CN105906039A - Oil refining catalyst sulfide-containing wastewater denitrification technology and application thereof - Google Patents
Oil refining catalyst sulfide-containing wastewater denitrification technology and application thereof Download PDFInfo
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- CN105906039A CN105906039A CN201610390818.8A CN201610390818A CN105906039A CN 105906039 A CN105906039 A CN 105906039A CN 201610390818 A CN201610390818 A CN 201610390818A CN 105906039 A CN105906039 A CN 105906039A
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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
- C02F3/28—Anaerobic digestion processes
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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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Abstract
The invention provides an oil refining catalyst sulfide-containing wastewater denitrification technology and application thereof. The technology includes the following steps that oil refining catalyst sulfide-containing wastewater subjected to desulfurization pretreatment is subjected to partial nitrosation treatment and anaerobic ammonia oxidation treatment, and denitrification treatment is finished. The method specifically includes the steps that the pH value of the oil refining catalyst sulfide-containing wastewater subjected to desulfurization pretreatment is controlled to be 8.5-8.8, part of the oil refining catalyst sulfide-containing wastewater is guided into a nitrosation reactor, part of ammonia nitrogen in the oil refining catalyst sulfide-containing wastewater subjected to desulfurization pretreatment is oxidized by ammonia oxidizing bacteria in the reactor to generate nitrite nitrogen, and outflow subjected to wastewater partial nitrosation treatment is obtained, wherein the mass ratio of the nitrogen content of nitrite nitrogen to the nitrogen content of remaining ammonia nitrogen is (0.8-1.32):1; the outflow wastewater is guided into an anaerobic ammonia oxidation and denitrification reactor, and nitrite nitrogen, remaining ammonia nitrogen and nitrate nitrogen are removed by anaerobic ammonia oxidation bacteria and denitrification bacteria in the reactor, wherein the denitrification rate is 90%.
Description
Technical field
The invention belongs to water-treatment technology field, relate to a kind of based on biological high salt, high ammonia nitrogen, sulfur-bearing and multiple heavy
Metal oil oil refining catalyst waste water half nitrifying anaerobic ammonia oxidation denitrification process, particularly relates to a kind of oil refining catalyst sulfur-bearing
Wastewater denitrification process and application thereof.
Background technology
Oil refinery's containing wastewater from catalyst has high salt (> 15000mg/L), high ammonia nitrogen (> 200mg/L) high difficult degradation has
Machine thing (COD>200mg/L), BOD content low (<50mg/L), high-sulfate (>800mg/L), high pH (>9.0)
And containing the feature such as various heavy and a large amount of colloidal substances, belong to petrochemical industry special waste.Such waste water is extensively deposited
Being all oil refineries and petrochemical enterprise, owing to water quality is special, the process of such waste water is oil refining and change
The difficult point of work business processes.Sewage, the waste water treatment process the most commonly used in this field are allusion quotations in water treatment field
The A of type2/ O technique, but this technique there is problems in that (1) is due to the ammonia-nitrogen content of oil refinery's containing wastewater from catalyst
Height, uses and ammonia nitrogen is fully oxidized to nitrate nitrogen, then carry out denitrifying technique, and in reaction system, biology can have
The Organic substance wretched insufficiency that effect utilizes, therefore, need to manually add large amount of organic to realize denitrification denitrogenation, cause
In technical process, ammonium oxidation needs to supply substantial amounts of dissolved oxygen (DO), consumes energy high；(2)A2Going out of/O technique
In water, sulphates content is high；(3) basicity of oil refinery's containing wastewater from catalyst is high, with A2/ O technique denitrogenation preposition instead
Nitrification environment contradicts, and causes nitric efficiency low, and in (4) oil refinery containing wastewater from catalyst, sulphates content is high,
A2The processing system of/O technique not only can cause the energy dissipation of reduction and oxidation unit, and, water is processed
Central mud flco is formed and the biological activity of antibacterial has obstruction and toxic action greatly.A at present2Science and engineering at/O
Skill, at petrochemical field, generally exists and is only capable of meeting water outlet ammonia nitrogen and does not exceeds standard, but its state discharged in a large number still in total nitrogen,
The total nitrogen emission control that distance petrochemical industry will be implemented differs greatly.
Summary of the invention
In view of the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of oil refining catalyst sulfur-containing waste water denitrogenation
Technique, this technique can be used in the sewage disposal of this complicated waste water of oil refinery's containing wastewater from catalyst, it is possible to creates preferably
Denitrogenation working condition, it is achieved efficient denitrification.
In order to reach aforesaid goal of the invention, the present invention provides a kind of oil refining catalyst sulfur-containing waste water denitrification process, its bag
Include following steps:
Oil refining catalyst sulfur-containing waste water through desulfurization pretreatment carries out partial nitrification process and Anammox process,
Complete denitrogenation processing；
The method that described partial nitrification processes is: control is through the pH of the oil refining catalyst sulfur-containing waste water of desulfurization pretreatment
Value is 8.8-8.5, by the oil refining catalyst sulfur-containing waste water lead-in portion nitrosation reactor through desulfurization pretreatment, by institute
The ammonia oxidizing bacteria described oil refining catalyst sulfur-bearing through desulfurization pretreatment of oxidation stated in partial nitrification reactor gives up
Part ammonia nitrogen in water, generates nitrite nitrogen, obtains the wastewater effluent processed through partial nitrification, wherein, nitrous
The nitrogen content of hydrochlorate nitrogen is (0.8-1.32) with the mass ratio of the nitrogen content of residue ammonia nitrogen: 1；
The method that described Anammox processes is: the waste water that processes through partial nitrification is imported Anammox with
Denitrification reactor is thin by the anaerobic ammonium oxidizing bacteria in described Anammox and denitrification reactor and denitrification
Bacterium, removes nitrite nitrogen, residue ammonia nitrogen and nitrate nitrogen, and denitrification percent is 90%.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, control the described oil refining catalyst through desulfurization pretreatment and contain
The pH value of sulfur waste water is 8.8-8.5, supplements under basicity needs premise with this constantly meeting nitrification, controls response system
In free ammonia (FA) and free nitrous acid (FNA), suppression nitrate generate.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step that this partial nitrification processes,
The nitrogen content of described nitrite nitrogen is 1.1:1 with the mass ratio of the nitrogen content of residue ammonia nitrogen.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that described desulfurization pretreatment includes anaerobic hydrolysis
Process, biological sulphate reduction process, the process of sulfide coagulating kinetics, sulfur biological oxidation and biological sulfur coagulation sink
The combination of one or more in the process of shallow lake, but it is not limited to this.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that described desulfurization pretreatment includes anaerobism successively
The process of hydrolysis process, biological sulphate reduction, sulfide coagulating kinetics, sulfur biological oxidation process and biological sulfur mixes
Solidifying precipitation process.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method that described anaerobic hydrolysis processes is: to described refining
Adding Organic substance in oil catalyst sulfur-containing waste water and carry out anaerobic hydrolysis, obtain the first wastewater effluent, described first waste water goes out
Carbon in the effective Organic substance of organism in water is more than 2:1 with the mass ratio of the sulfur in described oil refining catalyst sulfur-containing waste water,
The pH value of described first wastewater effluent is less than 6.8.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described Organic substance can be having of this area routine employing
Machine thing.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, in described first wastewater effluent in biologically effective Organic substance
Carbon and described oil refining catalyst sulfur-containing waste water in the mass ratio of sulfur can be controlled by this area routine techniques means,
The pH value of described first wastewater effluent can also be controlled by this area routine techniques means.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method that described biological sulphate reduction processes is: will
Described first wastewater effluent imports sulfate reduction device, by the sulfate reduction in described sulfate reduction device
Bacterium sulphate reducing, generates S2-。
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described sulfate reducting bacteria can be this area routine sulfur
Hydrochlorate reducing bacteria.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described sulfate reducting bacteria is anti-at described sulfate reduction
Answering the concentration in device is 109Individual/more than mL.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the set-up mode of described sulfate reducting bacteria includes antibacterial
Embedded immobilization and/or apposition growth biomembrane.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, use antibacterial embedded immobilization and/or apposition growth raw
The mode of thing film arranges sulfate reducting bacteria in described sulfate reduction device can control this sulfate reducting bacteria
Loss.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, in the step that described biological sulphate reduction processes,
This step uses the mode that exteenal reflux processes, and is back to by the first wastewater effluent processed through biological sulphate reduction described
In sulfate reduction device, and capacity of returns enters described sulfate reduction for the first time with while refluxing
The ratio of the inflow of the first wastewater effluent of device is 4:1.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described sulfate reduction device arranges exteenal reflux
Device, in order to reflux.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described reflux can be this area normal reflux dress
Putting, its backflow ratio (4:1) is the optimal proportion found out through test.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the first waste water processed through biological sulphate reduction is gone out
Water is back in described sulfate reduction device, can increase mass-transfer efficiency, makes sulfate reducting bacteria more fully also
Ortho-sulfate, generates S2-。
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method for described sulfide coagulating kinetics is: control
The surface loading of sulfide precipitation processed is less than 0.5m3/m2.h, S is made2-Metal sulfur is formed with the heavy metal ion in raw wastewater
Compound precipitates, and obtains the second wastewater effluent.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described heavy metal ion is described oil refining catalyst sulfur-bearing
Heavy metal ion in waste water.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the first waste water will be processed through biological sulphate reduction and go out
Water is derived to sedimentation tank, then controls the load on this sedimentation tank surface less than 0.5m3/m2.h, make above-mentioned heavy metal from
Son and substantial amounts of S in this sedimentation tank2-Formation metal sulfide precipitates, thus effectively removes in this first wastewater effluent
Heavy metal ion.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method that described sulfur biological oxidation processes is: by described
Second wastewater effluent imports sulfur biooxidation reactions device, arranges sulfur-oxidizing bacteria and make S in sulfur biooxidation reactions device2-
The oxidized biology sulfur that generates, the biological sulphur concentration of control generation is less than 80mg/L.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described sulfur-oxidizing bacteria can be this area routine sulfur oxygen
Change antibacterial.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described sulfur-oxidizing bacteria is at described sulfur biooxidation reactions
Concentration in device is 106Individual/more than mL.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the growth pattern of described sulfur-oxidizing bacteria includes that attachment is raw
Growth film.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method for described biological sulfur coagulating kinetics is: control
The biological sulfur precipitation surface load of system is less than 0.3m3/m2.h, make described biological sulfur precipitation, form the refining through desulfurization pretreatment
Oil catalyst sulfur-containing waste water.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, when carrying out biological sulfur coagulating kinetics, control institute
State biological sulfur precipitation surface load less than 0.3m3/m2.h, can enter for the biological sulfur that the oxidation of above-mentioned sulfur-oxidizing bacteria is formed
Row is removed effectively, has the function of preferable desulfating.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the described oil refining catalyst sulfur-bearing through desulfurization pretreatment gives up
Sulfur content in water has basically reached discharge standard.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, at the process of described anaerobic hydrolysis, biological sulphate reduction
Reason, sulfide coagulating kinetics, sulfur biological oxidation process and biological sulfur coagulating kinetics can also be that this area is normal
Rule technical method.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that the method bag that described partial nitrification processes
Include employing bioencapsulation filler or use activated sludge process.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step that described partial nitrification processes
In, by adding Na in the oil refining catalyst sulfur-containing waste water of desulfurization pretreatment to described2CO3And/or NaHCO3
Realize controlling the pH value of the described oil refining catalyst sulfur-containing waste water through desulfurization pretreatment.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, control the described oil refining catalyst through desulfurization pretreatment and contain
It is right that the pH value of sulfur waste water can realize free ammonia (FA) and free nitrous acid (FNA) during this partial nitrification processes
Effective control that nitrite-oxidizing bacteria (NOB) grows, it is suppressed that a large amount of productions of NOB, also is able to simultaneously
Meet the ammonium oxidation needs to basicity.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step that described partial nitrification processes
In, dissolved oxygen is 1.2-1.5, and ammonium oxidation speed is maintained at more than 100mg/L h.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, control the described oil refining catalyst through desulfurization pretreatment and contain
The pH value of sulfur waste water is 8.8-8.5, and controls the nitrogen content of described nitrite nitrogen and the matter of the nitrogen content of residue ammonia nitrogen
The ratio of amount is 0.8-1.32:1, and the dissolved oxygen (DO) that described partial nitrification can be made to process operation stage brings up to
1.2-1.5, and the part ammonium oxidation speed processing stage of making this is maintained at more than 100mg/L h.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described ammonia nitrogen does not include nitrate nitrogen, described nitrate nitrogen bag
Include nitrate nitrogen and/or nitrite nitrogen, i.e. in above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described ammonia nitrogen
Do not include nitrate nitrogen and nitrite nitrogen.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described ammonia oxidizing bacteria, anaerobic ammonium oxidizing bacteria and anti-
Nitrobacteria can be all the strain that this area is conventional.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step that described Anammox processes
In, described anaerobic ammonium oxidizing bacteria concentration in described Anammox and denitrification reactor is more than 108Individual/mL.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step that described Anammox processes
In, described denitrifying bacteria concentration in described Anammox and denitrification reactor is more than 107Individual/mL.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, described denitrifying bacteria (DNB) can remove former containing
In sulfur waste water, partial nitrification process course of reaction and by nitrate nitrogen produced by Anammox；Control described instead
The concentration of nitrobacteria (DNB) is more than 107Individual/mL, it is possible to nitrate nitrogen is reduced to nitrite nitrogen, then
Reacted by Anammox or anti-nitration reaction is removed.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in described Anammox processes, institute
State anaerobic ammonium oxidizing bacteria to exist in granular form or exist with bioencapsulation form of bio-carrier；Described denitrifying bacteria with
Particle form exists or exists with bioencapsulation form of bio-carrier.
According to specific embodiments, the method that described partial nitrification processes is: by the described oil refining through desulfurization pretreatment
Catalyst sulfur-containing waste water lead-in portion nitrosation reactor, controls the described oil refining catalyst sulfur-bearing through desulfurization pretreatment and gives up
The pH value of water is 8.8-8.5, supplements under basicity needs premise with this constantly meeting nitrification, controls in response system
Free ammonia (FA) and free nitrous acid (FNA), suppression nitrate generate, and in partial nitrification reactor with
Activated sludge or antibacterial embedded immobilization form of bio-carrier add ammonia oxidizing bacteria and aoxidize the described oil refining through desulfurization pretreatment
The ammonia nitriding compound of catalyst sulfur-containing waste water, generates nitrite nitrogen, obtains the wastewater effluent processed through partial nitrification；
Described in the wastewater effluent that partial nitrification processes, the nitrogen content of described nitrite nitrogen is nitrogenous with residue ammonia nitrogen
The mass ratio of amount is (0.8-1.32): 1.
According to specific embodiments, the method that described Anammox processes is: process described through partial nitrification
Wastewater effluent imports Anammox and denitrification reactor, in Anammox and denitrification reactor, with antibacterial
Embedding form arranges anaerobic ammonium oxidizing bacteria and denitrifying bacteria, remove through partial nitrification process waste water in contain
Nitrite nitrogen, nitrate nitrogen and residue ammonia nitrogen, until final denitrification percent reaches 90%.
The oil refining catalyst sulfur-containing waste water denitrification process of the present invention, processes aerobic process section high ammonia-nitrogen wastewater based on waste water
Partial nitrification, the Anammox of anaerobic technique section and denitrification combination, it is achieved that effective removal of ammonia nitrogen in waste water.
Wherein: the ammonia nitrogen partial oxidation in waste water is nitrite based on ammonia oxidizing bacteria by aerobic process section partial nitrification
Nitrogen, it is achieved the ratio that this process section water outlet basically reaches nitrite nitrogen and ammonia nitrogen meets the formation of next anaerobic technique section and detests
The condition that anaerobic ammonium oxidation reaction substrate requires；Anaerobic part antibacterial is by substantial amounts of anaerobic ammonium oxidizing bacteria (AAOB)
Form with a small amount of denitrifying bacteria (DNB).Why anaerobic part has also mixed DNB in addition to AAOB, is
Because the polluted by nitrogen of oil refinery's containing wastewater from catalyst is not exclusively ammonia nitrogen, also part nitrate mixes, in order to ensure place
The total nitrogen index of reason water outlet, mixes DNB in anaerobism section and utilizes DNB that this part nitrate nitrogen can be made to pass through exactly
Anti-nitration reaction changes into nitrite nitrogen, realizes waste water by Anammox reaction and anti-nitration reaction more total
Nitrogen removal more thoroughly.
The present invention also provides for above-mentioned oil refining catalyst sulfur-containing waste water denitrification process in oil refining catalyst sulfur-containing waste water denitrogenation work
Application in skill.
In above-mentioned application, oil refining catalyst sulfur-containing waste water can be realized as ammonia nitrogen, nitrate nitrogen, sulfate, with much money
Effective removal of the materials such as genus, former hydrocolloid.
The technique effect that the present invention highlights:
(1) take full advantage of the combination advantage of anaerobic ammonium oxidizing bacteria and denitrifying bacteria, consider that former sulfur-bearing gives up comprehensively
The spy that many nitrate nitrogens (nitrate nitrogen, nitrite nitrogen) exist is also had while a large amount of ammonia nitriding compounds exist in water
Different situation, during partial nitrification processes, when utilizing ammonia oxidizing bacteria that ammonia nitriding compound is oxidized to nitrite nitrogen, examines
Considered the existence of nitrate nitrogen, it is proposed that the portfolio ratio of optimum nitrite nitrogen and residue ammonia nitriding compound, make be
System water outlet total nitrogen can be effectively controlled；
(2) the optimum bacterial number of each bacterioid during science and engineering skill everywhere is determined；
(3) by the effective control to free ammonia (FA) and free nitrous acid (FNA), it is achieved that ammonia nitrogen chemical combination
In thing nitrosation system for handling under conditions of the high supply of dissolved oxygen (DO), ammonium oxidation speed is made to reach conventional
More than 5 times of activated sludge process ammonium oxidation speed, reach more than 100mg/L h；
(4) by the reduction process of sulfate in former sulfur-containing waste water, it is achieved that former sulfur-containing waste water sulfate and a huge sum of money
The effective removal belonged to, has reached the purpose of waste recycling, for such complicated ammonia nitrogen in waste water oxidizing process and the removal of total nitrogen
Create good condition, improve such waste water simultaneously comprehensively and process the water quality of water outlet；
(5) high ammonia-nitrogen wastewater is achieved that the denitrogenation of waste water by partial nitrification, Anammox, owing to abandoning
Nitrite nitrogen is oxidized to the further oxidizing process of nitrate nitrogen, compared with the flow process commonly used, the present invention
Technical scheme decrease the supply of oxygen in nitrifying process, it is achieved that energy-conservation, simultaneously because use Anammox technology,
Thus to organic demand during eliminating conventional denitrification, it is achieved that the low effective content of organics of such high ammonia nitrogen
The denitrogenation target of waste water.
The oil refining catalyst sulfur-containing waste water denitrification process of the present invention is primarily directed to high salt height ammonia nitrogen oil refinery catalyst
The efficient denitrification of this complicated special waste processes, and on the basis of this core purpose, the present invention is to whole process technique
Echo before and after flow scheme design, technological parameter and the effluent index of each process section is made that strict combination requirement, combine
Close and consider sulfate removal, heavy metals removal, the removal of salt, Bacterial Salt Tolerance domestication, operating mode and each process section water
The factors such as matter condition control, create preferable denitrogenation working condition, only in the rigorous path combination of the present invention and parameter
Under cooperation, ammonia nitrogen, nitrate nitrogen, sulfate, heavy metal, Yuan Shui in oil refining catalyst sulfur-containing waste water can be realized
Effective removal of colloidal substance etc., is finally reached the qualified discharge of this kind of wastewater effluent.Therefore, the oil refining of the present invention is urged
Agent sulfur-containing waste water denitrification process processes and total nitrogen emission control field at oil refinery's catalyst high salt high ammonia-nitrogen wastewater
It is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the processing system of the oil refining catalyst sulfur-containing waste water denitrification process that embodiment 1 is set up.
Reference numeral illustrates:
1 hydrolytic tank, 2 sulfate reduction devices, 3A the first coagulating basin, 3B the first sedimentation tank, 4 sulfur biology oxygen
Change reactor, 5A the second coagulating basin, 5B the second sedimentation tank, 6 partial nitrification reactors, 7 anaerobism ammonia oxygen
Change and denitrification reactor
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that can the restriction of practical range to the present invention.
Embodiment 1
Present embodiments provide a kind of oil refining catalyst sulfur-containing waste water denitrification process.
The oil refining catalyst sulfur-containing waste water that the present embodiment uses is raw wastewater, and wherein the content of sulfate is 3600mg/L,
The nitrogen content of nitrogen ammonia is 120mg/L, and the nitrogen content of nitrate nitrogen (including NO3-N and NO2-N) is 25mg/L, weight
The content of metal Cd is 12mg/L, possibly together with other heavy metals in this raw wastewater；
Set up the processing system of oil refining catalyst sulfur-containing waste water denitrification process, as shown in Figure 1:
Anaerobic hydrolysis process section: this oil refinery's containing wastewater from catalyst is imported in hydrolytic tank (1), carries out anaerobic hydrolysis
Process, with the larger molecular organics of wherein difficult degradation of degrading, i.e. hydrocolloid material, form the first wastewater effluent, and control
The pH value making this first wastewater effluent is 6.8, and carbon is 2:1 with the mass ratio of sulfur；
Biological sulphate reduction process section: described first wastewater effluent is guided in sulfate reduction device (2),
Being provided with sulfate reducting bacteria in this sulfate reduction device (2), this sulfate reducting bacteria is fixing with antibacterial embedding
Change and arrange, under conditions of adding foreign aid's carbon source, through the reduction of sulfate reducting bacteria, described first wastewater effluent
In sulfate be reduced generation S2-, the concentration of this process section sulfate reducting bacteria is 109Individual/more than mL, described
Sulfate reduction device arranges external reflux device on (2), is returned the water part processed through biological sulphate reduction
It flow in described sulfate reduction device (2), control its capacity of returns and enter for the first time with while refluxing
The ratio of the inflow of the first wastewater effluent of described sulfate reduction device (2) is 4:1；This effluent recycling can increase
Add mass-transfer efficiency, use the mode of antibacterial embedded immobilization that sulphuric acid is set in described sulfate reduction device (2)
Salt reducing bacteria can control the loss of this sulfate reducting bacteria；
Sulfide coagulation-settlement process section: the water outlet processed through biological sulphate reduction is guided to the first coagulating basin
(3A) carry out coagulation in, make a large amount of S that in sulfate reduction device (2) generate2-With this first wastewater effluent
In heavy metal ion form metal sulfide, obtain the first mixed liquor, the most again this first mixed liquor imported first
In sedimentation tank (3B), the load controlling this sedimentation tank surface is 0.5m3/m2.h, metal sulfide and float are carried out
Precipitation process, effectively to go sulphur removal and heavy metal, form the second wastewater effluent；
Sulfur biological oxidation process section: importing in sulfur oxidation reactor (4) by described second wastewater effluent, this sulfur aoxidizes
Reactor is provided with sulfur-oxidizing bacteria in (4), and this sulfur-oxidizing bacteria is arranged in the biomembranous mode of apposition growth, dense
Degree is 106Individual/mL, to the S in described second waste water2-Carry out sulfur biological oxidation process, form biological sulfur, control raw
The biological sulphur concentration become is less than 80mg/L；
Biological sulfur coagulation-settlement process section: the second wastewater effluent processed through sulfur biological oxidation is guided to the second coagulating basin
(5A) in, carrying out coagulation, be then introduced in the second sedimentation tank (5B), the load controlling this sedimentation tank surface is
0.3m3/m2.h, carry out biological sulfur precipitation process, make described biological sulfur precipitation remove, form the 3rd wastewater effluent (i.e.
Oil refinery's containing wastewater from catalyst through desulfurization pretreatment)；
Partial nitrification process section: by described 3rd wastewater effluent lead-in portion nitrosation reactor (6), this portion
Dividing in nitrosation reactor (6) and be provided with ammonia oxidizing bacteria, this ammonia oxidizing bacteria is with antibacterial embedded immobilization filler shape
Formula is arranged, and adds Na in described partial nitrification reactor (6)2CO3And NaHCO3, control the described 3rd
The pH value of wastewater effluent is 8.0-8.5, carries out partial nitrification process, aoxidizes the ammonia nitrogen in the 3rd wastewater effluent,
Form the 4th wastewater effluent (the oil refinery's containing wastewater from catalyst i.e. processed through partial nitrification), control the nitrous generated
The amount of hydrochlorate nitrogen, makes the quality of the nitrogen content at the 4th wastewater effluent Nitrite Nitrogen and the nitrogen content of residue ammonia nitrogen
Ratio is maintained at 0.8-1.32:1, and wherein, the dissolved oxygen (DO) in described partial nitrification reactor (6) controls
1.2-1.5, ammonium oxidation speed can be maintained at more than 100mg/L h；Control ph is that 8.0-8.5 can realize this
In partial nitrification process, free ammonia (FA) and free nitrous acid (FNA) are to nitrite-oxidizing bacteria (NOB)
Effective control of growth, it is suppressed that a large amount of productions of NOB, also is able to the needs meeting ammonium oxidation to basicity simultaneously；
Anaerobic ammonia oxidation process section: described 4th wastewater effluent is imported Anammox and denitrification reactor (7)
In, this Anammox and denitrification reactor (7) are provided with anaerobic ammonium oxidizing bacteria (AAOB) and anti-nitre
Change antibacterial (DNB), in described Anammox and denitrification reactor (7), described anaerobic ammonium oxidizing bacteria
(AAOB) and denitrifying bacteria (DNB) in granular form or bioencapsulation form of bio-carrier exist, described anaerobism ammonia
The concentration of oxidizing bacteria (AAOB) is 108Individual/more than mL, described denitrifying bacteria (DNB) concentration is 107
Individual/more than mL, described anaerobic ammonium oxidizing bacteria (AAOB) and denitrifying bacteria (DNB) in granular form or give birth to
Thing embedding form of bio-carrier exists, and utilizes described denitrifying bacteria (DNB) by the nitrate in described 4th wastewater effluent
Nitrogen is reduced to nitrite nitrogen, then utilizes anaerobic ammonium oxidizing bacteria (AAOB) to carry out Anammox process, complete
Become denitrification process.
After above-mentioned oil refining catalyst sulfur-containing waste water denitrification process processes, this oil refinery's containing wastewater from catalyst reaches discharge
Standard, in last discharge water, the content of sulfate is less than 240mg/L, and heavy metal is (such as: the content of Cd is little
In 0.08mg/L, discharge is less than 0.1mg/L's) meet wastewater discharge standard requirement, total nitrogen content is less than 25mg/L,
Achieve effective removal of ammonia nitrogen, nitrate nitrogen, sulfate, heavy metal, hydrocolloid material etc..
To above-mentioned set up process system, with this oil refinery's containing wastewater from catalyst, the present embodiment is also that former water has been carried out little
Examination, pilot experiment, all achieve the high-quality denitrogenation of containing wastewater from catalyst of high salt height ammonia nitrogen oil refinery, due to this technology
Research, expanded the application of Anammox technology, ammonia oxidizing bacteria, anaerobic ammonium oxidizing bacteria (AAOB)
The effectively domestication carried out for high salt height ammonia nitrogen oil refinery containing wastewater from catalyst with denitrifying bacteria (DNB) is implemented and work
The design effectively of skill parameter, it is achieved that effectively controlling of high salt height ammonia nitrogen oil refinery's containing wastewater from catalyst polluted by nitrogen.
The present embodiment, for the special waste of above-mentioned oil refinery this complexity of catalyst, utilizes biological sulphate reduction skill
Art, sulfur biological oxidation technology, as the preconditioning technique of oil refining catalyst sulfur-containing waste water denitrification process, first realize desulfurization
With the removal of heavy metal, then utilize partial nitrification technology to carry out the partial nitrification of ammonia nitriding compound, utilize anti-nitre
Change the nitrosation conversion process realizing nitrate nitrogen in waste water, finally utilize Anammox technology to realize the effective of total nitrogen
Remove, the flow scheme design strict regulations of whole technique, echo before and after the technological parameter of each process section, each process section water outlet
Index request is strict, under the most rigorous path combination coordinates, finally realizes the qualified discharge of this kind of wastewater effluent.
As can be seen here, when oil refining catalyst sulfur-containing waste water denitrification process of the present invention processes oil refinery's containing wastewater from catalyst, really
Determine the optimum bacterial number of each bacterioid in variety of processes；By to the reduction of sulfate in former sulfur-containing waste water
Journey, it is achieved that former sulfur-containing waste water sulfate and effective removal of heavy metal, has reached the purpose of waste recycling, for such
The removal of complicated ammonia nitrogen in waste water oxidizing process and total nitrogen creates good condition, simultaneously by free ammonia (FA)
Effective control with free nitrous acid (FNA), it is achieved that at dissolved oxygen in ammonia nitriding compound nitrosation system for handling
(DO), under conditions of high supply, ammonium oxidation speed is made to reach the 5 of conventional activated sludge method ammonium oxidation speed
More than Bei, reach more than 100mg/L h；And the combination that takes full advantage of anaerobic ammonium oxidizing bacteria and denitrifying bacteria is excellent
Gesture, considers that in former sulfur-containing waste water, a large amount of ammonia nitrogens also have many nitrate nitrogen (nitrate nitrogen, nitrous acid while existing comprehensively
Salt nitrogen) special circumstances that exist, during partial nitrification processes, utilizing ammonia oxidizing bacteria is nitrite by ammonium oxidation
During nitrogen, it is contemplated that the existence of nitrate nitrogen, it is proposed that optimum nitrite nitrogen and the portfolio ratio of residue ammonia nitrogen, make
System water outlet total nitrogen can be effectively controlled；Additionally, due to abandoned, nitrite nitrogen is oxidized to nitrate nitrogen
Oxidizing process further, compared with the flow process commonly used, technical scheme decreases oxygen in nitrifying process
Supply, it is achieved that energy-conservation, simultaneously because use Anammox technology, thus right during eliminating conventional denitrification
Organic demand, it is achieved that the denitrogenation target of the low effective content of organics waste water of such high ammonia nitrogen, improves this comprehensively
Class waste water processes the water quality of water outlet.
In sum, technical scheme processes and the most nitrogen discharged at oil refinery's catalyst high salt high ammonia-nitrogen wastewater
Control field is with a wide range of applications, and is expected to solve such waste water at present comprehensively and processes the problem existed, it is achieved I
Oil refinery and the Environmental capacity of petrochemical enterprise oil refining catalyst waste water that state is vast discharge.
Claims (10)
1. an oil refining catalyst sulfur-containing waste water denitrification process, it comprises the following steps:
Oil refining catalyst sulfur-containing waste water through desulfurization pretreatment carries out partial nitrification process and Anammox process,
Complete denitrogenation processing；
The method that described partial nitrification processes is: control is through the pH of the oil refining catalyst sulfur-containing waste water of desulfurization pretreatment
Value is 8.8-8.5, by the oil refining catalyst sulfur-containing waste water lead-in portion nitrosation reactor through desulfurization pretreatment, by institute
The ammonia oxidizing bacteria described oil refining catalyst sulfur-bearing through desulfurization pretreatment of oxidation stated in partial nitrification reactor gives up
Part ammonia nitrogen in water, generates nitrite nitrogen, obtains the wastewater effluent processed through partial nitrification, wherein, nitrous
The nitrogen content of hydrochlorate nitrogen is (0.8-1.32) with the mass ratio of the nitrogen content of residue ammonia nitrogen: 1；
The method that described Anammox processes is: the waste water that processes through partial nitrification is imported Anammox with
Denitrification reactor is thin by the anaerobic ammonium oxidizing bacteria in described Anammox and denitrification reactor and denitrification
Bacterium, removes nitrite nitrogen, residue ammonia nitrogen and nitrate nitrogen, and denitrification percent is 90%.
Oil refining catalyst sulfur-containing waste water denitrification process the most according to claim 1, it is characterised in that: described
In the step that partial nitrification processes, the nitrogen content of described nitrite nitrogen with the mass ratio of the nitrogen content of residue ammonia nitrogen is
1.1:1.
Oil refining catalyst sulfur-containing waste water denitrification process the most according to claim 1, it is characterised in that: described de-
Sulfur pretreatment includes anaerobic hydrolysis process, biological sulphate reduction process, sulfide coagulating kinetics, sulfur biology oxygen
Change processes and the combination of one or more in biological sulfur coagulating kinetics；
Preferably, described desulfurization pretreatment includes that anaerobic hydrolysis processes, biological sulphate reduction processes, sulfide successively
Coagulating kinetics, sulfur biological oxidation process and biological sulfur coagulating kinetics.
Oil refining catalyst sulfur-containing waste water denitrification process the most according to claim 1, it is characterised in that: described portion
The method dividing nitrosation to process includes using bioencapsulation filler or using activated sludge process.
Oil refining catalyst sulfur-containing waste water denitrification process the most according to claim 1, it is characterised in that: described
In the step that partial nitrification processes, by adding in the oil refining catalyst sulfur-containing waste water of desulfurization pretreatment to described
Na2CO3And/or NaHCO3Realize controlling the pH value of the described oil refining catalyst sulfur-containing waste water through desulfurization pretreatment.
Oil refining catalyst sulfur-containing waste water denitrification process the most according to claim 1, it is characterised in that: described
In the step that partial nitrification processes, dissolved oxygen is 1.2-1.5, and ammonium oxidation speed is maintained at more than 100mg/L h.
Oil refining catalyst sulfur-containing waste water denitrification process the most according to claim 1, it is characterised in that: described
In the step that Anammox processes, described anaerobic ammonium oxidizing bacteria is in described Anammox and denitrification reactor
Concentration more than 108Individual/mL.
Oil refining catalyst sulfur-containing waste water denitrification process the most according to claim 1, it is characterised in that: described
In the step that Anammox processes, dense in described Anammox and denitrification reactor of described denitrifying bacteria
Degree is more than 107Individual/mL.
Oil refining catalyst sulfur-containing waste water denitrification process the most according to claim 1, it is characterised in that: described
During Anammox processes, described anaerobic ammonium oxidizing bacteria exists in granular form or deposits with bioencapsulation form of bio-carrier
?；
Described denitrifying bacteria exists in granular form or exists with bioencapsulation form of bio-carrier.
10. the oil refining catalyst sulfur-containing waste water denitrification process described in any one of claim 1-9 is at oil refining catalyst sulfur-bearing
Application in wastewater denitrification process.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109095606A (en) * | 2018-08-29 | 2018-12-28 | 戚汝常 | A kind of sewage is from stirring nitrogen rejection facility and method |
| CN111072224A (en) * | 2019-12-24 | 2020-04-28 | 华南理工大学 | Wastewater treatment method for synchronously removing organic matters, sulfate radicals, heavy metals and total nitrogen |
| CN111320269A (en) * | 2020-03-20 | 2020-06-23 | 中国科学院生态环境研究中心 | Method for denitrifying ammonia-containing wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293826A (en) * | 2015-11-05 | 2016-02-03 | 江苏奥尼斯环保科技有限公司 | Anti-sulfuration anaerobic ammonium oxidation efficient desulphurization and denitrification method |
-
2016
- 2016-06-06 CN CN201610390818.8A patent/CN105906039B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293826A (en) * | 2015-11-05 | 2016-02-03 | 江苏奥尼斯环保科技有限公司 | Anti-sulfuration anaerobic ammonium oxidation efficient desulphurization and denitrification method |
Non-Patent Citations (2)
| Title |
|---|
| 王淑莹等: "《水质工程实验技术与应用》", 31 August 2009, 中国建筑工业出版社 * |
| 韩晓宇等: "以FA 与FNA 为控制因子的短程硝化启动与维持", 《环境科学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109095606A (en) * | 2018-08-29 | 2018-12-28 | 戚汝常 | A kind of sewage is from stirring nitrogen rejection facility and method |
| CN111072224A (en) * | 2019-12-24 | 2020-04-28 | 华南理工大学 | Wastewater treatment method for synchronously removing organic matters, sulfate radicals, heavy metals and total nitrogen |
| CN111072224B (en) * | 2019-12-24 | 2021-10-26 | 华南理工大学 | Wastewater treatment method for synchronously removing organic matters, sulfate radicals, heavy metals and total nitrogen |
| CN111320269A (en) * | 2020-03-20 | 2020-06-23 | 中国科学院生态环境研究中心 | Method for denitrifying ammonia-containing wastewater |
| CN111320269B (en) * | 2020-03-20 | 2021-11-05 | 中国科学院生态环境研究中心 | Method for denitrifying ammonia-containing wastewater |
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