CN203007070U - Device for preprocessing heavy oil refining sewage - Google Patents
Device for preprocessing heavy oil refining sewage Download PDFInfo
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- CN203007070U CN203007070U CN 201320005041 CN201320005041U CN203007070U CN 203007070 U CN203007070 U CN 203007070U CN 201320005041 CN201320005041 CN 201320005041 CN 201320005041 U CN201320005041 U CN 201320005041U CN 203007070 U CN203007070 U CN 203007070U
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Abstract
The utility model provides a device for preprocessing heavy oil refining sewage. The device comprises a homogenization and sedimentation tank, a demulsifying and deoiling tank, a coagulation and sedimentation tank, a primary ozone oxidation device and a secondary ozone catalytic oxidation device which are sequentially arranged, wherein the homogenization and sedimentation tank, the demulsifying and deoiling tank, the coagulation and sedimentation tank, the primary ozone oxidation device and the secondary ozone catalytic oxidation device are sequentially communicated with one another through a sewage pipeline. According to the device provided by the utility model, high-oil-content heavily-polluted sewage produced during heavy oil refining is preprocessed by adopting a technical route of homogenized sedimentation, demulsified-deoiling desulfurization, coagulated-sedimentation desulfurization, primary ozone oxidation and secondary ozone catalytic oxidation, and preprocessed sewage meets the inlet water requirements of a biochemical processing process for ordinary oil refining wastewater processing plants; and when the device provided by the utility model is used for preprocessing the heavy oil refining sewage, multiple functions, such as oil resource recovery and malodorous gas pollution elimination, can also be realized.
Description
Technical field
The utility model relates to inferior heavy oil refinery sewage is carried out pretreated technology, and the pretreated device of especially a kind of sewage from thick oil refining belongs to the Refinery Wastewater Treatment Technology field.
Background technology
Viscous crude typically refers to viscosity greater than 1 * 10
2MPas or relative density are greater than 0.934g/cm
3Heavy crude asphalt petroleum, and with viscosity greater than 5 * 10
4The viscous crude of MPas is called super viscous crude.Viscous crude also has the characteristics such as high-sulfur nitrogen, high saliferous, high metal, high acid value, high impurity except the denominator with mink cell focuses such as low API degree, high viscosity, high-density, high carbon residue, non-hydrocarbon compound are abundant.
Along with the world economy accelerated development, the conventional oil reserves reduce day by day, and world's oil supply is tending towards heaviness, in poor quality, and 70% in global residual petroleum resource is viscous crude, and the viscous crude resource of the country such as Venezuela, Canada, China and Indonesia is the abundantest.The viscous crude amount of finish cumulative year after year of China refinery.Since 2010, CNPC's Liaohe River petro-chemical corporation year processing viscous crude reached 5,000,000 ton/years, ranks first in the country.
Sewage from thick oil refining (or claiming viscous crude refining waste water) is mainly from raw material storage tank, atmospheric and vacuum distillation unit, viscosity breaking plant, delayed coking unit, comprise the dehydration of high viscous crude storage tank, atmospheric and vacuum distillation unit deliming Electric Desalting Wastewater, delayed coking unit deliming Electric Desalting Wastewater, the water of condensation etc. that steams out greatly, sewage from thick oil refining petroleum class, COD content are high, emulsification is serious, the profit density difference is little, the difficult separation, biodegradability is poor.the former 60t/h of Liaohe River petro-chemical corporation (surpassing) sewage from thick oil refining pretreatment unit adopts the patented technology of ZL200610113947.9, mainly for From Liaohe Heavy Crude, the high oily(waste)water that super viscous crude raw material produces in refining process, what adopt is the agent technology route of " water quality and quantity adjusting-oil removal sedimentation-eddy flow oily water separation-floatation purification ", water pot is regulated in the sewage from thick oil refining input, tentatively remove oil content and silt particle in sewage, then breakdown of emulsion makes the oil content in water separate with water body, further implement oily water separation in the recycling oil-water separator, water with enter dissolved air floatation machine after coagulating agent and coagulant aids mix and implement floatation purification, the discharge water of flotation machine is sent into the sewage-farm and is carried out subsequent treatment process.The major objective of this technique is to reduce pollutant load, reclaims the viscous crude resource, and the means of employing are mainly the combinations of physical chemistry treatment process.
Yet, increase along with Liaohe River petro-chemical corporation processing Venezuela extra heavy oil, Canadian cold air lake wet goods high-sulfur high-nitrogen stock ratio, the phenols of sewage from thick oil refining, rate and inorganic sulphur content increase severely, the content of sulfur-bearing nitrogen heterocyclic ring polarity organic pollutant also increases considerably, water quality characteristic shows as bio-toxicity to be strengthened, the biodegradability variation.The defective to the regulation and control of water quality biodegradability in original pretreatment technology (technology of ZL200610113947.9) begins to manifest, this technique can not effectively be degraded to the sulfide in abominable water quality water body, bio-toxicity material, difficult degradation heterogeneous ring compound, and being difficult to provides biodegradability good influent quality for composite wastewater field, downstream.In addition, due to the high-speed friction effect of particle in sewage, the oil-water separator serious wear in former technique, cyclone pipe has to change frequent, affects long-period stable operation.In addition, because sulfur-containing foul material in sewage is more, when adopting dissolved air flotation device in former technique to process, near the foul gas concentration over-standard device zone causes certain safety and Health hidden danger.Enter 2009, domestic Petrochemical Enterprises begins to carry out successively the one-level A mark in country " cities and towns industrial sewage emission standard " (GB 18918-2002), the maximum concentration of externally discharged waste water COD will be controlled at below 50mg/L, and this just controls the source of sewage from thick oil refining and has proposed stricter pre-treatment requirement.
The utility model content
Main purpose of the present utility model is to process present situation based on present refinery sewage from thick oil refining, provide a kind of sewage from thick oil refining pretreated device, utilize this device to carry out pre-treatment to sewage from thick oil refining, make the high-concentration hardly-degradable oily(waste)water that produces in viscous crude refinery process can reach after pretreatment the water inlet requirement of general refinery wastewater treatment field biochemical process, solve the impact to the downstream wastewater treatment field that causes due to the viscous crude material property change.
For reaching above-mentioned purpose, the invention provides a kind of for the pretreated device of sewage from thick oil refining, this device comprises homogeneous slurry tank, breaking milk and removing oil tank, coagulating setting tank, one-level ozone-oxidizing device and the secondary device for catalyzing and oxidating ozone that order arranges, and is communicated with by the sewer pipeline order between homogeneous slurry tank, breaking milk and removing oil tank, coagulating setting tank, one-level ozone-oxidizing device and secondary device for catalyzing and oxidating ozone.
According to specific embodiments of the present utility model, in the pretreated device of sewage from thick oil refining of the present utility model:
Be provided with acid-alkali accommodation equipment in described homogeneous slurry tank, also be provided with the oil slick that reclaims water body top in the homogeneous slurry tank, the equipment of thick dispersed oil, and the equipment that reclaims the macrobead silt particle of homogeneous slurry tank bottom sedimentation;
Described breaking milk and removing oil tank is provided with the finely divided oil, the oil in water emulsion breakdown of emulsion that reclaim water body top in the breaking milk and removing oil tank and forms the equipment than larger oil droplet, and the equipment that reclaims the suspended solid that metallic sulfide precipitates, breakdown of emulsion forms of breaking milk and removing oil pot bottom sedimentation;
Described coagulating setting tank is provided with the residue oil in water emulsion breakdown of emulsion formation on water body top in the recovery coagulating setting tank than the equipment of larger oil droplet, and the metallic sulfide of recovery coagulant precipitation pot bottom precipitates, the equipment of the suspended solid of coagulation formation.
According to specific embodiments of the present utility model, in the pretreated device of sewage from thick oil refining of the present utility model, described one-level ozone-oxidizing device, secondary device for catalyzing and oxidating ozone can adopt the ozone-oxidizing device of prior art.In the utility model preferably:
Described one-level ozone-oxidizing device and secondary device for catalyzing and oxidating ozone comprise respectively: ozone generation system, ozone dissolved air water produce system, ozone oxidation system and oxidizing reaction separation system; Ozone generation system produces system entry with the ozone dissolved air water and is connected, the refluxing opening of oxidizing reaction separation system also is connected with ozone dissolved air water generation system, the ozone dissolved air water produces system outlet and is connected in the ozone oxidation system entry, and the ozone oxidation system outlet is connected in the oxidizing reaction separation system; The ozone that is produced by ozone generation system and the partial reflux sewage of oxidizing reaction separation system enter ozone dissolved air water generation system and form the ozone dissolved air water, the ozone dissolved air water enters the ozone oxidation system and carries out the degraded of organic pollutant, the water outlet of ozone oxidation system and pending sewage are mixed into the oxidizing reaction separation system, carry out the continuation degraded of the separation of non-dissolved pollutant in sewage and solubilised state organic pollutant, and complete separating of residual ozone and water body; The pressure of described ozone oxidation system is higher than normal pressure.
According to specific embodiments of the present utility model, in the pretreated device of sewage from thick oil refining of the present utility model, be filled with heterogeneous catalyst in described secondary device for catalyzing and oxidating ozone.
According to specific embodiments of the present utility model, the pretreated device of sewage from thick oil refining of the present utility model, in one-level ozone-oxidizing device and secondary device for catalyzing and oxidating ozone, the pressure range of described ozone oxidation system is 0.4MPa-0.6MPa, and the temperature range of ozone oxidation is 60 ℃-80 ℃.
According to specific embodiments of the present utility model, in the pretreated device of sewage from thick oil refining of the present utility model:
Described ozone dissolved air water produces system and is comprised of gas fluid mixture pump and respective valves thereof;
Described ozone generation system order is made of air compressor machine, gas-holder, freeze drier, oxygenerator, ozonizer;
Described ozone oxidation system is made of high pressure contact reaction tower and pressure maintaining valve;
Described oxidizing reaction separation system is made of ozone dissolved air water reliever, oxidizing reaction separate tank, slag scraper.
According to specific embodiments of the present utility model, in the pretreated device of sewage from thick oil refining of the present utility model, also airfloat equipment can be set further in described one-level ozone-oxidizing device.Residual oil in water emulsion and SS in water body removed in oxidation to harness emulsion effect by air supporting effect and ozone.
According to specific embodiments of the present utility model, in the pretreated device of sewage from thick oil refining of the present utility model, also be provided with flocculant concentration equipment between described coagulating setting tank and one-level ozone-oxidizing device.By adding the flocculation agent such as inorganic aluminate, can make and remove residual non-dissolved pollutant in water body in the one-level ozone-oxidizing device.
Utilize device of the present utility model to carry out pretreated method to sewage from thick oil refining and comprise step:
Sewage from thick oil refining is inputted the homogeneous slurry tank, this homogeneous slurry tank arranges acid-alkali accommodation equipment and possesses the function of sewage being carried out homogeneous in slurry tank, the pH value scope of utilizing described acid-alkali accommodation equipment to regulate water body is carried out homogeneous between 6.5-8.5 and to sewage, be incubated afterwards at 70 ℃-80 ℃, by the free setting more than 12 hours, oil slick, thick dispersed oil are separated with water body float up to the top recovery of homogeneous sedimentation tank body, macrobead silt particle and water body separate and subside are removed to homogeneous sedimentation tank base, and the macrobead silt particle is removed in sedimentation;
The water outlet of homogeneous slurry tank is passed through with oil removing-sulphur removal compound inputted the breaking milk and removing oil tank after line mixer fully mixes, insulation is at 70 ℃-80 ℃, through the sedimentation more than 12 hours, finely divided oil, oil in water emulsion breakdown of emulsion in water body are formed than larger oil droplet, separate with water body and float up to the top recovery of breaking milk and removing oil tank body, the suspended solid that metallic sulfide precipitation, breakdown of emulsion form separates with water body, is settled down to the breaking milk and removing oil tank base and removes;
The water outlet of breaking milk and removing oil tank is passed through with coagulation-sulphur removal compound inputted coagulating setting tank after line mixer fully mixes, insulation is at 70 ℃-80 ℃, through the sedimentation more than 12 hours, residue oil in water emulsion breakdown of emulsion in water body is formed than larger oil droplet, separate with water body and float up to the top recovery of coagulant precipitation tank body, the suspended solid that metallic sulfide precipitation, coagulation form separates with water body, is settled down to the bottom removal of coagulant precipitation tank body;
With coagulating setting tank water outlet input one-level ozone-oxidizing device, water temperature remains on 60 ℃-80 ℃, hierarchy of control pressure 0.4-0.6MPa, the dosage of ozone is the 200-300g/t staying water, total hydraulic detention time is removed remaining oil in water emulsion and suspended solid (SS), degradation biological toxicant and part heterocycle polarity organic pollutant in 20min, reduce the water body bio-toxicity, tentatively improve the water body biodegradability;
The water outlet of one-level ozone-oxidizing device enters the secondary device for catalyzing and oxidating ozone, and water temperature remains on 60 ℃-80 ℃, hierarchy of control pressure 0.4-0.6MPa, and the dosage of ozone is the 200-300g/t staying water, total hrt is more than 30min; Heterogeneous catalyst and ozone simultaneously in the presence of, further degrade remaining bio-toxicity material and solubilised state macromole heterocycle polarity organic pollutant improve the biodegradability of water body;
The water outlet of secondary device for catalyzing and oxidating ozone enters refinery wastewater treatment field biochemical process and carries out subsequent disposal.
The creator shows by lot of experiments, inorganic sulphide (S
2-), aldehydes matter, benzene homologues be the principal element that causes the sewage from thick oil refining acute biological toxicity, in sewerage pretreatment method of the present utility model, special design for the solution of bio-toxicity, wherein, utilized before this physical chemistry method to adopt sweetening agent to remove inorganic sulfur, and made it to enter the body refuse subsequent disposal, then adopt the ozone oxidation method to come degrading phenol and benzene homologues, and the degraded organosulfur, bio-toxicity is reduced.In addition, show according to correlative study, sulfur-bearing nitrogen heterocyclic ring polarity organic pollutant is the major cause that causes the saprobia degradation property poor, in sewerage pretreatment method of the present utility model, be to adopt the catalytic ozonation method heterocycle polarity organic pollutant of degrading, improve the biodegradability of sewage.Through above preprocessing process of the present utility model, reached the water inlet standard of general refinery wastewater treatment field biochemical process from the water outlet of secondary device for catalyzing and oxidating ozone, can continue to complete subsequent disposal according to the treatment process of general refinery sewage.And the sump oil of telling from homogeneous slurry tank, breaking milk and removing oil tank and coagulating setting tank can be introduced slop oil tank or contaminated-oil basin by pipeline, runs up to a certain amount of blowback petroleum tank dehydration freshening; The scum silica frost that the silt particle that each produces in stage and device for catalyzing and oxidating ozone produce, bed mud are introduced the body refuse pond by pipeline, deliver at any time or regularly " three mud " treatment system.
According to specific embodiments of the present utility model, described homogeneous slurry tank is namely to have set up acid-alkali accommodation equipment on the basis of the common slurry tank of prior art, thereby has possessed the function of sewage being carried out homogeneous, is called the homogeneous slurry tank in the utility model.In the utility model, by sewage is carried out homogenization treatment, can also give security for follow-up emulsion splitter can play a role under suitable pH condition.In the utility model, after regulating pH value of sewage water and homogenization treatment, be incubated free settings more than 12 hours in 70 ℃-80 ℃, oil slick in sewage from thick oil refining, thick dispersed oil are separated with water body float up to homogeneous sedimentation tank body top and reclaimed, the macrobead silt particle in sewage and water body separate and subside to homogeneous sedimentation tank base is removed.
According to specific embodiments of the present utility model, described oil removing-sulphur removal compound forms by emulsion splitter, sulfur elimination, coagulating agent and water are composite; Described emulsion splitter effective constituent is the multipolymer of acrylamide and vinylformic acid dimethylamino methyl methyl chloride, and described sulfur elimination is zinc sulfate, and described coagulating agent is Tai-Ace S 150; In oil removing-sulphur removal compound, the mass content of emulsion splitter is 5%, and the mass content of sulfur elimination is 4.5%～5.5%, and the mass content of coagulating agent is 20%; The dosage of oil removing-sulphur removal compound is 3.0-5.0 kg/ton staying water.Described emulsion splitter, sulfur elimination, coagulating agent be commercially available acquisition all, and for example, described effective constituent is that the multipolymer emulsion splitter of acrylamide and vinylformic acid dimethylamino methyl methyl chloride can be for available from the general vertical clear PRAESTOL650BC of Germany.The utility model is on Practical Project uses, and the consisting of of preferred oil removing-sulphur removal compound: the mass content of emulsion splitter is 5%, and the mass content of sulfur elimination is 5%, and the mass content of coagulating agent is 20%, and surplus is water; The concentration that can suitably adjust sulfur elimination when the fluctuation of water inlet sulfide is 4.5%～5.5%, and the concentration of emulsion splitter and coagulating agent is preferably constant.
according to specific embodiments of the present utility model, the structure of described breaking milk and removing oil tank is consistent with slurry tank, the water outlet of homogeneous slurry tank enters with the slight drag water distribution mode at the breaking milk and removing oil pot bottom, water body in this breaking milk and removing oil tank, breakdown of emulsion occurs under oil removing-sulphur removal compound effect, except reaction of Salmon-Saxl, through the gravity settling that is incubated more than 12 hours at 70 ℃-80 ℃, can make the finely divided oil in water body, the oil in water emulsion breakdown of emulsion forms than larger oil droplet, separate with water body and float up to breaking milk and removing oil tank body top and reclaimed, and make the metallic sulfide precipitation in water body, the suspended solid that breakdown of emulsion forms separates with water body, be settled down to the breaking milk and removing oil tank base and removed.
According to specific embodiments of the present utility model, described coagulation-sulphur removal compound forms by coagulating agent, sulfur elimination, coagulant aids and water are composite; Described coagulating agent is Tai-Ace S 150, and described sweetening agent is zinc sulfate, and described coagulant aids is cationic polyacrylamide; In coagulation-sulphur removal compound, the mass content of coagulating agent is 18～22%, and the mass content of sulfur elimination is 22.5%～27.5%, and the mass content of coagulant aids is 13.5%～16.5%; Coagulation-sulphur removal compound dosage is 1.3-2.0 kg/ton staying water.According to preferred embodiment of the utility model, in coagulation-sulphur removal compound, the mass content of coagulating agent is 20%, and the mass content of sulfur elimination is 25%, and the mass content of coagulant aids is 15%, and surplus is water.
According to specific embodiments of the present utility model, described coagulant precipitation jar structure is consistent with the breaking milk and removing oil tank, the water inlet operating method is also consistent, water body in this coagulating setting tank, under the effect of coagulation-sulphur removal compound, through the sedimentations that are incubated more than 12 hours at 70 ℃-80 ℃, residue oil in water emulsion breakdown of emulsion in water body is formed than larger oil droplet, separate with water body and float up to coagulant precipitation tank body top and reclaimed, and the suspended solid that makes metallic sulfide precipitation, coagulation form separates with water body, is settled down to coagulant precipitation tank body bottom and is removed.
In the utility model, described " homogeneous sedimentation-breaking milk and removing oil sulphur removal-coagulant precipitation sulphur removal " operation is mainly to reclaim to greatest extent the viscous crude resource by the materialization means, remove the non-dissolved pollutants such as body refuse, SS, experiment shows, utilize technology of the present utility model, process through described " homogeneous sedimentation-breaking milk and removing oil sulphur removal-coagulant precipitation sulphur removal ", the inorganic sulphide substrate concentration that has bio-toxicity in sewage from thick oil refining can be down to below 5mg/L.
According to specific embodiments of the present utility model, the water sample after described " homogeneous sedimentation-breaking milk and removing oil sulphur removal-coagulant precipitation sulphur removal " processed further passes through the two-stage ozone Oxidation Treatment, with the acute biological toxicity of reduction water quality, and improves biodegradability.
According to specific embodiments of the present utility model, the utility model is by controlling dosage and the hydraulic detention time of ozone in the one-level ozone-oxidizing device, under specific high-temperature and high-pressure conditions, can effectively remove oil in water emulsion and SS remaining in water body, degradation biological toxicant and part heterocycle polarity organic pollutant, reduce the water body bio-toxicity, tentatively improve the water body biodegradability.The utility model has considered energy consumption that treatment effect, temperature, pressure etc. bring and safety factors etc., has determined that best condition of high voltage is 0.4-0.6MPa, and treatment temp is 60 ℃-80 ℃, and the dosage of ozone is the 200-300g/t staying water; Under such treatment condition, can strengthen the degradation efficiency to pollutents such as phenols, benzene homologues, the acute biological toxicity materials such as the phenols of the overwhelming majority, benzene homologues in the water body of can effectively degrading in 20min, and the degraded part is encircled more, heterogeneous ring compound.According to preferred embodiment of the present utility model, in control one-level ozone-oxidizing device, total hydraulic detention time is 15～20min.
According to specific embodiments of the present utility model, the utility model is by controlling dosage (200-300g/t staying water), hydraulic detention time (more than 30min) and the high-temperature and high-pressure conditions of ozone in the secondary device for catalyzing and oxidating ozone, under the synergy of catalyzer, remaining phenols in water body, arene and macromole heterocycle polar compound are degraded, and the biodegradability of water body is effectively promoted.According to preferred embodiment of the present utility model, in control secondary device for catalyzing and oxidating ozone, total hydraulic detention time is 30～40min.
According to specific embodiments of the present utility model, in described secondary device for catalyzing and oxidating ozone, heterogeneous catalyst is made of supported carrier active ingredient transition metal oxide; Described carrier is silochrom; Described active ingredient comprises primary activity component and auxiliary activity component, and the metal of described primary activity component is Mn, and the metal of auxiliary activity component is selected from one or more in Fe, Zr, Ti, is preferably Fe.Preferably, the loading of described transition metal is the 1～15wt% (in metal) of silochrom.Preferably, described silochrom mean pore size is 8.0～10.0nm, specific surface area 300～400m
2/ g, pore volume 0.8～1.0ml/g.Preferably, in described active ingredient, the mass ratio of primary activity component is 60-80% (in metal), and the mass ratio of auxiliary activity component is 20-40% (in metal).Adopt the heterogeneous catalyst of the utility model preferred version, remaining bio-toxicity material and solubilised state macromole heterocycle polarity organic pollutant in the water body of can degrading better, the biodegradability of raising water body.
According to specific embodiments of the present utility model, in described secondary device for catalyzing and oxidating ozone, the loadings of catalyzer per hour is preferably the 3m%-5m% for the treatment of capacity.
More specifically, in the utility model secondary device for catalyzing and oxidating ozone, heterogeneous catalyst used prepares in accordance with the following methods:
1) with silochrom at 100 ℃～120 ℃ temperature dry 8～12 hours, add 1～10% hydrogen peroxide solution, soaked stagnant 12～36 hours, take out, dry in the shade, standby;
2) the silochrom equal-volume is soaked stagnant in transition metal salt solution, soaked stagnant 12～36 hours, at 100 ℃～120 ℃ temperature, drying is 8～12 hours, calcined under 300～550 ℃ 4～8 hours again, obtain the catalyzer for catalytic oxidation treatment waste water, the loading of transition metal is the 1～15wt% (in metal) of silochrom.
In the process of above-mentioned preparation heterogeneous catalyst, preferred calcining temperature is 450～550 ℃, the heterogeneous catalyst for preparing under this preferred calcination temperature condition, than the catalyzer of other calcining temperatures, has treatment effect preferably for water body bio-toxicity material and the solubilised state macromole heterocycle polarity organic pollutant of secondary device for catalyzing and oxidating ozone.
According to specific embodiments of the present utility model, when the oil in water emulsion in former water, SS and sulfide content are higher, also can add appropriate oil removing-sulphur removal compound before entering the homogeneous slurry tank, improve the recovering effect to the water body petroleum class.In practical application, when only running into worst water quality (for example due to electric desalting cut water mishandle occurs and cause the profit not stratified), just can add oil removing-sulphur removal compound or other emulsion splitter breakdowns of emulsion before the homogeneous oil removing pot.
According to specific embodiments of the present utility model, can also first add the inorganic aluminate flocculation agent before input one-level ozone-oxidizing device in the coagulating setting tank water outlet, make and remove residual non-dissolved pollutant (as SS, petroleum-type) in water body in the one-level ozone-oxidizing device.selecting of this scheme is mainly to work as from non-dissolved pollutant in (surpassing) sewage from thick oil refining of surge tank (as SS, when petroleum-type) content is higher, after oil removing desulfurization process through the front, may have the residual of some SS and oil in water emulsion in water body, by first add appropriate inorganic aluminate flocculation agent in the water body before input one-level ozone-oxidizing device, also can further add coagulant aids, help the degree of depth of residual non-dissolved pollutant in water body to remove, thereby ensured the steady running of secondary catalytic ozonation, as avoided catalyzer dirty stifled, increase the service life, improve ozone degradation efficient etc., improve overall craft to the decontamination effect improving of water quality.The conventional flocculation agent in field under concrete inorganic aluminate flocculation agent can adopt, its dosage can according to SS in water body after the oil removing desulfurization process and oil in water emulsion residual quantity what and suitably definite with reference to prior art.The selection of described coagulant aids and consumption carry out with reference to the prior art in affiliated field.
In the utility model, the operational example of not mentioning in detail as how to regulate pH value etc. all can adopt under the prior art in field carry out.Do not mention in detail each unit and the system of structure, such as described slurry tank, acid-alkali accommodation equipment, breaking milk and removing oil tank, coagulating setting tank, one-level ozone-oxidizing device and secondary device for catalyzing and oxidating ozone etc., the existing installation in field under all can adopting.According to specific embodiments of the present utility model, homogeneous slurry tank, breaking milk and removing oil tank, coagulating setting tank sedimentation and sewer pipeline all adopt insulation design, take full advantage of this sewage remaining energy, make sewage temperature be not less than 70 ℃, ensure the efficient recovery of sump oil, for heterogeneous catalytic ozonation provides high-temperature water quality, reduce the activation energy of contaminant degradation simultaneously.
The beneficial effects of the utility model:
The utility model provides a kind of sewage from thick oil refining pretreated device, utilize this device, adopt the technological line of " homogeneous sedimentation-breaking milk and removing oil sulphur removal-coagulant precipitation sulphur removal-one-level ozone oxidation-secondary catalytic ozonation ", the serious pollution sewage that (surpassing) viscous crude is produced in the refinery process carries out pre-treatment, strengthened the removal to bio-toxicity in sewage, can reach general refinery wastewater treatment field biochemical process water inlet standard from the discharge water of secondary device for catalyzing and oxidating ozone, the stably reaching standard operation of more efficiently support composite wastewater field; Can realize simultaneously reclaiming the petroleum-type resource, reduce pollutant load, improve the water quality biological degradation property, alleviate the multiple effects such as foul gas pollution.Solve (surpass) sewage from thick oil refining to the impact of downstream wastewater treatment field, the one-level A that promotes (surpass) viscous crude processing refinery externally discharged waste water comprehensively to satisfy in national " cities and towns industrial sewage emission standard " (GB 18918-2002) marks.
Description of drawings
Fig. 1 is apparatus structure and the process flow sheet of the utility model embodiment 1.
Fig. 2 is the device for catalyzing and oxidating ozone structure iron that adopts in embodiment 2.
Fig. 3 is the plan structure schematic diagram of device for catalyzing and oxidating ozone shown in Figure 2.
Fig. 4, Fig. 5 and Fig. 6 are respectively nitrogen adsorption desorption graphic representation, pore size distribution curve figure and the transmission electron microscope pictures of the ozone heterogeneous catalysis agent of employing in embodiment 3.
Embodiment
Introduce in detail implementation process of the present utility model and the beneficial effect that produces below in conjunction with the drawings and specific embodiments, be intended to help the reader to understand better spiritual place of the present utility model, but but can not be interpreted as any restriction to the utility model practical range.
Embodiment 1 (surpassing) condensed oil sewage pretreatment technology flow process
See also Fig. 1, the pretreated device of sewage from thick oil refining of the present utility model comprises homogeneous slurry tank 10, breaking milk and removing oil tank 20, coagulating setting tank 30, one-level ozone-oxidizing device 40 and the secondary device for catalyzing and oxidating ozone 50 that order arranges, and is communicated with by the sewer pipeline order between homogeneous slurry tank 10, breaking milk and removing oil tank 20, coagulating setting tank 30, one-level ozone-oxidizing device 40 and secondary device for catalyzing and oxidating ozone 50.In addition, also be provided with the slop oil tank 60 of collecting from the oil slick of homogeneous slurry tank 10, breaking milk and removing oil tank 20, coagulating setting tank 30 in the pretreated device of this sewage from thick oil refining.Between coagulating setting tank 30 and one-level ozone-oxidizing device 40, surge tank 304 is set.
at first (surpassing) condensed oil sewage enters homogeneous slurry tank 10, enter the surge tank of pretreatment system as sewage, this homogeneous slurry tank 10 arranges acid-alkali accommodation equipment and possesses the function of sewage being carried out homogeneous in slurry tank, the pH value scope of utilizing NaOH or HCl to regulate water body is carried out homogeneous between 6.58.5 and to sewage, for process operation provides stable water quality and quantity, and by the 70 ℃ 80 ℃ free settings of insulation more than 12 hours, make oil slick in water body, thick dispersed oil separates with water body and floats up to homogeneous sedimentation tank body top and reclaim, macrobead silt particle and water body separate and subside to homogeneous sedimentation tank base is removed, thereby complete oil slick in sewage and the removal that disperses oil recovery and silt,
The water outlet of homogeneous slurry tank 10 with mix in pipeline from the oil removing of pharmacy jar-sulphur removal compound after promoted by pump and enter breaking milk and removing oil tank 20, in this operation, described oil removing sulphur removal compound forms by emulsion splitter, sulfur elimination, coagulating agent and water are composite; Described emulsion splitter effective constituent is the multipolymer of acrylamide and vinylformic acid dimethylamino methyl methyl chloride, and described sulfur elimination is zinc sulfate, and described coagulating agent is Tai-Ace S 150; In oil removing sulphur removal compound, the mass content of emulsion splitter is 5%, and the mass content of sulfur elimination is 5%, and the mass content of coagulating agent is 20%; The dosage of oil removing sulphur removal compound is 3.0-5.0 kg/ton staying water; In this breaking milk and removing oil tank, insulation is at 70 ℃-80 ℃, through the sedimentation more than 12 hours, finely divided oil, oil in water emulsion breakdown of emulsion in water body are formed than larger oil droplet, separate with water body and float up to the top recovery of breaking milk and removing oil tank body, the suspended solid that metallic sulfide precipitation, breakdown of emulsion form separates with water body, is settled down to the breaking milk and removing oil tank base and removes; That is, most oil in water emulsion and dispersed oil in this stage recovery water body are removed most inorganic sulphide;
The water outlet of breaking milk and removing oil tank 20 with mix in pipeline from the coagulation of pharmacy jar-sulphur removal compound after promoted by pump and enter coagulating setting tank 30, described coagulation sulphur removal compound forms by coagulating agent, sulfur elimination, coagulant aids and water are composite; Described coagulating agent is Tai-Ace S 150, and described sweetening agent is zinc sulfate, and described coagulant aids is cationic polyacrylamide; In coagulation sulphur removal compound, the mass content of coagulating agent is 20%, and the mass content of sulfur elimination is 25%, and the mass content of coagulant aids is 15%; Coagulation sulphur removal compound dosage is 1.3-2.0 kg/ton staying water; In this coagulating setting tank, insulation is at 70 ℃-80 ℃, through the sedimentation more than 12 hours, residue oil in water emulsion breakdown of emulsion in water body forms than larger oil droplet, separate with water body and float up to the top recovery of coagulant precipitation tank body, the suspended solid that metallic sulfide precipitation, coagulation form separates with water body, is settled down to the bottom removal of coagulant precipitation tank body; That is, remaining oil in water emulsion in this stage recovery water body is removed remaining non-dissolved pollutant and inorganic sulphide;
30 water outlets of coagulation oil removing pot are introduced into surge tank 304; Water in surge tank 304 is sent into one-level ozone-oxidizing device 40 according to suitable flow after the lift pump pressurization, in one-level ozone-oxidizing device 40, water temperature remains on 60 ℃-80 ℃, hierarchy of control pressure 0.4-0.6MPa, the dosage of ozone is the 200-300g/t staying water, total hydraulic detention time is in 20min, and tentatively degradation biological toxicant and macromole heterocycle polarity organic pollutant, improve the water body biodegradability;
One-level ozone-oxidizing device 40 flow by gravities enter secondary device for catalyzing and oxidating ozone 50, in secondary device for catalyzing and oxidating ozone 50, water temperature remains on 60 ℃-80 ℃, hierarchy of control pressure 0.4-0.6MPa, the dosage of ozone is the 200-300g/t staying water, and total hrt is more than 30min; Heterogeneous catalyst and ozone simultaneously in the presence of, further degradation biological toxicant and macromole heterocycle polarity organic pollutant, the biodegradability of raising water body.
(surpassing) sewage from thick oil refining can satisfy the water inlet requirement of the biochemical segment process of the general wastewater treatment field in refinery through the total draining after above main process.The sump oil of telling in homogeneous slurry tank, breaking milk and removing oil tank and coagulating setting tank can be introduced slop oil tank or contaminated-oil basin by pipeline, runs up to a certain amount of blowback petroleum tank dehydration freshening; The scum silica frost that the silt particle that each produces in stage and device for catalyzing and oxidating ozone produce, bed mud are introduced the body refuse pond by pipeline, deliver at any time or regularly " three mud " treatment system.
As shown in Figure 1, when the oil in water emulsion in former water, SS and sulfide content are higher, also can add appropriate oil removing-sulphur removal compound before entering homogeneous slurry tank 10, improve the recovering effect to the water body petroleum class.Non-dissolved pollutant (as SS, petroleum-type) is when content is higher in from (surpassing) sewage from thick oil refining of surge tank, also first add appropriate inorganic aluminate flocculation agent before input one-level ozone-oxidizing device 40, or further add coagulant aids, improve overall craft to the decontamination effect improving of water quality.
The one-level ozone-oxidizing device 40 that uses in the device flow process of embodiment 1, the structure of secondary device for catalyzing and oxidating ozone 50 are basic identical, just loading catalyst in the secondary device for catalyzing and oxidating ozone.Particularly, the structure of described one-level ozone-oxidizing device and secondary device for catalyzing and oxidating ozone such as Fig. 2, Fig. 3 describe.
As shown in Figure 2 and Figure 3, this ozone (catalysis) oxidation unit 100 (one-level ozone-oxidizing device 40, secondary device for catalyzing and oxidating ozone 50) comprises that the ozone generation system 1, the ozone dissolved air water that are linked in sequence by pipeline produce system 2, ozone (catalysis) oxidation system 3 and oxidizing reaction separation system 4; Ozone generation system 1 produces system's 2 entrances with the ozone dissolved air water and is connected, the refluxing opening 413 of oxidizing reaction separation system 4 also produces system 2 with the ozone dissolved air water and is connected, the ozone dissolved air water produces system's 2 outlets and is connected in ozone (catalysis) oxidation system 3 entrances, and 3 outlets of ozone (catalysis) oxidation system are connected in oxidizing reaction separation system 4; The ozone that is produced by ozone generation system 1 and the partial reflux sewage of oxidizing reaction separation system 4 enter ozone dissolved air water generation system 2 and form the ozone dissolved air water, the ozone dissolved air water enters ozone (catalysis) oxidation system 3 and carries out the degraded of organic pollutant, ozone (catalysis) oxidation system 3 water outlets (dissolved air water ozoniferous) are mixed into oxidizing reaction separation system 4 with pending sewage, carry out the continuation degraded of the separation of non-dissolved pollutant in sewage and solubilised state organic pollutant, and complete separating of residual ozone and water body; The pressure of described ozone (catalysis) oxidation system 3 is higher than normal pressure.In the present embodiment, the pressure range of described ozone (catalysis) oxidation system 3 is 0.4MPa-0.6MPa, and the temperature range of ozone (catalysis) oxidation is 60 ℃-80 ℃.
Further, described ozone generation system 1 order is made of air compressor machine 11, gas-holder 12, freeze drier 13, oxygenerator 14, ozonizer 15.At first, air enters gas-holder 12 after air compressor machine 11 compressions, and gas-holder 12 pressurized air out enters oxygenerator 14 after freeze drier 13 dryings, and oxygenerator 14 produces pure oxygen and enters ozonizer 15, produces ozone after ozonizer 15 reactions.
Described oxidizing reaction separation system 4 is made of oxidizing reaction separate tank 41, ozone dissolved air water reliever 42 and slag scraper 43; Oxidizing reaction separate tank 41 is provided with waste water import 411, wastewater outlet 412, refluxing opening 413, waste sludge discharge mouth 414 and sewage draining exit 415;
Described ozone dissolved air water produces system 2 and is comprised of gas fluid mixture pump 21 and respective valves (not shown) thereof; Described ozone (catalysis) oxidation system 3 is made of high pressure contact reaction tower 31 and pressure maintaining valve (not shown).The ozone that ozone generation system 1 produces enters in gas fluid mixture pump 21, the partial reflux sewage of oxidizing reaction separation system 4 flows out from refluxing opening 413, enter again in gas fluid mixture pump 21, ozone and partial reflux sewage form the ozone dissolved air waters by gas fluid mixture pump 21, and enter the degraded of carrying out organic pollutant in the high pressure contact reaction tower 31 of ozone (catalysis) oxidation system 3; 3 water outlets of ozone (catalysis) oxidation system enter oxidizing reaction separation system 4 by corresponding pipeline again, mix with pending sewage, carry out the continuation degraded of the separation of non-dissolved pollutant in sewage and solubilised state organic pollutant, and complete separating of residual ozone and water body.
In the present embodiment, the connecting tube between described treatment unit 100 and each system all adopts the 316L stainless material.
during application, ozone generation system starts, the high-concentrated ozone of desired number is satisfied in generation, gas fluid mixture pump is started working, in ozone while suction pump with device backflow sewage and proper ratio, form the ozone dissolved air water and enter ozone high pressure (catalysis) oxidation system, ozone under high pressure dissolves into sewage and Accelerative mass transfer, produce fast the OH free radical under catalyst action, attack many rings and heterocycle polar contaminants in sewage, after reaching treatment effect, ozone dissolved air water and pending sewage enter the oxidizing reaction separate tank, under condition of normal pressure, residual ozone continuation in sewage is carried out oxidizing reaction until reach the biodegradability requirement with the residue organic pollutant in sewage.
The preparation of embodiment 3 ozone heterogeneous catalysis agent
(described silochrom mean pore size is 8.0～10.0nm, specific surface area 300～400m to take silochrom
2/ g, pore volume 0.8～1.0ml/g; ) 18 grams under 110 ℃ dry 10 hours, add 5% hydrogen peroxide solution, soaked stagnant 14 hours, take out, dry in the shade, standby; The silochrom equal-volume of above-mentioned processing is soaked stagnantly be made in mixing solutions to 6 gram Xiao Suan Manganese and 4 gram iron nitrates, kept 20 hours, 110 ℃ of dryings 10 hours, then calcining 5 hours under 500 ℃ obtain the catalyzer for catalytic oxidation treatment sewage.
Fig. 4, Fig. 5 and Fig. 6 are respectively nitrogen adsorption desorption graphic representation, pore size distribution curve figure and the transmission electron microscope pictures of the ozone heterogeneous catalysis agent of preparation in embodiment 3.
Liaohe River petrochemical industry branch office of CNPC is take (surpassing) viscous crude as main raw material, along with the processing ratio of external inferior heavy oil raw material increases gradually, and the further upgrading of wastewater disposition standard, (surpassing) pre-treatment of sewage from thick oil refining is in urgent need of strengthening.According to flow process and the operation of embodiment 1 and embodiment 2, the pretreated improvement process application of (surpassing) condensed oil sewage is optimized Capacity Expansion Project in the super sewage from thick oil refining pretreatment unit of Liaohe River petro-chemical corporation.Engineering design processing power 150t/h; Comprise processing unit and capital construction, 1,500 ten thousand yuan of total investment of engineering volumes; 6.06 yuan/tons of sewage of direct operating cost, viscous crude reclaim year wound effect more than 4,000,000 yuan/year.Downstream composite wastewater sewer outside the venue satisfies one-level A mark in country " cities and towns industrial sewage emission standard " (GB 18918-2002) comprehensively, CODcr＜45mg/L wherein, BOD
5＜8mg/L, petroleum-type＜3mg/L reaches the expection operating performance.
(surpassing) sewage from thick oil refining of Liaohe River petrochemical industry branch office of CNPC is implemented pretreated idiographic flow operation referring to the description of embodiment 1, wherein, oil removing sulphur removal compound dosage 5 kg/ton sewage, coagulation sulphur removal compound dosage 2 kg/ton sewage, float apparatus for collecting oil and automatic sludge discharger conventional in prior art all are equipped with in homogeneous slurry tank, breaking milk and removing oil tank and coagulating setting tank inside.Fully mix with the oil removing sulphur removal compound that adds in the pipeline of homogeneous slurry tank water outlet before entering the breaking milk and removing oil tank.Fully mix with the coagulation sulphur removal compound that adds in the pipeline of breaking milk and removing oil tank water outlet before entering the coagulation oil removing pot.Added 100mg/L Tai-Ace S 150 in the surge tank outlet conduit.
In the one-level ozone-oxidizing device, water temperature remains between 60 ℃-80 ℃, and hierarchy of control pressure is 0.5MPa approximately, and the dosage of ozone is about the 240-260g/t staying water, and total hydraulic detention time is 15-20min approximately; In the secondary device for catalyzing and oxidating ozone, catalyzer adopts the catalyzer of embodiment 3, and the amount of adding is 6 tons; Water temperature remains on 60 ℃-80 ℃, and hierarchy of control pressure is 0.5MPa approximately, and the dosage of ozone is about the 240-260g/t staying water, and total hrt is at 30min.
The effect of this pretreatment technology to sewage disposal:
More than the average 4500mg/L of water inlet petroleum class content from source of sewage, more than the average 8600mg/L of CODcr, more than the average 6000mg/L of SS, the average less than 0.18 of BOD5/COD; The effluent quality of secondary device for catalyzing and oxidating ozone is basicly stable, oil-containing (petroleum content) is lower than 80mg/L, and SS is lower than 50mg/L, and CODcr is lower than 1500mg/L, BOD5/COD is promoted to 0.23 left and right, can directly enter the biochemical segment process of wastewater treatment field fully and carry out subsequent disposal.The effluent index of each technique unit sees Table 1.
The effluent index of table 1, each technique unit
。
Claims (8)
1. pretreated device of sewage from thick oil refining, it is characterized in that, this device comprises homogeneous slurry tank, breaking milk and removing oil tank, coagulating setting tank, one-level ozone-oxidizing device and the secondary device for catalyzing and oxidating ozone that order arranges, and is communicated with by the sewer pipeline order between homogeneous slurry tank, breaking milk and removing oil tank, coagulating setting tank, one-level ozone-oxidizing device and secondary device for catalyzing and oxidating ozone.
2. the pretreated device of sewage from thick oil refining according to claim 1 is characterized in that:
Be provided with acid-alkali accommodation equipment in described homogeneous slurry tank, also be provided with the oil slick that reclaims water body top in the homogeneous slurry tank, the equipment of thick dispersed oil, and the equipment that reclaims the macrobead silt particle of homogeneous slurry tank bottom sedimentation;
Described breaking milk and removing oil tank is provided with the finely divided oil, the oil in water emulsion breakdown of emulsion that reclaim water body top in the breaking milk and removing oil tank and forms the equipment than larger oil droplet, and the equipment that reclaims the suspended solid that metallic sulfide precipitates, breakdown of emulsion forms of breaking milk and removing oil pot bottom sedimentation;
Described coagulating setting tank is provided with the residue oil in water emulsion breakdown of emulsion formation on water body top in the recovery coagulating setting tank than the equipment of larger oil droplet, and the metallic sulfide of recovery coagulant precipitation pot bottom precipitates, the equipment of the suspended solid of coagulation formation.
3. the pretreated device of sewage from thick oil refining according to claim 1 is characterized in that:
Described one-level ozone-oxidizing device and secondary device for catalyzing and oxidating ozone comprise respectively: ozone generation system, ozone dissolved air water produce system, ozone oxidation system and oxidizing reaction separation system; Ozone generation system produces system entry with the ozone dissolved air water and is connected, the refluxing opening of oxidizing reaction separation system also is connected with ozone dissolved air water generation system, the ozone dissolved air water produces system outlet and is connected in the ozone oxidation system entry, and the ozone oxidation system outlet is connected in the oxidizing reaction separation system; The ozone that is produced by ozone generation system and the partial reflux sewage of oxidizing reaction separation system enter ozone dissolved air water generation system and form the ozone dissolved air water, the ozone dissolved air water enters the ozone oxidation system and carries out the degraded of organic pollutant, the water outlet of ozone oxidation system and pending sewage are mixed into the oxidizing reaction separation system, carry out the continuation degraded of the separation of non-dissolved pollutant in sewage and solubilised state organic pollutant, and complete separating of residual ozone and water body; The pressure of described ozone oxidation system is higher than normal pressure.
4. the pretreated device of sewage from thick oil refining according to claim 3, is characterized in that: be filled with heterogeneous catalyst in described secondary device for catalyzing and oxidating ozone.
5. the pretreated device of sewage from thick oil refining according to claim 3 is characterized in that:
In one-level ozone-oxidizing device and secondary device for catalyzing and oxidating ozone, the pressure range of described ozone oxidation system is 0.4MPa-0.6MPa, and the temperature range of ozone oxidation is 60 ℃-80 ℃.
6. the pretreated device of sewage from thick oil refining according to claim 3 is characterized in that:
Described ozone dissolved air water produces system and is comprised of gas fluid mixture pump and respective valves thereof;
Described ozone generation system order is made of air compressor machine, gas-holder, freeze drier, oxygenerator, ozonizer;
Described ozone oxidation system is made of high pressure contact reaction tower and pressure maintaining valve;
Described oxidizing reaction separation system is made of ozone dissolved air water reliever, oxidizing reaction separate tank, slag scraper.
7. the pretreated device of sewage from thick oil refining according to claim 1, is characterized in that: in described one-level ozone-oxidizing device, airfloat equipment is set.
8. the according to claim 1 or 7 pretreated devices of described sewage from thick oil refining, is characterized in that: also be provided with flocculant concentration equipment between described coagulating setting tank and one-level ozone-oxidizing device.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043829A (en) * | 2013-01-05 | 2013-04-17 | 中国石油大学(北京) | Method and device for pretreating thickened oil refining sewage |
| CN103663811A (en) * | 2013-07-17 | 2014-03-26 | 新疆天业（集团）有限公司 | Treatment method of tar-containing wastewater for tail gas purification of calcium carbide furnace |
| CN103819060A (en) * | 2014-03-05 | 2014-05-28 | 青岛新天地固体废物综合处置有限公司 | Integrated disposal technology for waste emulsion liquid, electroplating wastewater and landfill leachate |
-
2013
- 2013-01-05 CN CN 201320005041 patent/CN203007070U/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043829A (en) * | 2013-01-05 | 2013-04-17 | 中国石油大学(北京) | Method and device for pretreating thickened oil refining sewage |
| CN103043829B (en) * | 2013-01-05 | 2013-10-30 | 中国石油大学(北京) | Method and device for pretreating thickened oil refining sewage |
| CN103663811A (en) * | 2013-07-17 | 2014-03-26 | 新疆天业（集团）有限公司 | Treatment method of tar-containing wastewater for tail gas purification of calcium carbide furnace |
| CN103819060A (en) * | 2014-03-05 | 2014-05-28 | 青岛新天地固体废物综合处置有限公司 | Integrated disposal technology for waste emulsion liquid, electroplating wastewater and landfill leachate |
| CN103819060B (en) * | 2014-03-05 | 2016-04-06 | 青岛新天地固体废物综合处置有限公司 | A kind of waste emulsified mixture, electroplating wastewater, Landfill joint disposal technology |
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