CN106865908A - The processing system and processing method of a kind of waster water of alkaline residul from oil refinery - Google Patents
The processing system and processing method of a kind of waster water of alkaline residul from oil refinery Download PDFInfo
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- CN106865908A CN106865908A CN201710205495.5A CN201710205495A CN106865908A CN 106865908 A CN106865908 A CN 106865908A CN 201710205495 A CN201710205495 A CN 201710205495A CN 106865908 A CN106865908 A CN 106865908A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
Abstract
The processing system and processing method of a kind of waster water of alkaline residul from oil refinery, including salkali waste storage tank, denitrification unit, one-level biochemistry unit, secondary biochemical unit, ozone catalytic oxidation unit and de-nitrification unit.Processing system of the present invention and processing method being capable of most CODs effectively in steady removal alkaline sewage, mitigate the treatment load of follow-up common biochemical processing process, improve the impact resistance in whole sewage farm, stable effluent quality, easy to operate, construction costs and operating cost are low, will obtain wide application in the field of the alkaline residue high-concentration sewage treatment of oil refining petrochemical industry.
Description
Technical field
The present invention relates to a kind of alkaline sewage treatment technology, produced in more particularly to a kind of petroleum refining and process
The alkaline sewage high-performance bio treatment technology containing high density sulfides and hardly degraded organic substance.
Background technology
The alkaline sewage produced in petroleum refining process, has containing a large amount of neutral oils, organic acid, volatile phenol and sulfide etc.
Malicious noxious pollutant, waste water is in dark brown, and with foul odour, intractability is always petrochemical refining of puzzlement China greatly
One problem of enterprise.Therefore, the process problem for alkaline residue how being solved in more economical way is each Petrochemical Enterprises urgent problem.
At present, the alkaline sewage processing method of China's petrochemical industry mainly has direct facture, method of chemical treatment and biology
Oxidizing process.
Direct facture has deep well injection, landfill, river course/ocean disposal and burning method etc., wherein based on burning method.River
The methods such as road/ocean are to be shifted pollutant, harmless treatment are not reached, therefore all regarded in many countries
Method not meet environmental requirement.Burning is a kind of reliable oxidizing treatment, is characterized in simple to operate, and can meet and reach
Mark emission request.Burning makes sulfide be oxidized to sulfate under high temperature (950 DEG C) and normal pressure, generates organic hydrocarbon compounds
CO2And H2O, makes NaOH change into sodium carbonate.But it has the disadvantage that energy consumption is big, and running cost is high.
Method of chemical treatment generally uses wet air oxidation technology (abbreviation WAO), i.e., in 150~350 DEG C, 0.5~20MPa
Under conditions of, using the sulfide in oxygen direct oxidation removal alkaline residue, reach the purpose of alkaline residue pretreatment.The treatment effect of alkaline residue
Fruit is limited by the temperature and pressure of oxidation reaction system, and contaminant removal efficiency is higher, temperature and pressure needed for corresponding system
Also higher, the service condition of the high equipment investment amount of WAO methods and running cost and harshness is with being subject to its popularization and application
Limitation.
Direct facture and method of chemical treatment are all investment, operating cost treatment technology very high, limit its popularization
Using.By contrast, processed using biological oxidation process, its investment, operating cost all only have catalytic wet, burning method it is several
/ mono- or 1/tens, operational management is simple, treatment effect stabilization, with preferable technological value.
Biological oxidation process is that alkaline residue carried out into appropriate dilution (10~20 times) first, control sulfide 1000~
3000mg/L, after neutralization, using special bioreactor, makes sulfur bacteria, degradation of oils bacterium, photosynthetic bacteria etc. in biological respinse
Biological oxidation bed is formed in device, it is pre- so as to reach alkaline residue using dioxygen oxidation sulfide and phenol in air by biological effect
The purpose for the treatment of.Biological oxidation process has the advantages that low operating cost, mild condition, treatment effeciency be high, stable operation is safe.But
Because the sulfide and phenolic comp ' ds pollution of high concentration are to the toxic effect of microorganism in waste water routine biochemistry processing system, make often
The intractability for advising biochemical processing process is very big.Therefore sulfide and phenolic comp ' ds pollution must be eliminated to routine using suitable process
The inhibitory action of microorganism.Sulfide and phenols are the pollutants of bio-degradable, and these pollutants all possess stronger biology
Oxidisability, can under given conditions cultivate a large amount of efficiently special degradation bacterias of domestication, such as sulfur bacteria and bite phenol bacterium, make sulfide
Can be degraded by simple biological treatment mode under normal temperature, normal pressure with phenolic comp ' ds pollution.
Current existing treatment technology use cost is very high, and high water process take has turned into one of Petrochemical Enterprises seriously
Burden.Therefore, there is development of efficient, low cost the technology to China Petroleum to be significant for exploitation.
The content of the invention
To make up the deficiencies in the prior art, processing system and treatment side the invention provides a kind of waster water of alkaline residul from oil refinery
Method.
What the present invention was realized in：
For process waster water of alkaline residul from oil refinery interior circulation microinverse biological oxidation composite processing system include salkali waste storage tank,
Denitrification unit, one-level biochemistry unit, secondary biochemical unit, ozone catalytic oxidation unit and de-nitrification unit.Described denitrification
Unit is denitrification reactor, described one-level biochemistry unit by two or more than two interior circulation aerobe reactor simultaneously
Joint group is into described secondary biochemical unit is made up of BAF, and described ozone catalytic oxidation unit is ozone catalytic
Reactor, described de-nitrification unit is nitrator.Salkali waste storage tank is connected with denitrification reactor, denitrification reactor with it is interior
Circulation aerobe reactor is connected respectively, and interior circulation aerobe reactor is connected with BAF, aeration and biological filter
Pond is connected with catalytic ozonation reactor.A return duct is provided with the pipeline that salkali waste storage tank is connected with denitrification reactor
Road, the return line is connected with nitrator.
Further, described denitrification reactor includes：Reactor body, water inlet pipe I, outlet pipe I, cross water sieve plate I,
Biofilter material, backwash gas distribution pipe, denitrification liquid circulating pump, denitrification liquid circulating line, overflow weir notch.The water inlet pipe I
In the side bottom of reactor one, biofilter material is housed on the surface for crossing water sieve plate, loads height and separately calculated according to disposal ability.Always
Combined sewage enters denitrification reactor by the water inlet pipe positioned at bottom, by the outlet pipe at top by the way of bottom in and top out
Outflow.Denitrification liquid circulating pump is connected with circulation fluid water inlet pipe, circulation fluid outlet pipe, it is therefore an objective to sewage is filled with facultative microbe
Divide stirring mixing.
Further, described interior circulation aerobe reactor include reactor body, water inlet pipe II, outlet pipe II,
Discharge pipeline, aeration head, aeration head fixes sleeve, aeration branch pipe, rising cylinder, rising cylinder fixes sleeve, taper sub-assembly A, taper
Sub-assembly B, cone bottom steel construction, overflow weir notch and exhaust port.Cone bottom steel construction is connected positioned at reactor bottom with discharge pipeline
Connect, cylinder fixes sleeve is risen with annular spread on the base plate of cone bottom steel structure connection, aeration is provided with rising in cylinder fixes sleeve
Head fixes sleeve.Rise cylinder upper end open, lower end insertion rises cylinder fixed sleeving, is bolted.Insert aeration head bottom
Aeration head fixes sleeve, aeration head top is connected with aeration branch pipe.Overflow weir notch is located at reactor head, around reactor body
One circle is fixed, and downflow weir grooved ring shape groove width 150mm can be located at interior circulation aerobe reactor body interior or outside.
Further, taper sub-assembly is divided into upper and lower two parts, and top is divided into taper sub-assembly A, and the bottom of the structure is
The inverted tubaeform that 18 ° of cone angle, middle part is straight tube shape, and top is that 30 ° of cone angle is just tubaeform, there is fixed capping on horn mouth；Bottom
It is divided into taper sub-assembly B, is made up of two inverted tubaeforms, two horn mouths is in 90 ° along interior circulation aerobe reactor inwall
Lay a circle.
Further, described BAF is by BAF body, water inlet pipe III, outlet pipe III, aeration
Pipe, biofilter material B, backwash air inlet pipe A, backwash water inlet pipe A, excessively backwash outlet pipe A, water sieve plate II, tail gas discharging pipe.
Aeration tube, water inlet pipe III, backwash water inlet pipe A, backwash air inlet pipe A are provided with BAF bottom, in aeration and biological
Filter tank top is provided with outlet pipe III, backwash outlet pipe A.Water sieve plate was provided with BAF, water sieve plate was being crossed
Surface is equipped with biofilter material B, loads height and is separately calculated according to disposal ability.
Further, described ozone catalytic reactor includes ozone catalytic reactor body, water inlet pipe IV, outlet pipe
IVth, backwash outlet pipe B, ozone air inlet pipe, backwash water inlet pipe B, backwash air inlet pipe B, support type ozone catalyst, ceramics
Ball pad layer, excessively water sieve plate 3, discharge port and exhaust port.The side of body be provided with backwash outlet pipe B, ozone air inlet pipe,
Water inlet pipe IV and backwash air inlet pipe B；Outlet pipe IV, discharge port and backwash water inlet pipe B are provided with the opposite side of body；Ozone
The perforate of air inlet pipe, backwash water inlet pipe B and backwash air inlet pipe B is that downward-sloping 45 ° of dislocation are split, in mistake water sieve plate
Surface loads Ceramic Balls and support type ozone catalyst successively from bottom to up, and to reach more preferable effect, described crosses water sieve plate
On Ceramic Balls of filling diameter 50mm, 30mm, 10mm respectively from bottom to up, then load support type ozone catalyst, filler dress
Raising degree is separately calculated according to disposal ability.Catalytic ozonation tower top end is provided with exhaust port, and lower end is provided with discharge port.
Further, the nitrator includes nitrator body, water inlet pipe V, outlet pipe V, aeration tube, mistake
Water sieve plate IV, biofilter material C, backwash water inlet pipe C, backwash outlet pipe C, backwash air inlet pipe C, nitrification liquid return duct and tail
Gas delivery pipe, biofilter material C is equipped with the surface for crossing water sieve plate IV, is loaded height and is separately calculated according to disposal ability.Nitrification is single
Unit is also required to provide aeration wind, and to provide the dissolved oxygen in reactor needed for aerobic microbiological, nitrator top is provided with tail
Gas delivery pipe.
Further, the outlet pipe of described de-nitrification unit connects with spent lye electrolytic oxidation apparatus or with oil-polluted water system
Connect.
Further, alkaline residue measuring pump, dilution water metering are provided with salkali waste storage tank and denitrification reactor connecting line
Pump, acid solution measuring pump, nutritive salt measuring pump and nitrification liquid reflux pump.
Further, the tail gas of denitrification unit, one-level biochemistry unit, secondary biochemical unit and ozone catalytic oxidation unit
Tapping equipment is connected with exhaust system.
Another object of the present invention is the processing method that above-mentioned combined apparatus are claimed, and is comprised the following steps that：It is useless
Alkali lye mixes according to a certain percentage with dilution water after metering, combined sewage and the de-nitrification unit recirculation water from device least significant end
Mixed diluting, adds the concentrated sulfuric acid and sodium dihydrogen phosphate in the duct again.Total combined sewage is pumped up entering denitrification list
Unit, then flow through one-level biochemistry unit, secondary biochemical unit, ozone catalytic oxidation unit and nitre successively by way of flow by gravity
Change unit, this four processing units are equipped with spoil disposal and exhaust collection pipeline, and the complete waste water part of final process flows back and gives up
Alkali lye mixes, a part of standard discharge.
The present invention is by denitrification anaerobic reactor, one-level biochemistry interior circulation aerobe reactor, secondary biochemical reactor
With the coupling of catalytic ozonation reactor, integration combined apparatus once up to standard are constituted, realize that interior circulation microinverse is given birth to
Thing oxide compound is processed, and its operation principle is：High-concentration wastewater containing alkaline mud is by after big reflux dilution, carrying out biological oxidation and senior
The treatment of oxidation technology, by hardly degraded organic substance (special biostatic agent) oxidation Decomposition in waste water, reduces the life of waste water
Thing toxicity, improves biodegradability energy, and an oxidation water outlet part enters biochemical process device pollutant as raw water dilution water management
Concentration, another part standard discharge.
The core that the process combination is used is that biochemical technology and oxidation technology are coupled together to cooperate with treatment waste water, can be given birth to
Change pollutant to be processed using biotechnology, difficult biochemical or antibiotic pollutant is processed using mode of oxidizing, gives full play to system
The advantage of biochemical process, reduces investment and operating cost, and can flexibly control biochemical water inlet dense according to raw water quality situation
Degree and degree of oxidation, reduce the risk and cost of plant running.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) interior circulation microinverse biological oxidation combined treatment process as waster water of alkaline residul from oil refinery treatment technology, it is most
Big advantage is low cost, and the method with other treatment alkaline residues compares, and no matter reinvests on cost, or operating cost aspect,
Expense is lower.The handling process is one kind using special biochemical reactor culture domestication sulfur bacteria and bites phenol bacterium, for oil refining
A kind of new work of waste soda residue (alkaline residue such as gasoline, the diesel oil, liquid hydrocarbon) exploitation produced in system and petrochemicals subtractive process
Skill, this technique can be greatly reduced the influent load in sewage farm, can effectively oxidation processes oil refinery waste alkali lye, protect
Normal operation and the qualified discharge of existing sewage disposal system are demonstrate,proved.Processed through suitable condition, can also be by sulfides from wastewater
Reclaimed in the form of elemental sulfur, so as to eliminate the harm of sulfide and phenolic comp ' ds pollution in alkaline sewage.Additionally, the micro- ladder of interior circulation
Degree biological oxidation group technology treatment Alkaline Residue In Oil Refineries have low mild condition, energy consumption, small investment, are imitated without chemical sludge, treatment
The advantages of rate is high, stable operation is safe, thus in the processing method of alkaline sewage, at interior circulation microinverse biological oxidation combination
Science and engineering skill is economic, practical, efficient method.
(2) microorganism in activated sludge needs various organic and inorganic nutrients, this technique in degradable organic pollutant
In, the nutrient formulation for using only needs sodium dihydrogen phosphate, not only increases growth adaptability of the microorganism again under high concentration environment, right
The growth of activated sludge has fabulous nutrition facilitation, and lower on cost expenses.By the continuous culture to strain
And domestication, draw the strain of the treatment alkaline sewage of maturation.By after the treatment of interior circulation microinverse biological oxidation group technology
Waster water of alkaline residul from oil refinery, reached regulation emission request.
(3) processing unit of the invention using larger ratio of height to diameter design, with floor space it is few, capital cost is low, design is tight
The characteristics of gathering, compared with prior art, is greatly reduced production cost；In operation, the air oxygen trans-utilization rate of device is high, oxygen
The rate of transform is up to more than 50%, and the air turbulence shear action of device biochemistry part is strong, and the mud granule of formation is in small, broken bits, micro- life
Thing density is big, and biochemical reaction degree is high and surplus sludge volume is few；In management, biochemical environment capacity of resisting impact load is strong, operation
Steadily, manual intervention operational ton is few, high degree of automation, and organic wastewater with high concentration is once up to standard.
Brief description of the drawings
Fig. 1 is interior circulation microinverse biological oxidation combined treatment process flow chart of the present invention；
Fig. 2 is denitrification reactor structural representation；
Fig. 3 is interior circulation aerobe reactor structural representation；
Fig. 4 is BAF structural representation
Fig. 5 is ozone catalytic structure of reactor schematic diagram；
Fig. 6 is nitrator structural representation.
Wherein, 1.1, water inlet pipe I, 1.2, outlet pipe I, 1.3, cross water sieve plate I, 1.4, biofilter material A, 1.5, recoil washes cloth
Tracheae, 1.6, denitrification liquid circulating pump, 1.7, denitrification liquid circulating line, 1.8, overflow weir, 2.1, water inlet pipe II, 2.2, go out
Water pipe II, 2.3, discharge pipeline, 2.4, aeration head, 2.5, aeration head fixes sleeve, 2.6, aeration branch pipe, 2.7, rise cylinder, 2.8,
Rise cylinder fixes sleeve, 2.9, taper sub-assembly A, 2.10, taper sub-assembly B, 2.11, cone bottom steel construction, 2.12, downflow weir
Groove, 2.13, exhaust port, 3.1, water inlet pipe III, 3.2, outlet pipe III, 3.3, aeration tube, 3.4, biofilter material B, 3.5, anti-
Rinse air inlet pipe A, 3.6, backwash water inlet pipe A, 3.7, backwash outlet pipe A, 3.8, cross water sieve plate II, 3.9, exhaust emissions
Pipe, 4.1, water inlet pipe IV, 4.2, outlet pipe IV, 4.3, backwash outlet pipe B, 4.4, ozone air inlet pipe, 4.5, backwash water inlet
Pipe B, 4.6, backwash air inlet pipe B, 4.7, support type ozone catalyst, 4.8, Ceramic Balls bed course, 4.9, cross water sieve plate III,
4.10th, discharge port, 4.11, exhaust port, 5.1, water inlet pipe V, 5.2, outlet pipe V, 5.3, aeration tube, 5.4, cross water sieve plate
IV, 5.5, biofilter material C, 5.6, backwash water inlet pipe C, 5.7, backwash outlet pipe C, 5.8, backwash air inlet pipe C, 5.9, nitre
Change liquid return duct, 5.10, tail gas discharging pipe.
Specific embodiment
The present invention is further described by the following examples, but is not used in and is limited the scope of the invention, such as nothing
Specified otherwise, chemical reagent involved in the present invention is commercially available.
Embodiment 1
As shown in figures 1 to 6, for processing the interior circulation microinverse biological oxidation composite processing system of waster water of alkaline residul from oil refinery
By salkali waste storage tank, denitrification reactor, two interior circulation aerobe reactors, nitrator, ozone catalytic reactor and
Nitrator.Salkali waste storage tank is connected with denitrification reactor, is provided with salkali waste storage tank with denitrification reactor connecting line
Alkaline residue measuring pump, dilution water measuring pump, acid solution measuring pump, nutritive salt measuring pump and nitrification liquid reflux pump.Two interior circulations are aerobic
Bioreactor is arranged in parallel, and denitrification reactor is connected with interior circulation aerobe reactor respectively by pipeline, interior circulation
Aerobe reactor is connected with BAF, and BAF is connected with catalytic ozonation reactor, and ozone is urged
Oxidation device is connected with nitrator, and the composite processing system also includes that aeration unit, backwash unit and auxiliary are single
Unit.The aeration unit uses a typhoon amount 4m3The roots blower of/min, power 11kw, is one-level biochemistry unit, secondary biochemical
Unit and de-nitrification unit are aerated, a diameter of DN100 of aerated conduit.Backwash unit mainly makes the suspension being deposited on filtering material particle
Solid comes off and disposes, and filtrate is kept cleaning, and secondary biochemical unit, ozone are urged by the way of combined water and air backwash
Change oxidation unit and de-nitrification unit is backwashed.Auxiliary unit is built with alkaline residue, dilution water, 98% sulfuric acid, 4%wt di(2-ethylhexyl)phosphates
Four kinds of liquid of hydrogen sodium are added by measuring pump.
The water inlet pipe I 1.1 of described denitrification reactor is located at the side bottom of reactor one, and outlet pipe I 1.2 is located at reactor
The top of homonymy, the backwash gas distribution pipe 1.5, denitrification circulating pump 1.6 and denitrification liquid circulating line 1.7 are located at reactor
Opposite side.Biofilter material is housed on the surface for crossing water sieve plate I 1.3, is loaded height and is separately calculated according to disposal ability.Total mixing
Sewage enters denitrification reactor by the water inlet pipe positioned at bottom, by the outlet pipe stream at top by the way of bottom in and top out
Go out.Denitrification liquid circulating pump 1.6 is connected with circulation fluid water inlet pipe, circulation fluid outlet pipe, it is therefore an objective to make sewage and facultative microbe
It is thoroughly mixed.
Described interior circulation aerobe reactor includes reactor body, water inlet pipe II 2.1, outlet pipe II 2.2, spoil disposal
Pipe 2.3, aeration head 2.4, aeration head fixes sleeve 2.5, aeration branch pipe 2.6, rising cylinder 2.7, rising cylinder fixes sleeve 2.8, cone
Shape sub-assembly A 2.9, taper sub-assembly B 2.10, cone bottom steel construction 2.11, overflow weir notch 2.12 and exhaust port 2.13.
The side of interior circulation aerobe reactor is provided with water inlet pipe II 2.1.Cone bottom steel construction 2.11 is located at reactor bottom and spoil disposal
Pipe 2.3 is connected, and annular spread rises cylinder fixes sleeve 2.8 on the base plate being connected with cone bottom steel construction 2.11, consolidates cylinder is risen
Determine to be provided with aeration head fixes sleeve 2.5 in sleeve 2.8.Rise the upper end of cylinder 2.7 open, lower end insertion rises cylinder fixed sleeving 2.8,
It is bolted.Aeration head fixes sleeve 2.5 is inserted in the bottom of aeration head 2.4, and the top of aeration head 2.4 connects with aeration branch pipe 2.6
Connect.Overflow weir notch 2.12 is located at reactor head, is enclosed around reactor body one and fixed, the annular groove width of the overflow weir notch 2.12
150mm or so, can be located at interior circulation aerobe reactor body interior or outside.It is provided with the lower section of overflow weir notch 2.12
Outlet pipe II 2.2.Taper sub-assembly is divided into upper and lower two parts, and top is divided into taper sub-assembly A 2.9, and the bottom of the structure is cone
The inverted tubaeform that 18 ° of angle, middle part is straight tube shape, and top is that 30 ° of cone angle is just tubaeform, there is fixed capping on horn mouth；Lower part
It is taper sub-assembly B 2.10, is made up of two inverted tubaeforms, two horn mouths is in 90 ° along interior circulation aerobe reactor
Wall lays a circle.Top is provided with exhaust port 2.13.
The bottom of the side of described BAF is provided with aeration tube 3.3, on the top of BAF homonymy
Be provided with outlet pipe III 3.1, backwash outlet pipe A 3.7, the bottom of BAF opposite side be provided with water inlet pipe III 3.2,
Backwash water inlet pipe A 3.6, backwash air inlet pipe A 3.5.Water sieve plate II 3.8 was provided with BAF, water was being crossed
The surface of sieve plate II 3.8 is equipped with biofilter material B, loads height and is separately calculated according to disposal ability.
The side of described ozone catalytic reactor is provided with backwash outlet pipe B 4.3, ozone air inlet pipe 4.4, water inlet pipe
IV 4.1 and backwash air inlet pipe B 4.6；Outlet pipe IV 4.2, backwash water inlet pipe B 4.5 are provided with the opposite side of body and unload
Material mouth 4.10；The perforate of ozone air inlet pipe 4.4, backwash water inlet pipe B 4.5 and backwash air inlet pipe B 4.6 is downward-sloping
45 ° of dislocation are split, and Ceramic Balls and support type ozone catalyst are loaded successively from bottom to up on the surface for crossing water sieve plate III 4.9, are
More preferable effect is reached, described crosses on water sieve plate III 4.9 ceramics for loading diameter 50mm, 30mm, 10mm respectively from bottom to up
Ball, then loads support type ozone catalyst, and filler filling height is separately calculated according to disposal ability.Ozone catalytic reactor top
End is provided with exhaust port 4.11.
The side of the nitrator is provided with nitrification liquid return duct 5.9, aeration tube 5.3, the and of backwash outlet pipe C 5.7
Outlet pipe V 5.2, water inlet pipe V 5.1, backwash air inlet pipe C 5.8 and backwash water inlet are provided with the opposite side of nitrator
Pipe C 5.6, nitrification liquid return duct 5.9 is connected on the pipeline between salkali waste flow container and denitrification unit by pipeline, in nitrification
Water sieve plate IV 5.4 was provided with reactor, biofilter material C was housed on the surface for crossing water sieve plate IV 5.4, loaded height according to treatment
Ability is separately calculated.De-nitrification unit is also required to provide aeration wind, to provide the dissolved oxygen in reactor needed for aerobic microbiological, nitre
Change reactor top and be provided with tail gas discharging pipe 5.10.
Embodiment 2
The interior circulation microinverse biological oxidation composite processing system processing method of the embodiment of the present invention 1 is as follows：
Salkali waste storage tank is connected by alkaline residue measuring pump with denitrification reactor, and dilution water metering is provided with the connecting line
Pump, acid solution measuring pump, nutritive salt measuring pump and nitrification liquid reflux pump.Spent lye is mixed according to a certain percentage with dilution water after metering
Close, combined sewage and the nitrator recirculation water from device least significant end mixed diluting again now control total combined sewage
COD in the range of design requirement (usual COD ≈ 3000mg/L or so).Concentrated sulfuric acid neutralization is added in the duct, and control is total
The pH of combined sewage is in the range of 8.5~10.5, while adding sodium dihydrogen phosphate as nutritive salt.
Total combined sewage initially enters denitrification unit, by the effect of facultative microbe, converts the nitrate nitrogen in water
Overflowed from waste water for nitrogen.The water outlet of denitrification unit enters one-level biochemistry unit, and one-level biochemistry unit is by two interior circulations
Aerobe reactor is constituted, two block response device parallel runnings, and denitrification unit water outlet shunting two-way is parallel respectively to follow in
Ring aerobe reactor, the delivery port by top by the way of bottom in and top out flows out.Every interior circulation aerobe is anti-
Answering device need to provide aeration wind, and aerating pipelines are entered by reactor head and rise cylinder, to provide in tank needed for aerobic microbiological
Dissolved oxygen.
Interior circulation aerobe reactor is divided into reaction zone and biological selecting area, and waste water enters interior circulation aerobe reaction
After device, raw water and treated waste water are mixed by strength lifting device and form mixed flow, form micro- concentration gradient, powerful
Recycle stream and gas lift air microbubble is formed in reactor, form very strong turbulent flow, air, waste water and microorganism are filled
Mix with dividing, the transmission between different phase materials is reached maximization, promote the formation and diffusion of microbubble, accelerate oxygen
Merged to the transfer in water, while microbic mass is divided into smaller group, increased the ratio table of activated bacterial number and microbic mass
Area, improves biological treatment efficiency and stability.Mixed liquor after treatment is automatically into biological selecting area, and active high-performance is good
Sludge all return to biochemical reaction zones and mixed flow hybrid reaction, the low sludge of activity is with water outflow system.High concentration has
In machine wastewater treatment, interior circulation aerobe biological oxidation technique can be rapidly turned out with waste water by the screening of dominant bacteria
Middle specific pollutants are the microorganism of nutrition, and make microorganism concn in growing trend, and the pollutant in waste water is innoxious,
Pollutant concentration inside effective control system, so as to reach the purpose of biological oxidation pretreatment.
After alkaline sewage is processed through interior circulation aerobe reactor, water outlet converges gravity flow and enters secondary biochemical unit, two
The biochemical unit of level is made up of a BAF, and flow path is bottom in and top out formula, and alkaline sewage is by positioned at aeration and biological
The water inlet pipe III 3.1 of filter tank bottom enters reactor, is flowed out by top outlet pipe III 3.2 by filtrate.Two grades in the process
Biochemical pot is also required to provide aeration wind provide the dissolved oxygen that Guan Nei Institute of Micro-biology needs.
Secondary biochemical unit water outlet gravity flow enters ozone catalytic oxidation unit, and ozone catalytic oxidation unit is that ozone catalytic is anti-
Device is answered, flow path is bottom in and top out formula.Ozone catalytic inside reactor is equipped with manganese dioxide beaded catalyst, in ozone catalytic
In oxidation tank, waste water enters with the ozone from ozone generator from tank bottom, and cocurrent passes through support type ozone catalytic oxidant layer, herein
During, the pollutant in waste water is aoxidized by ozone direct oxidation or by ozone through the hydroxyl radical free radical that catalyst is produced, and is reached
The purpose of purification, ozone admission line is equipped with metallic rotameter, so as to precise control ozone dosage.
Because salkali waste amount is more in waste water, during catalytic ozonation, these organonitrogen compounds are generally oxidized
It is ammonia, causes the ammonia nitrogen for aoxidizing water outlet (300mg/L~500mg/L) higher, therefore oxidation water outlet need to enter de-nitrification unit, by nitre
It is nitrate nitrogen to change unit by ammonium oxidation.Nitrator is also required to provide aeration wind to provide the dissolving in tank needed for nitrifier
Oxygen.Flow path is bottom in and top out formula, after waste water enters through bottom water inlet pipe, is excluded from top outlet pipe by biofilter material,
Nitrification liquid reflux pump is connected in nitrator bottom (sharing an interface with backwash water inlet) pipeline, through metering in the duct
Mixed with spent lye and dilution water.Remaining waste water is overflowed by reactor top delivery port, is disposed.
Application examples
Ningxia Petrochemical company of CNPC alkaline sewage processing item is followed in using apparatus and method of the present invention
Alkaline sewage is successfully processed up to standard by ring microinverse biological oxidation combined treatment process.
1st, project profile
This engineering alkaline sewage water is 500t/a, and design water is 0.06m3/h。
2nd, water quality characteristic
Ningxia Petrochemical Alkaline Residue In Oil Refineries are essentially from Atmospheric vacuum, the first normal top oil and catalytic gasoline, catalysis bavin of catalytic production
The oil products such as oil carry out alkali cleaning with alkali lye after waste liquid, because the product washed is different, the property of alkaline residue is also different, and usual COD exists
70000mg/L or so, belongs to high-concentration hardly-degradable pollution sources, it is necessary to up to standard to ensure general export sewage discharge by pretreatment.
Design Inlet and outlet water water quality such as table 1.
The CNPC's Ningxia Petrochemical alkaline sewage processing item design Inlet and outlet water water quality of table 1
Main flow and technological parameter：
Alkaline residue adds sulfuric acid to mix (pH=8.5~10.5, COD ≈ 2600mg/L) with recirculation water after dilution and initially enters
Denitrification reactor, denitrifying bacteria under anoxic conditions, reduces nitrate, discharges molecular nitrogen (N2) or nitrous oxide
(N2O).In pH is for neutrality to weakly alkaline anaerobic environment, nitrogen (N2) is primary product.By the effect of denitrifying bacteria,
Nitrate nitrogen in composite waste is converted into nitrogen and is overflowed from waste water.It is simultaneously to make alkaline residue in tank, dilution water, sulfuric acid, backflow
Nitrification liquid, nutritive salt are sufficiently mixed, and design increases denitrification liquid circulating pump (Q=4m3/h), to help each component liquid
Mix and manufacture good anaerobic environment.The water outlet of denitrification unit shunts the parallel entrance one-level biochemical device of two-way, one-level it is biochemical by
Two interior circulation aerobe reactions.Two tank parallel runnings, every interior circulation aerobe reactor need to provide aeration wind (wind
Amount >=1.0Nm3/min, blast >=0.0588MPa) with provide Guan Nei Institute of Micro-biology need dissolved oxygen.
Secondary biochemical unit BAF inside is equipped with 12m3The volcanic rock filtrate of medium grain size, top seals and fills
There is tail gas collecting device.Secondary biochemical tank is aerated wind (air quantity >=0.60Nm3/ min, blast >=0.0588MPa) providing in tank
The dissolved oxygen that Institute of Micro-biology needs.Secondary biochemical unit water outlet gravity flow enters ozone catalytic reactor, ozone catalytic inside reactor
Equipped with manganese dioxide beaded catalyst, ozone comes from Ningxia Petrochemical sewage disposal plant area ozone generator, and ozone output is 3kg/
H, ozone concentration is 20~30mg/L.Ozone dosage is 300g/h~500g/h.Nitrator inside is equipped with 12m3Granule
The volcanic rock filtrate in footpath.Nitrator is aerated wind (air quantity >=0.60Nm3/min, blast >=0.0588MPa).
Salkali waste and effluent index after being processed through apparatus of the present invention and method is as shown in table 2.
The salkali waste index of table 2 and system effluent index
The application examples confirms that the present invention has further the advantage that compared with prior art：
(1) interior circulation microinverse biological oxidation combined treatment process uses nature acclimated microorganism technology, without adding spy
Different strain.
(2) Airlift aeration technology enhances exchanging for medium between sewage and organism, improves the treatment of reactor
Efficiency.
(3) microinverse biochemical environment technology --- waste water enter reactor after, raw water and through process waste water by airlift
Device mixes and forms mixed flow, and micro- concentration gradient is formed in inside reactor, and powerful recycle stream is with gas lift air anti-
Answer and microbubble formed in device, form very strong turbulent flow, air, waste water are sufficiently mixed with microorganism together with, make difference
Transmission between phase material reaches maximization.When high-concentration waste water enters reactor, raw water is obtained ratio in moment and mix, make
Pollutant concentration gradient in whole pond is greatly lowered, and so just efficiently avoid microorganism and is subjected to organic matter or Toxic
The impact of matter, so as to provide the environment of stabilization for growth of microorganism.
The present invention can effective steady removal most COD, mitigate the treatment load of follow-up common biochemical processing process, carry
The impact resistance in whole sewage farm high, stable effluent quality, easy to operate, construction costs and operating cost are low, will
Wide application is obtained in the field of the alkaline residue high-concentration sewage treatment of oil refining petrochemical industry.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of processing system of waster water of alkaline residul from oil refinery, it is characterised in that including salkali waste storage tank, denitrification unit, one-level life
Change unit, secondary biochemical unit, ozone catalytic oxidation unit and de-nitrification unit；Described denitrification unit is anti-nitration reaction
Device, described one-level biochemistry unit is composed in parallel by the interior circulation aerobe reactor of two or more than two, and described two
The biochemical unit of level is made up of BAF, and described ozone catalytic oxidation unit is ozone catalytic reactor, described nitre
Change unit is nitrator；Salkali waste storage tank is connected with denitrification reactor, and denitrification reactor is anti-with interior circulation aerobe
Device is answered to connect respectively, interior circulation aerobe reactor, BAF, catalytic ozonation reactor and nitrator
Be sequentially connected, a return line be provided with the pipeline that salkali waste storage tank is connected with denitrification reactor, the return line with nitrification
Reactor is connected.
2. the processing system of waster water of alkaline residul from oil refinery according to claim 1, it is characterised in that described anti-nitration reaction
Device includes：Reactor body, water inlet pipe I (1.1), outlet pipe I (1.2), cross water sieve plate I (1.3), biofilter material A (1.4), anti-
Rinse gas distribution pipe (1.5), denitrification liquid circulating pump (1.6), denitrification liquid circulating line (1.7) and overflow weir (1.8)；It is described
Water inlet pipe I (1.1) is provided with outlet pipe I (1.2) positioned at the side bottom of reactor one above its homonymy, backwashes gas distribution pipe
(1.5), denitrification liquid circulating pump (1.6), denitrification liquid circulating line (1.7) positioned at reactor opposite side, inside reactor
Water sieve plate I (1.3) was provided with, biofilter material A (1.4) was housed on the surface for crossing water sieve plate I (1.3).
3. the processing system of waster water of alkaline residul from oil refinery according to claim 1, it is characterised in that described interior circulation is aerobic
Bioreactor include reactor body, water inlet pipe II (2.1), outlet pipe II (2.2), discharge pipeline (2.3), aeration head (2.4),
Aeration head fixes sleeve (2.5), aeration branch pipe (2.6), rising cylinder (2.7), rising cylinder fixes sleeve (2.8), taper sub-assembly A
(2.9), taper sub-assembly B (2.10), cone bottom steel construction (2.11), overflow weir notch (2.12) and exhaust port (2.13)；
The side of interior circulation aerobe reactor is provided with water inlet pipe II (2.1), cone bottom steel construction (2.11) positioned at reactor bottom with
Discharge pipeline (2.3) is connected, and is distributed on the base plate being connected with cone bottom steel construction (2.11) and rises cylinder fixes sleeve (2.8), upper
Rise in cylinder fixes sleeve (2.8) and be provided with aeration head fixes sleeve (2.5)；Rise cylinder (2.7) upper end open, lower end insertion rises cylinder
Fixed sleeving (2.8)；Insert aeration head fixes sleeve (2.5), aeration head (2.4) top and aeration branch in aeration head (2.4) bottom
Pipe (2.6) connection；Overflow weir notch (2.12) is located at reactor head, is enclosed around reactor body one and fixed, in overflow weir notch
(2.12) outlet pipe II (2.2) is provided with below；The bottom of taper sub-assembly A (2.9) is the inverted tubaeform of 18 ° of cone angle, middle part
It is straight tube shape, top is that 30 ° of cone angle is just tubaeform, there is fixed capping on horn mouth；Taper sub-assembly B (2.10), is fallen by two
Tubaeform to be in 90 ° and lay a circle along interior circulation aerobe reactor inwall, reactor head is provided with exhaust port (2.13).
4. the processing system of waster water of alkaline residul from oil refinery according to claim 1, it is characterised in that the BAF
By BAF body, water inlet pipe III (3.1), outlet pipe III (3.2), aeration tube (3.3), biofilter material B (3.4), anti-
Air inlet pipe A (3.5), backwash water inlet pipe A (3.6) are rinsed, outlet pipe A (3.7) is backwashed, is crossed water sieve plate II (3.8) and tail gas
Delivery pipe (3.9) is constituted, and the bottom of the side of the BAF is provided with aeration tube (3.3), is set on the top of its homonymy
There are outlet pipe III (3.1), backwash outlet pipe A (3.7), water inlet pipe III is provided with the bottom of BAF opposite side
(3.2), backwash water inlet pipe A (3.6), backwash air inlet pipe A (3.5), were provided with water sieve plate II in BAF
(3.8) biofilter material B (3.4), is housed on the surface for crossing water sieve plate II (3.8).
5. the processing system of waster water of alkaline residul from oil refinery according to claim 1, it is characterised in that described ozone catalytic is anti-
Answering device includes ozone catalytic reactor body, water inlet pipe IV (4.1), outlet pipe IV (4.2), backwash outlet pipe B (4.3), smelly
Oxygen air inlet pipe (4.4), backwash water inlet pipe B (4.5), backwash air inlet pipe B (4.6), support type ozone catalyst (4.7), pottery
Porcelain ball pad layer (4.8), excessively water sieve plate III (4.9), discharge port (4.10) and exhaust port (4.11)；Described ozone catalytic is anti-
The side of device is answered to be provided with backwash outlet pipe B (4.3), ozone air inlet pipe (4.4), water inlet pipe IV (4.1) and backwash air inlet pipe B
(4.6)；Outlet pipe IV (4.2), backwash water inlet pipe B (4.5) and discharge port (4.10) are provided with the opposite side of reactor body；
The perforate of ozone air inlet pipe (4.4), backwash water inlet pipe B (4.5) and backwash air inlet pipe B (4.6) is downward-sloping 45 ° of mistakes
Position is split, and Ceramic Balls bed course (4.8) and support type ozone catalytic are loaded successively from bottom to up on the surface for crossing water sieve plate III (4.9)
Agent (4.7), ozone catalytic reactor top is provided with exhaust port (4.11).
6. the processing system of waster water of alkaline residul from oil refinery according to claim 1, it is characterised in that the nitrator bag
Include nitrator body, water inlet pipe V (5.1), outlet pipe V (5.2), excessively aeration tube (5.3), water sieve plate IV (5.4), biology
Filtrate C (5.5), backwash water inlet pipe C (5.6), backwash outlet pipe C (5.7), backwash air inlet pipe C (5.8), nitrification liquid are returned
Flow tube (5.9) and tail gas discharging pipe (5.10)；The side of the nitrator is provided with nitrification liquid return duct (5.9), aeration tube
(5.3), backwash outlet pipe C (5.7) and outlet pipe V (5.2), water inlet pipe V is provided with the opposite side of nitrator
(5.1), backwash air inlet pipe C (5.8) and backwash water inlet pipe C (5.6), nitrification liquid return duct (5.9) are connected to by pipeline
On pipeline between salkali waste flow container and denitrification unit, water sieve plate IV (5.4) was provided with nitrator, was crossing water sieve plate
IV (5.4) surface is equipped with biofilter material C (5.5), and nitrator top is provided with tail gas discharging pipe (5.10).
7. the processing system of waster water of alkaline residul from oil refinery according to claim 6, it is characterised in that described de-nitrification unit
Outlet pipe V (5.2) is connected with spent lye electrolytic oxidation apparatus or with oil-polluted water system.
8. the processing system of waster water of alkaline residul from oil refinery according to claim 1, it is characterised in that in salkali waste storage tank and anti-nitre
Change reactor connecting line and be provided with alkaline residue measuring pump, dilution water measuring pump, acid solution measuring pump, nutritive salt measuring pump and nitrification liquid
Reflux pump.
9. the processing system of waster water of alkaline residul from oil refinery according to claim 1, it is characterised in that denitrification unit, one-level
The gas emission device of biochemical unit, secondary biochemical unit and ozone catalytic oxidation unit is connected with exhaust system.
10. the method that the processing system described in a kind of use claim 1 processes alkaline sewage, it is characterised in that step is as follows：
Spent lye mixes according to a certain percentage with dilution water after metering, and mixed sewage mixes dilute again with de-nitrification unit recirculation water
Release, while adding the concentrated sulfuric acid and sodium dihydrogen phosphate in the duct, total combined sewage is pumped up entering denitrification unit, then leads to
The mode for crossing flow by gravity flows through one-level biochemistry unit, secondary biochemical unit, ozone catalytic oxidation unit and de-nitrification unit successively,
Each unit is equipped with spoil disposal and exhaust collection pipeline, and a waste water part for final process is mixed through de-nitrification unit backflow and spent lye
Close, another part standard discharge.
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| CN108975642A (en) * | 2018-09-28 | 2018-12-11 | 南京理工大学泰州科技学院 | Integrated ozone catalysis oxidation-biological aerated filter |
| CN112125478A (en) * | 2020-09-25 | 2020-12-25 | 中蓝连海设计研究院有限公司 | Biochemical treatment-ozone oxidation coupled sewage treatment method and application thereof |
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| JP2002186994A (en) * | 2000-12-20 | 2002-07-02 | Hitachi Zosen Corp | Method for water treatment |
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| CN108516634A (en) * | 2018-05-15 | 2018-09-11 | 济南云水腾跃环保科技有限公司 | A kind of catalytic ozonation processing method of alkalinity organic wastewater containing stink |
| CN108975642A (en) * | 2018-09-28 | 2018-12-11 | 南京理工大学泰州科技学院 | Integrated ozone catalysis oxidation-biological aerated filter |
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