CN105906039B - A kind of oil refining catalyst sulfur-containing waste water denitrification process and its application - Google Patents
A kind of oil refining catalyst sulfur-containing waste water denitrification process and its application Download PDFInfo
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- CN105906039B CN105906039B CN201610390818.8A CN201610390818A CN105906039B CN 105906039 B CN105906039 B CN 105906039B CN 201610390818 A CN201610390818 A CN 201610390818A CN 105906039 B CN105906039 B CN 105906039B
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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
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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 present invention provides a kind of oil refining catalyst sulfur-containing waste water denitrification process and its applications.The technique is the following steps are included: carry out partial nitrification processing and Anammox processing, completion denitrogenation processing for the oil refining catalyst sulfur-containing waste water through desulfurization pretreatment；Method particularly includes: the pH value of oil refining catalyst sulfur-containing waste water of the control through desulfurization pretreatment is 8.8-8.5, lead-in portion nitrosation reactor, part ammonia nitrogen in the oil refining catalyst sulfur-containing waste water Jing Guo desulfurization pretreatment is aoxidized by the ammonia oxidizing bacteria in reactor, generate nitrite nitrogen, obtain the wastewater effluent handled through partial nitrification, wherein, the mass ratio of the nitrogen content of nitrite nitrogen and the nitrogen content of remaining ammonia nitrogen is (0.8-1.32): 1；Wastewater effluent is imported into Anammox and denitrification reactor, by the anaerobic ammonium oxidizing bacteria and denitrifying bacteria removal nitrite nitrogen, remaining ammonia nitrogen and nitrate nitrogen in the reactor, denitrification percent 90%.
Description
Technical field
The invention belongs to water-treatment technology fields, are related to a kind of with high salt, high ammonia nitrogen, sulfur-bearing and an a variety of huge sum of moneys based on biology
Belong to half nitrifying anaerobic ammonia oxidation denitrification process of oil refinery's containing wastewater from catalyst more particularly to a kind of oil refining catalyst sulfur-containing waste water is de-
Nitrogen technique and its application.
Background technique
Oil refinery's containing wastewater from catalyst has (> 15000mg/L) with high salt, high ammonia nitrogen (> 200mg/L) high hardly degraded organic substance
(COD>200mg/L), BOD content low (<50mg/L), high-sulfate (>800mg/L), high pH (>9.0) and containing there are many a huge sum of moneys
The features such as category and a large amount of colloidal substances, belong to petrochemical industry special waste.Such waste water be widely present in all oil refineries and
Petrochemical enterprise, since water quality is special, the processing of such waste water is the difficult point of oil refining and chemical company's processing.Exist at present
Sewage that the field generallys use, waste water treatment process are typical A in water treatment field2/ O technique, but the technique exist with
Lower problem: (1) since the ammonia-nitrogen content of oil refinery containing wastewater from catalyst high, it is fully oxidized to nitrate nitrogen using by ammonia nitrogen, so
After carry out denitrifying technique, the organic matter wretched insufficiency that biology can efficiently use in reaction system, therefore, in order to realize anti-nitre
Large amount of organic need to manually be added by changing denitrogenation, and ammonium oxidation in technical process is caused to need to supply a large amount of dissolved oxygen (DO), be consumed
It can be high；(2)A2Sulphates content is high in the water outlet of/O technique；(3) basicity of oil refinery's containing wastewater from catalyst is high, with A2/ O work
The Prepositive denitrification environment of skill denitrogenation contradicts, and causes nitric efficiency low, and sulfate contains in (4) oil refinery containing wastewater from catalyst
Amount is high, in A2It not only will cause reduction and the energy dissipation of oxidation unit in the processing system of/O technique, moreover, for water process
Sludge wadding body is formed in the middle and the bioactivity of bacterium has greatly obstruction and toxic action.A at present2/ O treatment process is in stone
Change field, the generally existing water outlet ammonia nitrogen that is only able to satisfy is not exceeded, but its state for largely discharging still in total nitrogen, apart from petrochemical industry row
The total nitrogen emission control that industry will be implemented differs greatly.
Summary of the invention
The shortcomings that in view of the above-mentioned prior art, the purpose of the present invention is to provide a kind of oil refining catalyst sulfur-containing waste water denitrogenations
Technique, the technique can be used in the sewage treatment of this complicated waste water of oil refinery's containing wastewater from catalyst, can create preferable de-
Nitrogen working condition realizes efficient denitrification.
In order to reach goal of the invention above-mentioned, the present invention provides a kind of oil refining catalyst sulfur-containing waste water denitrification process, packet
Include following steps:
Oil refining catalyst sulfur-containing waste water through desulfurization pretreatment is subjected to partial nitrification processing and Anammox processing,
Complete denitrogenation processing；
The method of the partial nitrification processing are as follows: the pH value of oil refining catalyst sulfur-containing waste water of the control through desulfurization pretreatment
For 8.8-8.5, by the oil refining catalyst sulfur-containing waste water lead-in portion nitrosation reactor Jing Guo desulfurization pretreatment, by the part
Ammonia oxidizing bacteria in nitrosation reactor aoxidizes the part in the oil refining catalyst sulfur-containing waste water by desulfurization pretreatment
Ammonia nitrogen, generate nitrite nitrogen, obtain through partial nitrification handle wastewater effluent, wherein the nitrogen content of nitrite nitrogen with
The mass ratio of the nitrogen content of remaining ammonia nitrogen is (0.8-1.32): 1；
The method of Anammox processing are as follows: will be imported by the waste water of partial nitrification processing Anammox and
Denitrification reactor, by the Anammox and denitrification reactor anaerobic ammonium oxidizing bacteria and denitrifying bacteria, go
Except nitrite nitrogen, remaining ammonia nitrogen and nitrate nitrogen, denitrification percent 90%.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, controls the oil refining catalyst through desulfurization pretreatment and contain
The pH value of sulphur waste water is 8.8-8.5, with this under the premise of continuous satisfaction nitrification supplement basicity needs, controls the trip in reaction system
From ammonia (FA) and free nitrous acid (FNA), nitrate is inhibited to generate.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step of partial nitrification is handled,
The mass ratio of the nitrogen content of the nitrite nitrogen and the nitrogen content of remaining ammonia nitrogen is 1.1:1.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that the desulfurization pretreatment includes anaerobic hydrolysis
Processing, biological sulphate reduction processing, the processing of sulfide coagulating kinetics, sulphur biological oxidation and biological sulphur coagulating kinetics
One or more of combination, but not limited to this.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that the desulfurization pretreatment successively includes anaerobism
Hydrolysis process, biological sulphate reduction processing, the processing of sulfide coagulating kinetics, sulphur biological oxidation and biological sulphur coagulating sedimentation
Processing.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method for the anaerobic hydrolysis processing are as follows: to the refining
Organic matter is added in oily catalyst sulfur-containing waste water and carries out anaerobic hydrolysis, the first wastewater effluent is obtained, in first wastewater effluent
The mass ratio of carbon in biologically effective organic matter and the sulphur in the oil refining catalyst sulfur-containing waste water is 2:1 or more, described first
The pH value of wastewater effluent is less than 6.8.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, what the organic matter can routinely use for this field has
Machine object.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, in first wastewater effluent in biologically effective organic matter
The mass ratio of carbon and the sulphur in the oil refining catalyst sulfur-containing waste water can be controlled by conventional technical means in the art, it is described
The pH value of first wastewater effluent can also be controlled by conventional technical means in the art.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method for the biological sulphate reduction processing are as follows: will
First wastewater effluent imports sulfate reduction device, also by the sulfate reducing bacteria in the sulfate reduction device
Ortho-sulfate generates S2-。
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the sulfate reducing bacteria can be this field routine sulphur
Hydrochlorate reducing bacteria.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the sulfate reducing bacteria is anti-in the sulfate reduction
Answering the concentration in device is 109A/mL or more.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the set-up mode of the sulfate reducing bacteria includes bacterium
Embedded immobilization and/or apposition growth biomembrane.
It is raw using bacterium embedded immobilization and/or apposition growth in above-mentioned oil refining catalyst sulfur-containing waste water denitrification process
Sulfate reducing bacteria, which is arranged, in the mode of object film in the sulfate reduction device can control the stream of the sulfate reducing bacteria
It loses.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, in the step of biological sulphate reduction is handled,
The mode that the step uses exteenal reflux to handle, is back to the sulfuric acid for the first wastewater effluent handled through biological sulphate reduction
In salt reduction reactor, and regurgitant volume and first of first time entrance sulfate reduction device while being flowed back
The ratio between inflow of wastewater effluent is 4:1.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, exteenal reflux is set on the sulfate reduction device
Device, to flow back.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the reflux unit can fill for this field normal reflux
It sets, reflux ratio (4:1) is through testing the optimal proportion found out.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the first waste water handled through biological sulphate reduction is gone out
Water is back in the sulfate reduction device, can increase mass-transfer efficiency, makes sulfate reducing bacteria more fully reduced sulphur
Hydrochlorate generates S2-。
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method for the sulfide coagulating kinetics are as follows: control
The surface loading of sulfide precipitation processed is less than 0.5m3/m2.h, make S2-Metal sulfide is formed with the heavy metal ion in raw wastewater
Precipitating, obtains the second wastewater effluent.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the heavy metal ion is the 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 handled by biological sulphate reduction and gone out
Water is exported into sedimentation basin, and the load for then controlling the precipitating pool surface is less than 0.5m3/m2.h, make above-mentioned heavy metal ion and be somebody's turn to do
A large amount of S in sedimentation basin2-Formed metal sulfide precipitating, thus the heavy metal being effectively removed in first wastewater effluent from
Son.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method for the sulphur biological oxidation processing are as follows: will be described
Second wastewater effluent imports sulphur biooxidation reactions device, and sulfur-oxidizing bacteria is arranged in sulphur biooxidation reactions device makes S2-Through aoxidizing
Biological sulphur is generated, the biological sulphur concentration for controlling generation is less than 80mg/L.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the sulfur-oxidizing bacteria can be this field routine sulphur oxygen
Change bacterium.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the sulfur-oxidizing bacteria is in the sulphur biooxidation reactions
Concentration in device is 106A/mL or more.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the growth pattern of the sulfur-oxidizing bacteria includes attachment life
Growth film.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the method for the biology sulphur coagulating kinetics are as follows: control
It makes biological sulphur precipitation surface load and is less than 0.3m3/m2.h, the biological sulphur is precipitated, the refining catalytic through desulfurization pretreatment is formed
Agent sulfur-containing waste water.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, when carrying out biological sulphur coagulating kinetics, institute is controlled
Biological sulphur precipitation surface load is stated less than 0.3m3/m2.h, can aoxidize the biological sulphur to be formed for above-mentioned sulfur-oxidizing bacteria is had
The removal of effect ground, has the function of preferable desulfating.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the oil refining catalyst sulfur-bearing through desulfurization pretreatment is useless
Sulfur content in water has basically reached discharge standard.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, at the anaerobic hydrolysis processing, biological sulphate reduction
Reason, the processing of sulfide coagulating kinetics, sulphur biological oxidation and biological sulphur coagulating kinetics may be this field routine skill
Art method.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that the method packet of the partial nitrification processing
It includes using bioencapsulation filler or using activated sludge process.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step of partial nitrification is handled
In, by adding Na into the oil refining catalyst sulfur-containing waste water through desulfurization pretreatment2CO3And/or NaHCO3To realize control
The pH value of the oil refining catalyst sulfur-containing waste water through desulfurization pretreatment.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, controls the oil refining catalyst through desulfurization pretreatment and contain
Free ammonia (FA) and free nitrous acid (FNA) may be implemented in partial nitrification processing to nitrite oxygen in the pH value of sulphur waste water
Change effective control of bacterium (NOB) growth, it is suppressed that the mass production of NOB, while also can satisfy ammonium oxidation to basicity
It needs.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step of partial nitrification is handled
In, dissolved oxygen 1.2-1.5, ammonium oxidation rate is maintained at 100mg/Lh or more.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, controls the oil refining catalyst through desulfurization pretreatment and contain
The pH value of sulphur waste water is 8.8-8.5, and control the nitrogen content of the nitrite nitrogen and the nitrogen content of remaining ammonia nitrogen quality it
Than that the dissolved oxygen (DO) in the partial nitrification treatment process stage can be made to be increased to 1.2-1.5 for 0.8-1.32:1, and make
The part ammonium oxidation rate of the processing stage is maintained at 100mg/Lh or more.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the ammonia nitrogen does not include nitrate nitrogen, the nitrate nitrogen packet
Nitrate nitrogen and/or nitrite nitrogen are included, i.e., in above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the ammonia nitrogen does not include
Nitrate nitrogen and nitrite nitrogen.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the ammonia oxidizing bacteria, anaerobic ammonium oxidizing bacteria and anti-
Nitrobacteria all can be this field routine strain.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step of Anammox is handled
In, concentration of the anaerobic ammonium oxidizing bacteria in the Anammox and denitrification reactor is greater than 108A/mL.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that in the step of Anammox is handled
In, concentration of the denitrifying bacteria in the Anammox and denitrification reactor is greater than 107A/mL.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, the denitrifying bacteria (DNB) can remove former sulfur-bearing
In waste water, the partial nitrification processing reaction process and nitrate nitrogen as caused by Anammox；It is thin to control the denitrification
The concentration of bacterium (DNB) is greater than 107Nitrate nitrogen can be reduced to nitrite nitrogen by a/mL, then anti-by Anammox
It answers or anti-nitration reaction is removed.
In above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, it is preferable that described in Anammox processing
Anaerobic ammonium oxidizing bacteria exists in granular form or with the presence of bioencapsulation form of bio-carrier；The denitrifying bacteria is with granulated
Formula exists or with the presence of bioencapsulation form of bio-carrier.
According to specific embodiment, the method for the partial nitrification processing are as follows: by the oil refining through desulfurization pretreatment
Catalyst sulfur-containing waste water lead-in portion nitrosation reactor controls the oil refining catalyst sulfur-containing waste water through desulfurization pretreatment
PH value is 8.8-8.5, with this under the premise of continuous satisfaction nitrification supplement basicity needs, controls the free ammonia (FA) in reaction system
With free nitrous acid (FNA), nitrate is inhibited to generate, and solid with activated sludge or bacterium embedding in partial nitrification reactor
Surely change form of bio-carrier and the ammonia nitrogen chemical combination that ammonia oxidizing bacteria aoxidizes the oil refining catalyst sulfur-containing waste water through desulfurization pretreatment is added
Object generates nitrite nitrogen, obtains the wastewater effluent handled through partial nitrification；In the waste water handled through partial nitrification
In water outlet, the mass ratio of the nitrogen content of the nitrogen content of the nitrite nitrogen and remaining ammonia nitrogen is (0.8-1.32): 1.
According to specific embodiment, the method for Anammox processing are as follows: handled described through partial nitrification
Wastewater effluent imports Anammox and denitrification reactor is embedded in Anammox and denitrification reactor with bacterium
Anaerobic ammonium oxidizing bacteria and denitrifying bacteria is arranged in form, removes the nitrous acid contained in the waste water handled through partial nitrification
Salt nitrogen, nitrate nitrogen and remaining ammonia nitrogen, until final denitrification percent is up to 90%.
Oil refining catalyst sulfur-containing waste water denitrification process of the invention, based on wastewater treatment aerobic process section high ammonia-nitrogen wastewater
Partial nitrification, the Anammox of anaerobic technique section and denitrification combination, realize effectively removing for ammonia nitrogen in waste water.Wherein:
Ammonia nitrogen partial oxidation in waste water is nitrite nitrogen based on ammonia oxidizing bacteria by aerobic process section partial nitrification, realizes the work
The water outlet of skill section basically reaches nitrite nitrogen and the ratio of ammonia nitrogen meets next anaerobic technique section formation Anammox reaction bottom
The condition that object requires；Anaerobic part bacterium is by a large amount of anaerobic ammonium oxidizing bacteria (AAOB) and a small amount of denitrifying bacteria (DNB)
Composition.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 endless
It is ammonia nitrogen entirely, there are also part nitrate to mix, and in order to ensure the total nitrogen index of processing water outlet, mixing DNB in anaerobism section is exactly benefit
This part nitrate nitrogen can be made to be converted to nitrite nitrogen by anti-nitration reaction with DNB, then pass through Anammox again
Reaction and anti-nitration reaction realize the removal of waste water total nitrogen more thoroughly.
The present invention also provides 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, heavy metal,
The substances such as raw water colloid effectively remove.
Present invention technical effect outstanding:
(1) combination advantage of anaerobic ammonium oxidizing bacteria and denitrifying bacteria is taken full advantage of, considers former sulfur-containing waste water comprehensively
In a large amount of ammonia nitrogen compounds there are while there are many more special circumstances existing for nitrate nitrogen (nitrate nitrogen, nitrite nitrogen),
In partial nitrification processing, when ammonia nitrogen compound being oxidized to nitrite nitrogen using ammonia oxidizing bacteria, it is contemplated that nitrate nitrogen
Presence, propose the portfolio ratio of optimal nitrite nitrogen and remaining ammonia nitrogen compound, system water outlet total nitrogen enable to obtain
To effective control；
(2) the optimal bacterial number of all kinds of bacteriums during each treatment process has been determined；
(3) by effective control to free ammonia (FA) and free nitrous acid (FNA), ammonia nitrogen compound nitrosation is realized
In system for handling under conditions of the high supply of dissolved oxygen (DO), ammonium oxidation rate is made to reach conventional activated sludge method ammonia nitrogen oxygen
5 times or more for changing rate, reach 100mg/Lh or more；
(4) by the reduction process to sulfate in former sulfur-containing waste water, former sulfur-containing waste water sulfate and heavy metal are realized
Effectively remove, achieved the purpose that waste recycling, the removal for such complicated ammonia nitrogen in waste water oxidation process and total nitrogen creates
Good condition, while the water quality of such wastewater treatment water outlet is improved comprehensively；
(5) high ammonia-nitrogen wastewater is achieved that the denitrogenation of waste water by partial nitrification, Anammox, will due to having abandoned
Nitrite nitrogen is oxidized to the further oxidation process of nitrate nitrogen, compared with the process generally used, technical side of the invention
Case reduces the supply of oxygen in nitrifying process, realizes energy conservation, simultaneously because using Anammox technology, thus eliminate biography
It unites demand to organic matter in denitrification process, realizes the denitrogenation target of the low effective content of organics waste water of such high ammonia nitrogen.
Oil refining catalyst sulfur-containing waste water denitrification process of the invention is primarily directed to high ammonia nitrogen oil refinery catalyst with high salt
The efficient denitrification processing of this complexity special waste, on the basis of this core purpose, process of the present invention to whole processing technology
The effluent index of design, the front and back concord of technological parameter and each process section is made that stringent combination requirement, comprehensively considers
Sulfate removal, heavy metals removal, the removal of salt, Bacterial Salt Tolerance domestication, operating condition and each process section condition of water quality control etc. because
Element creates preferable denitrogenation working condition, only under the present invention rigorous path combination and parameter coordination, can realize refining
Ammonia nitrogen, nitrate nitrogen, sulfate, heavy metal, raw water colloidal substance etc. effectively remove in oily catalyst sulfur-containing waste water, finally reach
To the qualified discharge of this kind of wastewater effluent.Therefore, oil refining catalyst sulfur-containing waste water denitrification process of the invention is urged in oil refinery
Agent high ammonia-nitrogen wastewater processing with high salt and total nitrogen emission control field are with a wide range of applications.
Detailed description of the invention
Fig. 1 is the processing system for the oil refining catalyst sulfur-containing waste water denitrification process that embodiment 1 is established.
Accompanying drawings symbol description:
1 hydrolytic tank, 2 sulfate reduction devices, the first coagulating basin of 3A, the first sedimentation basin of 3B, 4 sulphur biooxidation reactions
Device, the second coagulating basin of 5A, the second sedimentation basin of 5B, 6 partial nitrification reactors, 7 Anammoxs and denitrification reactor
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out following detailed description, but should not be understood as the restriction to enforceable range of 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, heavy metal Cd
Content is 12mg/L, other heavy metals are also contained in the raw wastewater；
The processing system of oil refining catalyst sulfur-containing waste water denitrification process is established, as shown in Figure 1:
Anaerobic hydrolysis process section: oil refinery's containing wastewater from catalyst is imported in hydrolytic tank (1), is carried out at anaerobic hydrolysis
Reason forms the first wastewater effluent with the wherein larger molecular organics difficult to degrade, i.e. hydrocolloid substance of degrading, and control this first
The pH value of wastewater effluent is 6.8, and the mass ratio of carbon and sulphur is 2:1；
Biological sulphate reduction process section: first wastewater effluent is guided in sulfate reduction device (2), should
Sulfate reduction device is provided with sulfate reducing bacteria in (2), which is arranged with bacterium embedded immobilization,
Under conditions of adding foreign aid's carbon source, the reduction through sulfate reducing bacteria, the sulfate in first wastewater effluent is gone back
It is primary at S2-, the concentration of the process section sulfate reducing bacteria is 109A/mL or more, on the sulfate reduction device (2)
External reflux device is set, the water part handled through biological sulphate reduction is back to the sulfate reduction device (2)
In, it controls its regurgitant volume and enters the first waste water of the sulfate reduction device (2) for the first time while being flowed back
The ratio between inflow of water outlet is 4:1；The effluent recycling can increase mass-transfer efficiency, in institute by the way of bacterium embedded immobilization
Stating setting sulfate reducing bacteria in sulfate reduction device (2) can control the loss of the sulfate reducing bacteria；
Sulfide coagulation-settlement process section: the water outlet handled through biological sulphate reduction is guided to the first coagulating basin (3A)
Middle carry out coagulation, a large amount of S for generating (2)2-With the heavy metal in first wastewater effluent from
Son forms metal sulfide, obtains the first mixed liquor, then again imports first mixed liquor in the first sedimentation basin (3B), control
The load of the precipitating pool surface is 0.5m3/m2.h, the precipitation process of metal sulfide and suspended matter is carried out, to be effectively removed sulphur
And heavy metal, form the second wastewater effluent；
Sulphur biological oxidation process section: second wastewater effluent is imported in sulphur oxidation reactor (4), the sulphur oxidation reaction
Device is provided with sulfur-oxidizing bacteria in (4), which is arranged in a manner of apposition growth biomembrane, concentration 106A/
ML, to the S in second waste water2-The processing of sulphur biological oxidation is carried out, biological sulphur is formed, the biological sulphur concentration for controlling generation is less than
80mg/L；
Biological sulphur coagulation-settlement process section: the second wastewater effluent handled through sulphur biological oxidation is guided to the second coagulating basin
In (5A), coagulation is carried out, is then introduced into the second sedimentation basin (5B), the load for controlling the precipitating pool surface is 0.3m3/m2.h, into
Row biology sulphur precipitation process makes the biological sulphur precipitate removal, forms (the petroleum refining i.e. through desulfurization pretreatment of third wastewater effluent
Oily containing wastewater from catalyst)；
Partial nitrification process section: by the third wastewater effluent lead-in portion nitrosation reactor (6), the part is sub-
Nitrator is provided with ammonia oxidizing bacteria in (6), which is arranged with bacterium embedded immobilization form of bio-carrier, and to
Na is added in the partial nitrification reactor (6)2CO3And NaHCO3, the pH value for controlling the third wastewater effluent is 8.0-
8.5, partial nitrification processing is carried out, the ammonia nitrogen in the third wastewater effluent is aoxidized, it is (i.e. sub- through part to form the 4th wastewater effluent
Oil refinery's containing wastewater from catalyst of nitrification processing), the amount of the nitrite nitrogen of generation is controlled, is made in the 4th wastewater effluent Central Asia
The mass ratio of the nitrogen content of nitrate nitrogen and the nitrogen content of remaining ammonia nitrogen is maintained at 0.8-1.32:1, wherein the part nitrous
The dissolved oxygen (DO) changed in reactor (6) is controlled in 1.2-1.5, and ammonium oxidation rate is able to maintain in 100mg/Lh or more；
Control pH value is that free ammonia (FA) and free nitrous acid (FNA) may be implemented in partial nitrification processing to nitrous in 8.0-8.5
Effective control of hydrochlorate oxidizing bacteria (NOB) growth, it is suppressed that the mass production of NOB, while also can satisfy ammonium oxidation pair
The needs of basicity；
Anaerobic ammonia oxidation process section: the 4th wastewater effluent is imported in Anammox and denitrification reactor (7),
It is provided with anaerobic ammonium oxidizing bacteria (AAOB) and denitrifying bacteria (DNB) in the Anammox and denitrification reactor (7),
In the Anammox and denitrification reactor (7), the anaerobic ammonium oxidizing bacteria (AAOB) and denitrifying bacteria (DNB) with
Particle form or bioencapsulation form of bio-carrier exist, and the concentration of the anaerobic ammonium oxidizing bacteria (AAOB) is 108A/mL or more,
Denitrifying bacteria (DNB) concentration is 107A/mL or more, the anaerobic ammonium oxidizing bacteria (AAOB) and denitrifying bacteria
(DNB) in granular form or bioencapsulation form of bio-carrier exist, the 4th waste water is gone out using the denitrifying bacteria (DNB)
Nitrate nitrogen in water is reduced to nitrite nitrogen, is then carried out at Anammox using anaerobic ammonium oxidizing bacteria (AAOB)
Reason completes denitrification process.
After the processing of above-mentioned oil refining catalyst sulfur-containing waste water denitrification process, which reaches discharge
Standard, in last discharge water, the content of sulfate is less than 240mg/L, heavy metal (such as: the content of Cd is less than 0.08mg/L,
Discharge is less than 0.1mg/L's) meet wastewater discharge standard requirement, total nitrogen content is less than 25mg/L, realizes ammonia nitrogen, nitrate
Nitrogen, sulfate, heavy metal, hydrocolloid substance etc. effectively remove.
To above-mentioned established process system, the present embodiment has also carried out using oil refinery's containing wastewater from catalyst as raw water small
Examination, pilot experiment, realize the denitrogenation of high ammonia nitrogen oil refinery containing wastewater from catalyst high quality with high salt, due to grinding for the technology
Study carefully, has expanded the application field of Anammox technology, ammonia oxidizing bacteria, anaerobic ammonium oxidizing bacteria (AAOB) and denitrifying bacteria
(DNB) design effectively of effective the domestication implementation and technological parameter carried out for high ammonia nitrogen oil refinery containing wastewater from catalyst with high salt,
Realize effective control of high ammonia nitrogen oil refinery containing wastewater from catalyst polluted by nitrogen with high salt.
The present embodiment is directed to the special waste of this complexity of above-mentioned oil refinery's catalyst, utilizes biological sulphate reduction skill
The preconditioning technique of art, sulphur biological oxidation technology as oil refining catalyst sulfur-containing waste water denitrification process, first realization desulfurization and again
Then the removal of metal carries out the partial nitrification of ammonia nitrogen compound using partial nitrification technology, realized using denitrification useless
The nitrosation conversion process of nitrate nitrogen in water finally realizes effectively removing for total nitrogen, entire work using Anammox technology
The technological parameter front and back of the process design strict regulations of skill, each process section is echoed, and each process section effluent index requires strictly, at this
Under the rigorous path combination cooperation of sample, the qualified discharge of this kind of wastewater effluent is finally realized.
It can be seen that when oil refining catalyst sulfur-containing waste water denitrification process processing oil refinery's containing wastewater from catalyst of the present invention, really
The optimal bacterial number of all kinds of bacteriums in variety of processes is determined；It is real by the reduction process to sulfate in former sulfur-containing waste water
Effectively removing for former sulfur-containing waste water sulfate and heavy metal is showed, has achieved the purpose that waste recycling, has been such complicated waste water ammonia
The removal of nitrogen oxidation process and total nitrogen creates good condition, while by free ammonia (FA) and free nitrous acid (FNA)
Effective control, realize in ammonia nitrogen compound nitrosation system for handling under conditions of the high supply of dissolved oxygen (DO), make ammonia
Nitrogen oxidation rate reaches 5 times or more of conventional activated sludge method ammonium oxidation rate, reaches 100mg/Lh or more；And it is sufficiently sharp
With the combination advantage of anaerobic ammonium oxidizing bacteria and denitrifying bacteria, consider comprehensively same existing for a large amount of ammonia nitrogens in former sulfur-containing waste water
When there are many more special circumstances existing for nitrate nitrogen (nitrate nitrogen, nitrite nitrogen), in partial nitrification processing, utilize ammonia oxygen
When to change bacterium by ammonium oxidation be nitrite nitrogen, it is contemplated that the presence of nitrate nitrogen, propose optimal nitrite nitrogen with
The portfolio ratio of remaining ammonia nitrogen enables system water outlet total nitrogen to be effectively controlled；Further, since having abandoned nitrite nitrogen
It is oxidized to the further oxidation process of nitrate nitrogen, compared with the process generally used, technical solution of the present invention reduces nitre
The supply of oxygen, realizes energy conservation during change, simultaneously because using Anammox technology, thus eliminate conventional denitrification mistake
To the demand of organic matter in journey, the denitrogenation target of the low effective content of organics waste water of such high ammonia nitrogen is realized, is improved comprehensively
The water quality of such wastewater treatment water outlet.
In conclusion technical solution of the present invention is in oil refinery's catalyst high ammonia-nitrogen wastewater with high salt processing and total nitrogen discharged
Control field is with a wide range of applications, be expected to comprehensively solve at present such wastewater treatment there are the problem of, realize China it is wide
The contamination control of big oil refinery and petrochemical enterprise oil refining catalyst waste water discharges.
Claims (9)
1. a kind of oil refining catalyst sulfur-containing waste water denitrification process comprising following steps:
Oil refining catalyst sulfur-containing waste water through desulfurization pretreatment is subjected to partial nitrification processing and Anammox processing, is completed
Denitrogenation processing；
The method of partial nitrification processing are as follows: the pH value of oil refining catalyst sulfur-containing waste water of the control through desulfurization pretreatment is
8.8-8.5, it is sub- by the part by the oil refining catalyst sulfur-containing waste water lead-in portion nitrosation reactor Jing Guo desulfurization pretreatment
Ammonia oxidizing bacteria in nitrator aoxidizes the part ammonia in the oil refining catalyst sulfur-containing waste water by desulfurization pretreatment
Nitrogen generates nitrite nitrogen, obtains the wastewater effluent handled through partial nitrification, wherein the nitrogen content of nitrite nitrogen and surplus
The mass ratio of the nitrogen content of remaining ammonia nitrogen is (0.8-1.32): 1；
The method of the Anammox processing are as follows: Anammox and anti-nitre will be imported by the waste water of partial nitrification processing
Change reactor, by the Anammox and denitrification reactor anaerobic ammonium oxidizing bacteria and denitrifying bacteria, removal it is sub-
Nitrate nitrogen, remaining ammonia nitrogen and nitrate nitrogen, denitrification percent 90%；
Wherein, the desulfurization pretreatment successively includes anaerobic hydrolysis processing, biological sulphate reduction processing, sulfide coagulating sedimentation
Processing, the processing of sulphur biological oxidation and biological sulphur coagulating kinetics.
2. oil refining catalyst sulfur-containing waste water denitrification process according to claim 1, it is characterised in that: in the part nitrous
In the step of changing processing, the mass ratio of the nitrogen content of the nitrogen content of the nitrite nitrogen and remaining ammonia nitrogen is 1.1:1.
3. oil refining catalyst sulfur-containing waste water denitrification process according to claim 1, it is characterised in that: the partial nitrification
The method of processing includes using bioencapsulation filler or using activated sludge process.
4. oil refining catalyst sulfur-containing waste water denitrification process according to claim 1, it is characterised in that: in the part nitrous
In the step of changing processing, by adding Na into the oil refining catalyst sulfur-containing waste water through desulfurization pretreatment2CO3And/or
NaHCO3To realize the pH value for controlling the oil refining catalyst sulfur-containing waste water through desulfurization pretreatment.
5. oil refining catalyst sulfur-containing waste water denitrification process according to claim 1, it is characterised in that: in the part nitrous
In the step of changing processing, dissolved oxygen 1.2-1.5, ammonium oxidation rate is maintained at 100mg/Lh or more.
6. oil refining catalyst sulfur-containing waste water denitrification process according to claim 1, it is characterised in that: in the anaerobism ammonia oxygen
In the step of changing processing, concentration of the anaerobic ammonium oxidizing bacteria in the Anammox and denitrification reactor is greater than
108A/mL.
7. oil refining catalyst sulfur-containing waste water denitrification process according to claim 1, it is characterised in that: in the anaerobism ammonia oxygen
In the step of changing processing, concentration of the denitrifying bacteria in the Anammox and denitrification reactor is greater than 107A/
mL。
8. oil refining catalyst sulfur-containing waste water denitrification process according to claim 1, it is characterised in that: in the anaerobism ammonia oxygen
In change processing, the anaerobic ammonium oxidizing bacteria exists in granular form or with the presence of bioencapsulation form of bio-carrier；
The denitrifying bacteria exists in granular form or with the presence of bioencapsulation form of bio-carrier.
9. the described in any item oil refining catalyst sulfur-containing waste water denitrification process of claim 1-8 are de- in oil refining catalyst sulfur-containing waste water
Application in nitrogen technique.
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