles the method and system of oil-containing dross |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216011A (en) * | 2017-07-11 | 2017-09-29 | 湖南大学 | Catalytic wet oxidation handles the method and system of oil-containing dross |
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