CN106277455A - The desulfurization deamination processing method of the waste water that oil refining hydrogenation technique produces and processing means - Google Patents
The desulfurization deamination processing method of the waste water that oil refining hydrogenation technique produces and processing means Download PDFInfo
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- CN106277455A CN106277455A CN201610770991.0A CN201610770991A CN106277455A CN 106277455 A CN106277455 A CN 106277455A CN 201610770991 A CN201610770991 A CN 201610770991A CN 106277455 A CN106277455 A CN 106277455A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/50—Inorganic acids
- B01D2251/506—Sulfuric acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/101—Sulfur compounds
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The present invention relates to a kind of refine oil the desulfurization deamination processing method of waste water that hydrogenation technique produces, including waste water carrying out desulfurization successively and sulfur recovery processes step and deamination and recovery ammonia processes step.The desulfurization deamination processing method to the waste water that oil refining hydrogenation technique produces that the present invention obtains, using pH value as crucial Control factors, realize the combination of each processing links, sulfur in efficient removal waste water and ammonia and nitrogen pollution, sulfur and ammonia-nitrogen content in processed waste water is made to reach the secondary discharge standard requirement in GB8978 1996 " integrated wastewater discharge standard ", and be recycling chemical products by the sulfur of removing, mineralized nitrogen, significant benefit it is respectively provided with, it is achieved green chemical industry in terms of economic worth and environmental protection.Additionally, the processing means that the present invention provides, operation and the operation of processing method the most of the present invention control, and conveniently and efficiently realize the desulfurization to waste water, ammonia nitrogen removal process and reclaim.
Description
Technical field
The present invention relates to a kind of waste water desulfurization deamination technical field, particularly relate to a kind of refine oil the waste water that hydrogenation technique produces
Desulfurization deamination processing method, and for the processing means of this processing method.
Background technology
Because of domestic to vehicle fuel oil, the lifting of lubricating oil quality, oil plant adds hydrogenation technique in oil refining process,
With the sulfydryl (-SH) contained in removing fuel oil, lubricating oil, amino (-NH2), nitro (-NO2), alcohol, aldehyde, the hydrophilic group such as ketone,
Reduce electromotor sulfur dioxide in oil product burning and exhausting and amount of nitrogen oxides, reduce the risk of emulsification of lubricant, promote
Oil quality.
After fuel oil, lube oil hydrogenation, sulfydryl (-SH), amino (-NH2), nitro (-NO2), alcohol, aldehyde, the hydrophilic group such as ketone
Group is converted into water, (NH4)2S and NH4NO3, after separating, form aqueous solution, sulphion (S in this aqueous solution with oil product2-) at concentrations up to
9000mg/L, ammonia nitrogen (NH4-N) at concentrations up to 15000mg/L, belong to ultrahigh concentration sulfur-bearing, nitrogen-containing wastewater, it is necessary to carry out
Desulfurization, ammonia nitrogen removal process.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides and a kind of refine oil the de-of waste water that hydrogenation technique produces
Sulfur deamination processing method, to remove sulfur and the ammonia and nitrogen pollution of high-load in waste water, makes sulfur in processed waste water reach with ammonia-nitrogen content
Secondary discharge standard requirement in GB8978-1996 " integrated wastewater discharge standard ", and sulfur acquisition sodium sulfide can be reclaimed, reclaim
Ammonia nitrogen obtains ammonium sulfate.
For achieving the above object, the invention provides and a kind of refine oil the desulfurization deamination process side of waste water that hydrogenation technique produces
Method, comprises the following steps:
A, desulfurization and sulfur recovery process step:
A1, desulfurization processing step: the waste water produced to oil refining hydrogenation technique adds dilution heat of sulfuric acid I, after regulation acid-base value
Spray, inversely contacts with air and carries out air stripping desulfurization process, and the waste water after desulfurization is delivered to de-ammonia treating step；Described de-
After sulfur, the pH value of waste water controls is 0.8～1.2；H in described dilution heat of sulfuric acid I2SO4Mass content be 30%～50%；
A2, sulfur recovery process step: will absorb through two-step desulfurization by escaping gas after described desulfurization processing step
Discharging after process, described two-step desulfurization absorption processes and includes by the first grade desulfurizing absorbing liquid of circulated sprinkling through described desulfurization
After reason step, escaping gas carries out first order desulfurization absorption and processes step, and by the two-grade desulfurizing absorbing liquid of circulated sprinkling and
The NaOH solution I supplementing spray carries out second level desulfurization to escaping gas after described first order desulfurization absorption processes step
Absorption processes step；The pH value controlling first grade desulfurizing absorbing liquid is 10.7～11.3, reclaims first grade desulfurizing absorbing liquid；Described NaOH
In solution I, the mass content of NaOH is 20%～22%, and described two-grade desulfurizing absorbing liquid is in second level desulfurization by NaOH solution I
Absorption processes recirculation spray after carrying out sulfur absorption in step and carries out the mixed solution that sulfur absorption obtains, and described first grade desulfurizing absorbs
Liquid carries out sulfur suction for recirculation spray after being carried out sulfur absorption by two-grade desulfurizing absorbing liquid in first order desulfurization absorption processes step
Receive the mixed solution obtained；
B, deamination and recovery ammonia process step:
B1, de-ammonia treating step: the waste water after desulfurization adds NaOH solution II, sprays, with air after regulation acid-base value
Reverse contact carries out air stripping deamination process, the discharge of wastewater after deamination；After described deamination, the pH value of waste water controls is 10.5
～11.5；In described NaOH solution II, the mass content of NaOH is 20～30%；
B2, recovery ammonia process step: will absorb through two-stage deamination by escaping gas after described de-ammonia treating step
Discharging after process, described two-stage deamination absorption processes and includes by the one-level deamination absorbing liquid of circulated sprinkling through described deamination
After reason step, escaping gas carries out first order deamination absorption and processes step, and by the two of circulated sprinkling grades of deamination absorbing liquids and
The dilution heat of sulfuric acid II supplementing spray carries out the second level to escaping gas after described first order deamination absorption processes step
Deamination absorption processes step；The pH value controlling one-level deamination absorbing liquid is 4.5～6.5, reclaims one-level deamination absorbing liquid；Described dilute
H in sulfuric acid solution II2SO4Mass content be 30%, described two grades of deamination absorbing liquids are for be taken off in the second level by dilution heat of sulfuric acid II
Ammonia absorption processes recirculation spray after carrying out ammonia absorption in step and carries out the mixed solution that ammonia absorption obtains, and described one-level deamination is inhaled
Receive liquid and carry out ammonia for recirculation spray after being carried out ammonia absorption by two grades of deamination absorbing liquids in first order deamination absorption processes step
Absorb the mixed solution obtained.
The waste water that the method for wastewater treatment of the present invention produces for oil refining hydrogenation technique has high-load sulfur, high-load ammonia nitrogen
Characteristic, use and carry out the mode that desulfurization and sulfur recovery process and deamination and recovery ammonia process successively, in efficient removal waste water
Sulfur and ammonia and nitrogen pollution, make sulfur and ammonia-nitrogen content in processed waste water reach in GB8978-1996 " integrated wastewater discharge standard " table 4
Secondary discharge standard requirement, and reclaim sulfur obtain sodium sulfide, reclaim ammonia nitrogen obtain ammonium sulfate, make pollutant change into available
Valuable chemical products, it is achieved green chemical industry.
Waste water is first carried out desulfurization process, by adding the soda acid of dilute sulfuric acid regulation waste water to waste water in processing method
Degree, the desulfurization on the one hand realizing being carried out by air purging waste water processes, and utilizes sulphuric acid as regulation acid to avoid air stripping
The effusion of the foreign-matter contamination of process vulcanisation hydrogen contamination beyond the region of objective existence, to ensure sulfur recovery effect and the air-treatment effect of subsequent step
Really；On the other hand the pH value of waste water after control desulfurization, to ensure the desulfurized effect of waste water, makes sulfur content in waste water be less than 1mg/L,
Reach the secondary discharge standard requirement in GB8978-1996 " integrated wastewater discharge standard " table 4.The dilute sulfuric acid amount added in waste water
After desulfurization, the pH value of waste water regulates and controls for standard, and after making desulfurization, the pH value of waste water maintains 0.8～1.2.The sulfur of removing is dirty
Dye thing enters into sulfur recovery process with hydrogen sulfide form with air and reclaims, successively via first grade desulfurizing absorbing liquid to major part
Hydrogen sulfide carries out first order circulated sprinkling absorption, forms the concentrate circulating based on NaHS, then absorbs via two-grade desulfurizing
Liquid and the NaOH solution supplemented carry out second level circulated sprinkling absorption to remaining a small amount of hydrogen sulfide, and formed based on sodium sulfide is lean
Liquid circulates；Described NaOH solution need to be supplemented in the way of spray, and maintains by controlling the pH value of first grade desulfurizing absorbing liquid
10.7～11.3 scopes, the supplementary spray flux of regulation and control NaOH solution, thus realize the thorough absorption to removing Air Hydrogen Sulfide,
Gas after absorption processes is made to reach " emission standard for odor pollutants " (GB14554-93)；It addition, supplement spray by limiting
NaOH solution mass content (20%～22%) and reclaim first grade desulfurizing absorbing liquid pH value range (10.7～
11.3), the mass content making the first grade desulfurizing absorbing liquid of recovery reach NaHS meets the standard of 28%, can being directly used as
Chemical product uses, as can be used for depilation and the tanning process etc. of rawhide in leather industry.
Waste water after processing via above-mentioned desulfurization carries out deamination process again, by adding NaOH solution regulation waste water to waste water
Acid-base value, the deamination on the one hand realizing being carried out by air purging waste water processes, and utilizes NaOH as regulation alkali to avoid sky
Air-blowing takes off the effusion of process foreign-matter contamination in addition to ammonia pollutant, to ensure at recovery ammonia effect and the air of subsequent step
Reason effect；On the other hand the pH value of waste water after control deamination, to ensure the deamination effect of waste water, makes ammonia-nitrogen content in waste water be less than
25mg/L, reaches the requirement of secondary discharge standard in GB8978-1996 " integrated wastewater discharge standard " table 4.Waste water adds
NaOH solution amount regulates and controls with the pH value of waste water after deamination for standard, after making deamination the pH value of waste water maintain 10.5～
11.5.The ammonia nitrogen pollutant of removing enters into ammonia recovering process with ammonia form with air and reclaims, and takes off via one-level successively
Ammonia absorbing liquid carries out first order circulated sprinkling absorption to major part ammonia, forms the circulating absorption solution based on ammonium sulfate, then warp
Carried out second level circulated sprinkling absorption by two grades of deamination absorbing liquids and the dilution heat of sulfuric acid supplemented to remaining a small amount of ammonia, formed with
Ammonium hydrogen sulfate is main circulating absorption solution；And maintain 4.5～6.5 scopes by controlling the pH value of one-level deamination absorbing liquid, adjust
The supplementary spray flux of control dilution heat of sulfuric acid, thus realize the thorough absorption to removing Ammonia in Air gas, make gas after absorption processes
Body reaches " emission standard for odor pollutants " (GB14554-93) standard；It addition, by limiting the dilution heat of sulfuric acid supplementing spray
Mass content (30%), and the pH value range (4.5～6.5) of one-level deamination absorbing liquid reclaimed, make the one-level of recovery take off
It is 40% that is near saturated ammonium sulfate solution that ammonia absorbing liquid reaches ammonium sulfate concentrations, meets the standard directly preparing solid ammonium sulfate,
The problem separating out crystal in simultaneously not appearing in absorption tower.
The processing method of the present invention, using pH value as crucial Control factors, it is achieved the combination of each processing links, enters
And complete oil refining hydrogenation technique is produced high-sulfur, the high-efficiency desulfurization of high ammonia-nitrogen wastewater, ammonia nitrogen removal process, and limit benefit in sulfur recovery
Fill the mass content of the dilution heat of sulfuric acid supplementing spray in the mass content of the NaOH solution of spray and recovery ammonia, it is achieved will removing
Sulfur, ammonia nitrogen be converted into recycling chemical products, in terms of economic worth and environmental protection, be respectively provided with significant benefit.
As the further restriction to aforesaid way, it is provided with after described step b2 and the one-level deamination absorbing liquid of recovery is depended on
Secondary be evaporated concentrating, decrease temperature crystalline and the step of centrifuge dehydration, obtain solid ammonium sulfide product.
The one-level deamination absorbing liquid reclaimed in processing method only need to be evaporated at concentration, decrease temperature crystalline and centrifuge dehydration
Reason, just can be met the solid ammonium sulfide product selling product standard, and the one-level deamination absorbing liquid reclaimed reaches near full
And ammonium sulfate, the energy can be saved greatly at evaporating concentration process, there is higher economic worth.
As the further restriction to aforesaid way, in step a1, described air stripping desulfurization processing procedure, air is with useless
The gas liquid ratio of water is (3000-5000): 1, and the void tower flow velocity of air is 1.0-2.0m/s.
As the further restriction to aforesaid way, in step a2, described first order desulfurization absorption processes step, gas with
The gas liquid ratio of first grade desulfurizing absorbing liquid is (30-100): 1；The desulfurization absorption of the described second level processes step, gas and two-grade desulfurizing
The gas liquid ratio of absorbing liquid is (30-100): 1.
As the further restriction to aforesaid way, in step b1, described air stripping deamination is processed as two-stage air and blows
De-deamination processes, and in every grade of air stripping deamination processing procedure, air is (3000-5000) with the gas liquid ratio of waste water: 1, empty
The void tower flow velocity of gas is 1.0-2.0m/s.
As the further restriction to aforesaid way, in step b2, described first order deamination absorbs processing procedure, gas with
The gas liquid ratio of one-level deamination absorbing liquid is (30-100): 1；Described second level deamination absorbs processing procedure, gas and two grades of deaminations
The gas liquid ratio of absorbing liquid is (30-100): 1.
Limit the gas liquid ratio of air stripping desulfurization processing procedure, void tower flow velocity in processing method further, at desulfurization absorption
The gas liquid ratio of reason process, the gas liquid ratio of air stripping deamination processing procedure, void tower flow velocity, deamination absorbs the gas liquid ratio of processing procedure
Deng operating parameter, make desulfurization and ammonia nitrogen removal process and reach optimum operation process, and then at the aspect such as treatment effect and processing cost
Reach all good.
Meanwhile, present invention also offers the desulfurization deamination processing means of the waste water that oil refining hydrogenation technique produces, including desulfurization
Processing mechanism and be connected to the deamination processing mechanism in desulfurization processing mechanism downstream；
Described desulfurization processing mechanism includes the first pipe-line mixer, on the first pipe-line mixer via acid adding dosing pump even
It is connected to the first acid solution tank, also includes the desulfurization stripping tower being connected to the first pipe-line mixer downstream, going out of described desulfurization stripping tower
Liquid mouth connects deamination processing mechanism, and the gas outlet of described desulfurization stripping tower connects sulfur recovery unit, and described sulfur recovery unit
Including concatenate mutually be respectively provided with reservoir and the first sulfur tail gas absorber of spray head being connected with reservoir via circulating pump and
Second sulfur tail gas absorber, the reservoir of the first sulfur tail gas absorber and the second sulfur tail gas absorber is connected, at the second sulfur tail
Gas absorption tower is provided with and supplements spray head, at the first sulfur tail gas absorber via adding the alkali liquor that alkali pump and the first alkali liquid tank be connected
Connect at reservoir and have overfall；
Second pipe blender that described deamination processing mechanism includes being sequentially connected in series, the first deamination stripping tower, the 3rd pipeline
Blender and the second deamination stripping tower, add alkali metering via first on second pipe blender and the 3rd pipe-line mixer respectively
Pump and second adds the connection of alkali dosing pump has the second alkali liquid tank, in the gas outlet of the first deamination stripping tower and the second deamination stripping tower also
Connection is connected to ammonia recovery unit, and described ammonia recovery unit includes that concatenate mutually is respectively provided with reservoir and via circulating pump and liquid storage
First ammonia tail gas absorber of the spray head that groove is connected and the second ammonia tail gas absorber, the first ammonia tail gas absorber and the second ammonia tail
The reservoir on gas absorption tower is connected, and is provided with the acid being connected via acid adding pump and the second acid solution tank on the second ammonia tail gas absorber
Liquid supplements spray head, and connecting at the reservoir of the first ammonia tail gas absorber has overfall；
Liquid outlet at described desulfurization stripping tower is provided with a PH detector, and described acid adding dosing pump controls to be connected in first
PH detector, the overfall at described first sulfur tail gas absorber is provided with the 2nd PH detector, described in add alkali pump control be connected in
2nd PH detector, the liquid outlet at described first deamination stripping tower and the second deamination stripping tower is respectively equipped with the 3rd PH detector
With the 4th PH detector, described 3rd PH detector and first adds alkali dosing pump and controls to couple, described 4th PH detector and the
Two add alkali pump controls to couple, and the overfall at the first ammonia tail gas absorber connects the 5th PH detector, and described acid adding pump controls
It is connected in the 5th PH detector.
As the further restriction to aforesaid way, it is serially connected with homogenizing tank in the upstream of the first pipe-line mixer.
As the further restriction to aforesaid way, connect in the downstream of described first ammonia tail gas absorber overfall and have collection
Liquid bath, and evaporation concentrator, crystallizer and the centrifuge being sequentially connected in series on collecting tank via delivery pump.
As the further restriction to aforesaid way, described in the second sulfur tail gas absorber, alkali liquor supplements spray head and is placed in
On spray head；Described in the second ammonia tail gas absorber, acid solution is supplemented spray head and is placed on spray head.
The processing means that the present invention provides is more conducive to the operation of above-mentioned processing method and runs control, it is possible to convenient, efficiently
Ground realizes the desulfurization to waste water, ammonia nitrogen removal processes, and makes the waste water after process meet GB8978-1996 " integrated wastewater discharge standard "
Secondary discharge standard in table 4, being more conducive to sulfur, the mineralized nitrogen of removing is recycling chemical products, it is achieved reclaim.
In sum, use technical scheme, it is thus achieved that to oil refining hydrogenation technique produce waste water desulfurization take off
Ammonia treatment method, uses and waste water carries out desulfurization and sulfur recovery process and deamination and the mode of recovery ammonia process successively, with pH value
As crucial Control factors, it is achieved the combination of each processing links, the sulfur in efficient removal waste water and ammonia and nitrogen pollution, make place
After reason, in waste water, sulfur and ammonia-nitrogen content reach the secondary discharge standard in GB8978-1996 " integrated wastewater discharge standard " table 4 and want
Ask, and be recycling chemical products by the sulfur of removing, mineralized nitrogen, be respectively provided with in terms of economic worth and environmental protection significantly
Benefit, it is achieved green chemical industry.Additionally, the processing means that the present invention provides, the operation of the most above-mentioned processing method and operation control
System, conveniently and efficiently realizes the desulfurization to waste water, ammonia nitrogen removal process and reclaims.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings and detailed description of the invention to the present invention make further describe in detail:
Fig. 1 is the desulfurization processing mechanism described in the embodiment of the present invention and the structure diagram of deamination processing mechanism；
Fig. 2 is the structure diagram of the sulfur recovery unit described in the embodiment of the present invention；
Fig. 3 is the structure diagram of the ammonia recovery unit described in the embodiment of the present invention；
Fig. 4 is the deamination absorbing liquid condensing crystallizing described in the embodiment of the present invention and the structure diagram of centrifugal treating part；
Fig. 5 is the structure diagram of the desulfurization stripping tower described in the embodiment of the present invention；
Fig. 6 is the structure diagram of the second sulfur tail gas absorber described in the embodiment of the present invention；
In figure: 1, the first pipe-line mixer；2, the first acid solution tank；3, acid adding dosing pump；4, desulfurization stripping tower；5, a PH
Detector；6, the first sulfur tail gas absorber；7, the second sulfur tail gas absorber；8, alkali pump is added；9, the first alkali liquid tank；10, the 2nd PH
Detector；11, second pipe blender；12, the first deamination stripping tower；13, the 3rd pipe-line mixer；14, the second deamination stripping
Tower；15, the second alkali liquid tank；16, first adds alkali dosing pump；17, second adds alkali dosing pump；18, the 3rd PH detector；19, the 4th
PH detector；20, the first ammonia tail gas absorber；21, the second ammonia tail gas absorber；22, acid adding pump；23, the second acid solution tank；24、
5th PH detector；25, homogenizing tank；26, overfall, 27, chimney, 28, overfall, 29, chimney, 30, tower body, 31, inlet,
32, stripping tower spray head, 33, filler, 34, liquid outlet, 35, gas outlet, 36, aerator, 37, tower body, 38, filler, 39, air inlet
Mouthful, 40, reservoir, 41, circulated sprinkling head, 42, alkali liquor supplement spray head, 43, gas outlet, 44, collecting tank, 45, heat exchanger,
46, delivery pump, 47, evaporation concentrator, 48, crystallizer, 49, centrifuge.
Detailed description of the invention
Embodiment
The present embodiment relates to processing the desulfurization deamination of the waste water that oil refining hydrogenation technique produces.
The desulfurization deamination processing means of waste water that the oil refining hydrogenation technique of the present embodiment produces, by shown in Fig. 1 to Fig. 4, its
Including desulfurization processing mechanism and the deamination processing mechanism that is connected to desulfurization processing mechanism downstream.
Wherein, desulfurization processing mechanism includes the first pipe-line mixer 1, and connecting in the first pipe-line mixer 1 upstream has first
Acid solution tank 2, in the first acid solution tank 2, the diluted acid of storage is by being arranged on adding between the first pipe-line mixer 1 and the first acid solution tank 2
Acid dosing pump 3 adds diluted acid to regulate and control the pH value of waste water in the first pipe-line mixer 1 to the first pipe-line mixer 1 quantification.?
First pipe-line mixer 1 downstream connects the desulfurization stripping tower 4 with aerator, and the liquid outlet of desulfurization stripping tower 4 is by promoting
Pump is connected to deamination processing mechanism, and sets up a PH detector 5, a PH detector 5 at the liquid outlet of desulfurization stripping tower 4
Couple and control acid adding dosing pump 3, in order to according to the pH value regulation and control acid adding dosing pump 3 of waste water at desulfurization stripping tower 4 liquid outlet, enter
And regulate and control the acid adding amount in the first pipe-line mixer 1.
Connecting in the gas outlet of desulfurization stripping tower 4 and have sulfur recovery unit, this sulfur recovery unit includes the first sulfur tail of concatenation
Gas absorption tower 6 and the second sulfur tail gas absorber 7.It is respectively provided with storage in the first sulfur tail gas absorber 6 and the second sulfur tail gas absorber 7
Liquid bath, and the circulated sprinkling head being connected with reservoir via the circulating pump arranged outside tower, the first sulfur tail gas absorber 6 and second
Reservoir in sulfur tail gas absorber 7 is also connected.In the second sulfur tail gas absorber 7, it is additionally provided with alkali liquor supplements spray head,
Alkali liquor supplements spray head and is connected to the first alkali liquid tank 9, for the second sulfur tail gas absorber via the alkali pump 8 that adds arranged outside tower
The NaOH solution stored in supplementing spray the first alkali liquid tank 9 in 7.
For giving full play to the supplementary assimilation effect of NaOH solution, alkali liquor supplements spray head and is placed in the second sulfur tail gas absorber 7
Above interior circulated sprinkling head.Connect at the reservoir of the first sulfur tail gas absorber 6 and have overfall, for the first sulfur tail gas
The discharge of absorbing liquid in absorption tower 6, the gas outlet of the second sulfur tail gas absorber 7 then connects chimney 27, for gas after absorbing
The discharge of body.Also the 2nd PH detector 10, the 2nd PH detector is set up at the overfall of the first sulfur tail gas absorber 6 reservoir
10 couple control adds alkali pump 8, in order to according to the pH value of the first grade desulfurizing absorbing liquid in the reservoir of the first sulfur tail gas absorber 6
Regulation and control add alkali pump 8, and then regulation and control supplement the caustic dosage of spray in the second sulfur tail gas absorber 7.
The deamination processing mechanism of the present embodiment includes the second pipe blender 11 being sequentially connected in series, with the first of aerator
Deamination stripping tower 12, and the 3rd pipe-line mixer 13 and the second deamination stripping tower 14 with aerator, the 3rd line-blending
Also elevator pump it is serially connected with between device 13 and the first deamination stripping tower 12.At second pipe blender 11 and the 3rd pipe-line mixer 13
Upper add alkali dosing pump 16 and second via first respectively and add alkali dosing pump 17 and connect the second alkali liquid tank 15, the second alkali liquid tank 15 internal memory
The alkali liquor of storage adds alkali dosing pump 16 and second by first respectively and adds alkali dosing pump 17 to second pipe blender 11 and the 3rd pipe
Road blender 13 quantification adds alkali liquor with the pH value of waste water in regulation and control second pipe blender 11 and the 3rd pipe-line mixer 13.
After waste water completes after sequentially passing through the first deamination stripping tower 12 and the second deamination stripping tower 14 to process, blow from being connected to the second deamination
Overfall bottom de-tower 14 is discharged, to send into Sewage Disposal or municipal wastewater pipe network.
Liquid outlet at the first deamination stripping tower 12 sets up the 3rd PH detector 18, and the 3rd PH detector 18 couples control
One adds alkali dosing pump 16, in order to add alkali dosing pump according to the pH value regulation and control first of waste water at the first deamination stripping tower 12 liquid outlet
16, and then the caustic dosage that regulation and control are in second pipe blender 11.Liquid outlet at the second deamination stripping tower 14 sets up the 4th PH
Detector 19, the 4th PH detector 19 couples control second and adds alkali dosing pump 17, in order to go out according to the second deamination stripping tower 14
At liquid mouth, the pH value regulation and control second of waste water add alkali dosing pump 17, and then the caustic dosage that regulation and control are in the 3rd pipe-line mixer 13.
The gas outlet of the first deamination stripping tower 12 and the second deamination stripping tower 14 is connected in parallel to ammonia recovery unit, and this ammonia returns
Receive unit and include the first ammonia tail gas absorber 20 and the second ammonia tail gas absorber 21 of concatenation, going out of the second ammonia tail gas absorber 21
QI KOU connects chimney 29.It is respectively provided with reservoir in the first ammonia tail gas absorber 20 and the second ammonia tail gas absorber 21, and
The circulated sprinkling head being connected with reservoir via the circulating pump arranged outside tower, the first ammonia tail gas absorber 20 and the second ammonia tail gas are inhaled
The reservoir received in tower 21 is also connected.Being additionally provided with acid solution in the second ammonia tail gas absorber 21 and supplement spray head, acid solution is mended
Fill spray head and be connected to the second acid solution tank 23, in the second ammonia tail gas absorber 21 via the acid adding pump 22 arranged outside tower
The dilution heat of sulfuric acid stored in supplementing spray the second acid solution tank 23.
For giving full play to the supplementary assimilation effect of dilution heat of sulfuric acid, acid solution is supplemented spray head and is placed in the second ammonia tail gas absorber
Above circulated sprinkling head in 21.Connect at the reservoir of the first ammonia tail gas absorber 21 and have overfall 28, for first
The discharge of absorbent solution in ammonia tail gas absorber 21.Also the 5th PH detector 24, the 5th PH detector is set up at overfall 28
24 couple control acid adding pump 22, in order to according to the pH of the one-level deamination absorbing liquid in the reservoir of the first ammonia tail gas absorber 21
Value regulation and control acid adding pump 22, and then regulation and control acid adding amount of supplementary spray in the second ammonia tail gas absorber 21.
Connecting in the downstream of the overfall 28 of the first ammonia tail gas absorber 21 and have collecting tank 44, the outlet at collecting tank 44 connects
Being connected to delivery pump 46, collecting tank 44 uses the internal container for cavity molten with the absorption collecting the first ammonia tail gas absorber 21 discharge
Liquid, delivery pump 46 uses centrifugal pump.Outlet at centrifugal pump 46 be sequentially connected in series heat exchanger 45, evaporation concentrator 47 and
Crystallizer 48 and centrifuge 49, as shown in Figure 4, use heat exchanger 45 can to carry out the steam that spontaneous evaporation concentrator 47 is discharged again
Secondary utilization, avoids steam evacuation to waste to make full use of, and removes heat exchanger 45 and also may be used in certain the present embodiment.Evaporation concentrator
47 use existing double-effect evaporation concentrator or three-effect evaporation and condensation device, and crystallizer uses the existing cooling carrying out decrease temperature crystalline
Crystallizer, centrifuge uses existing industrial centrifuge.Wherein, the centrifugal liquid that centrifuge 49 is discharged can be delivered to collecting tank
For again processing in 44.
In the present embodiment, for convenience of the process to waste water, also concatenate in the upstream of the first pipe-line mixer 1 and homogenizing tank is set
25, to be inputted to homogenizing tank 25 by the waste water that oil refining hydrogenation technique produces, and make waste water quality stable, homogenizing tank is also adopted by existing
Structure is had just may be used.In the present embodiment, Fig. 5 shows that the structure of desulfurization stripping tower 4, the first deamination stripping tower 12 and the second deamination are blown
The structure of de-tower 14 is essentially identical with the structure of desulfurization stripping tower 4, repeats no more herein.Shown in Fig. 5, desulfurization stripping tower 4
Including tower body 30, connecting and have aerator 36, and arrange liquid outlet 34 bottom tower body 30, tower body 30 top arranges gas outlet 35,
Then be provided with filler 33 in tower body 30, above filler 33, be then provided with stripping tower spray head 32, stripping tower spray head 32 with
The inlet 31 being arranged on tower body 30 top connects, and inlet 31 is then connected with the liquid outlet of homogenizing tank 25 by elevator pump.
In the present embodiment, Fig. 6 then shows the structure of the second sulfur tail gas absorber 7, and it includes tower body 37, tower body 37 inner bottom
Portion is reservoir 40, air inlet 39 above reservoir 40, and air inlet 39 is provided above filler 38, and the top of filler 38 is then arranged
Circulated sprinkling head 41 and alkali liquor supplement spray head 42, and alkali liquor supplements spray head 42 and arranges higher than circulated sprinkling head 41, circulated sprinkling
41 are connected to reservoir 40 by circulating pump, and alkali liquor supplements spray head 42 and is connected to the first alkali liquid tank 9, at the top of tower body 37
It is additionally provided with gas outlet 43.In the present embodiment, the structure of the second ammonia tail gas absorber 21 and the second basic phase of sulfur tail gas absorber 7
With, and the first sulfur tail gas absorber 6 and the first ammonia tail gas absorber 20 supplement spray head and acid solution is supplemented except being not provided with alkali liquor
Outside spray head, other structure is also essentially identical with the second sulfur tail gas absorber 7, the most also repeats no more.
Embodiment 1
Above-mentioned processing means is carried out the desulfurization deamination of the waste water that oil refining hydrogenation technique produces is processed, oil refining is hydrogenated with
(pollutant load is S to the waste water that technique produces2-: 9837mg/L；NH3-N:15329mg/L) input to homogenizing tank, then carry out
Hereinafter process:
A, desulfurization and sulfur recovery process step:
A1, desulfurization processing step: from homogenizing tank output waste water the first pipe-line mixer by add dilute sulfuric acid molten
Liquid I (mass content is 30%～50%) adjusts pH value, inputs to desulfurization stripping tower and spray after mix homogeneously, spray useless
Water inversely contacts with the air blown out from aerator at Ta Nei and carries out air stripping desulfurization process, and after desulfurization, waste water is from desulfurization stripping
The liquid outlet of tower is delivered to deamination processing mechanism and carries out de-ammonia treating step；The number that processing procedure detects according to a PH detector
Value controls acid adding dosing pump, to control the addition of dilute sulfuric acid, and then controls pH value of waste water (the i.e. the oneth PH detector inspection after desulfurization
The numerical value surveyed) maintain 0.8～1.2；
A2, sulfur recovery process step: carry out two from the input of desulfurization stripping tower gas outlet escaping gas to sulfur recovery unit
Level desulfurization absorption processes, and gas is carried out first by the first grade desulfurizing absorbing liquid of circulated sprinkling in being introduced into the first sulfur tail gas absorber
Level desulfurization absorption processes, and by the two-grade desulfurizing absorbing liquid of circulated sprinkling and supplements spray subsequently into the second sulfur tail gas absorber
NaOH solution I (mass content is 21 ± 1%) carries out second level desulfurization absorption and processes, from the second sulfur tail gas absorber gas outlet ease
The gas " emission standard for odor pollutants " (GB14554-93) gone out, can be directly discharged to air；Processing procedure is according to the 2nd PH
In the pH value of the first grade desulfurizing absorbing liquid of detector detection controls the second sulfur tail gas absorber, alkali liquor supplements spray head spray NaOH
The spray flux of solution I, the pH controlling first grade desulfurizing absorbing liquid reaches 10.7～11.3, and overflowing by the first sulfur tail gas absorber
Head piece reclaims first grade desulfurizing absorbing liquid, and the first grade desulfurizing absorbing liquid of recovery is hydrogen sulfide solution, can reach GB23937-2009
" industry NaHS " table 1 liquid L-3 standard-required, can be used for selling；Described two-grade desulfurizing absorbing liquid is to be existed by NaOH solution I
After carrying out sulfur absorption in second sulfur tail gas absorber recirculation spray carry out sulfur absorb obtain with sodium sulfide and sodium hydroxide be
Main mixed solution, described first grade desulfurizing absorbing liquid is for be carried out sulfur suction by two-grade desulfurizing absorbing liquid in the first sulfur tail gas absorber
After receipts, recirculation spray carries out the mixed solution based on NaHS that sulfur absorption obtains；
B, deamination and recovery ammonia process step:
B1, de-ammonia treating step: for the characteristic of ammonia-nitrogen content in waste water, from giving up that the liquid outlet of desulfurization stripping tower exports
Water can carry out two-stage air stripping deamination and process, and pollutes with complete removal of ammonia and nitrogen, and waste water first passes through in second pipe blender
Add NaOH solution II (mass content is 20%～30%) and adjust pH value, input after mix homogeneously to the first deamination stripping tower
Row spray, the waste water of spray inversely contacts with the air blown out from aerator at Ta Nei and carries out at first order air stripping deamination
Reason, then the liquid outlet from the first deamination stripping tower is delivered to the 3rd pipe-line mixer adjust pH by addition NaOH solution II
Value, inputs after mix homogeneously and sprays to the second deamination stripping tower, and the waste water of spray is at Ta Nei and the sky from aerator blowout
QI rising in reverse order carries out second level air stripping deamination to contact and processes, and processes through two-stage air stripping deamination, and waste water reaches GB8978-
Secondary discharge standard in 1996 " integrated wastewater discharge standard " table 4, completes to process, can be emitted into municipal wastewater pipe network；Process
The numerical control first that process detects according to the 3rd PH detector adds alkali dosing pump, molten to control NaOH in second pipe blender
The addition of liquid II, adds alkali dosing pump, to control the 3rd line-blending according to the numerical control second of the 4th PH detector detection
The addition of NaOH solution II in device, and then control pH value of waste water (the i.e. the 3rd PH detector, the 4th PH detector detection after deamination
Numerical value) maintain 10.5～11.5；
B2, recovery ammonia process step: escape from the first deamination stripping tower gas outlet and the second deamination stripping tower gas outlet
Gas jointly inputs and carries out two-stage deamination absorption process to ammonia recovery unit, and it is interior by following that gas is introduced into the first ammonia tail gas absorber
The one-level deamination absorbing liquid that ring spray is drenched carries out first order deamination absorption and processes, subsequently into the second ammonia tail gas absorber by circulating spray
The two grades of deamination absorbing liquids drenched and the dilution heat of sulfuric acid II (mass content is 30%) supplementing spray carry out second level deamination absorption
Process, reach " emission standard for odor pollutants " (GB14554-93) from the second ammonia tail gas absorber gas outlet escaping gas,
Can directly drain into air；Processing procedure controls the second ammonia according to the pH value of the one-level deamination absorbing liquid that the 5th PH detector detects
In tail gas absorber, acid solution supplements the spray flux of spray head spray dilution heat of sulfuric acid II, and the pH controlling one-level deamination absorbing liquid reaches
4.5～6.5, and reclaim one-level deamination absorbing liquid by the overfall of the first ammonia tail gas absorber, the one-level deamination of recovery absorbs
Liquid is the near saturated solution of ammonium sulfate, and ammonium sulfate mass content reaches 40%, and does not produce and separate out asking of crystal in absorption tower
Topic, processes further the one-level deamination absorbing liquid reclaimed, first passes through dense by the one-level deamination absorbing liquid being collected in collecting tank
Contracting crystallizing evaporator is evaporated concentrating, and then decrease temperature crystalline in decrease temperature crystalline device is finally delivered to centrifuge and is centrifuged
Dehydration, the solid ammonium sulfate obtained, ammonium sulfate can be met and sell the standard of product, be used for selling use, obtain from centrifuge
To solution be fed back to collecting tank, again carry out concentrating, crystallizing, circulation and stress ammonia；Described two grades of deamination absorbing liquids are by dilute sulfur
Acid solution II in the second ammonia tail gas absorber, carry out ammonia absorption after recirculation spray carry out ammonia absorb obtain with sulphuric acid and sulfur
Acid hydrogen ammonium is main mixed solution, described one-level deamination absorbing liquid be by two grades of deamination absorbing liquids in the first ammonia tail gas absorber
After carrying out ammonia absorption, recirculation spray carries out the mixed solution based on ammonium sulfate that ammonia absorption obtains.
Above-mentioned processing method, in step a1, in desulfurization stripping tower, air is (3000-5000) with the gas liquid ratio of waste water: 1
(m3/m3), the void tower flow velocity of air is 1.0-2.0m/s；In step a2, in the first sulfur tail gas absorber, gas liquid ratio is (i.e. through desulfurization
Process escaping gas and the ratio of first grade desulfurizing absorbing liquid after step) be (30-100): 1 (m3/m3), the second sulfur tail gas absorption
Gas liquid ratio in tower (i.e. the ratio of escaping gas and two-grade desulfurizing absorbing liquid after first order desulfurization absorption processes step) is
(30-100):1(m3/m3)；In step b1, the air in the first deamination stripping tower and the second deamination stripping tower and the gas-liquid of waste water
It is (3000-5000) than (i.e. the ratio of the waste water after air and desulfurization): 1 (m3/m3), the void tower flow velocity of air is 1.0-
2.0m/s；In step b2, (i.e. after de-ammonia treating step, escaping gas takes off the gas liquid ratio of the first ammonia tail gas absorber with one-level
The ratio of ammonia absorbing liquid) be (30-100): 1 (m3/m3)；The gas liquid ratio of the second ammonia tail gas absorber (i.e. absorbs through first order deamination
Process escaping gas and the ratio of two grades of deamination absorbing liquids after step) be (30-100): 1 (m3/m3)。
After testing, processed waste water COD < 120, NH3-N < 25mg/L, sulfide < 1mg/L.Meet GB8978-1996 " dirty
Water comprehensive discharge standard " table 4 secondary discharge standard
Pollutant load H in gas2S<1mg/m3, ammonia < 100mg/m3, meet " emission standard for odor pollutants "
(GB14554-93)。
Embodiment 2
The present embodiment relates to control conditions different in embodiment 1 processing method waste water, the impact of gas treatment result.
Embodiment 2.1
Using processing means same as in Example 1, and identical processing method, in the identical lower detection of other operating condition
PH control condition, on waste water, the impact of gas treatment result, is carried out shown in experiment according to the form below:
The result of above-mentioned experiment is as shown in the table:
As seen from the above table, in the desulfurization deamination processing method to the waste water that oil refining hydrogenation technique produces of the present invention, five
The pH value of link controls most important for the process of desulfurization, ammonia nitrogen removal, and the Optimal Control condition for this waste water is: desulfurization is given up
The pH of water controls at 0.8-1.2, and the first sulfur tail gas absorber overfall liquid (the first grade desulfurizing absorbing liquid i.e. reclaimed) pH controls
Control at 10.5-11.5 at 10.7-11.3, the pH of deamination waste water, the first ammonia tail gas absorber overfall liquid (i.e. reclaimed
Level deamination absorbing liquid) pH span of control is 4.5-6.5, the sulphur pollution in waste water, ammonia and nitrogen pollution can be made thoroughly to be processed, reach
Secondary discharge standard in GB8978-1996 " integrated wastewater discharge standard " table 4 and " emission standard for odor pollutants "
(GB14554-93), and be recycling chemical products by the sulfur of removing, mineralized nitrogen, it is achieved high efficiente callback.
Embodiment 2.2
Using processing means same as in Example 1, and identical processing method, in the identical lower detection of other operating condition
The control condition such as air velocity and gas liquid ratio, on waste water, the impact of gas treatment result, is carried out shown in experiment according to the form below:
The result of above-mentioned experiment is as shown in the table:
As seen from the above table, in the desulfurization deamination processing method to the waste water that oil refining hydrogenation technique produces of the present invention, each sky
The condition such as gas velocity and gas liquid ratio can affect the desulfurization to waste water, ammonia nitrogen removal result.
Embodiment 3
The present embodiment relates to the processing sequence of desulfurization and the ammonia nitrogen removal impact on result in the processing method on the present invention.
The waste water producing oil refining hydrogenation technique first carries out deamination process, i.e. first carries out waste water as described in Example 1
Deamination and recovery ammonia process step, and result is as shown in the table:
As seen from the above table, when the waste water producing oil refining hydrogenation technique first carries out deamination process, because NaHS is alkalescence,
It is easier to make hydrogen sulfide stripping go out, so the hydrogen sulfide content in gas exceeds standard after deamination, also needs hydrogen sulfide to carry out removing
Can discharge.It addition, the pH value of waste water after first desulfurization can make desulfurization raises alkali tune again, saving processes province's expense, therefore, the present invention
Processing method use with the order of first desulfurization deamination again, it is achieved the optimization process to the waste water that oil refining hydrogenation technique produces.
Claims (10)
1. refine oil the desulfurization deamination processing method of waste water that hydrogenation technique produces for one kind, it is characterised in that comprise the following steps:
A, desulfurization and sulfur recovery process step:
A1, desulfurization processing step: the waste water produced to oil refining hydrogenation technique adds dilution heat of sulfuric acid I, sprays after regulation acid-base value,
Inversely contacting with air and carry out air stripping desulfurization process, the waste water after desulfurization is delivered to de-ammonia treating step；After described desulfurization
It is 0.8～1.2 that the pH value of waste water controls；H in described dilution heat of sulfuric acid I2SO4Mass content be 30%～50%；
A2, sulfur recovery process step: will process through two-step desulfurization absorption by escaping gas after described desulfurization processing step
Rear discharge, described two-step desulfurization absorption processes and includes being processed step by the first grade desulfurizing absorbing liquid of circulated sprinkling to through described desulfurization
After rapid, escaping gas carries out first order desulfurization absorption process step, and by the two-grade desulfurizing absorbing liquid of circulated sprinkling with supplementary
The NaOH solution I of spray carries out second level desulfurization absorption to escaping gas after described first order desulfurization absorption processes step
Process step；The pH value controlling first grade desulfurizing absorbing liquid is 10.7～11.3, reclaims first grade desulfurizing absorbing liquid；Described NaOH solution
In I, the mass content of NaOH is 20%～22%, and described two-grade desulfurizing absorbing liquid is to be absorbed in second level desulfurization by NaOH solution I
Processing recirculation spray after carrying out sulfur absorption in step and carry out the mixed solution that sulfur absorption obtains, described first grade desulfurizing absorbing liquid is
By two-grade desulfurizing absorbing liquid first order desulfurization absorption process in step carry out sulfur absorption after recirculation spray carry out sulfur and absorb
The mixed solution arrived；
B, deamination and recovery ammonia process step:
B1, de-ammonia treating step: the waste water after desulfurization adds NaOH solution II, sprays after regulation acid-base value, reverse with air
Contact carries out air stripping deamination process, the discharge of wastewater after deamination；After described deamination waste water pH value control be 10.5～
11.5；In described NaOH solution II, the mass content of NaOH is 20～30%；
B2, recovery ammonia process step: will process through two-stage deamination absorption by escaping gas after described de-ammonia treating step
Rear discharge, described two-stage deamination absorption processes and includes being processed step by the one-level deamination absorbing liquid of circulated sprinkling to through described deamination
After rapid, escaping gas carries out first order deamination absorption process step, and by the two of circulated sprinkling grades of deamination absorbing liquids with supplementary
The dilution heat of sulfuric acid II of spray carries out second level deamination to escaping gas after described first order deamination absorption processes step
Absorption processes step；The pH value controlling one-level deamination absorbing liquid is 4.5～6.5, reclaims one-level deamination absorbing liquid；Described dilute sulfuric acid
H in solution II2SO4Mass content be 30%, described two grades of deamination absorbing liquids be by dilution heat of sulfuric acid II second level deamination inhale
Receipts process recirculation spray after carrying out ammonia absorption in step and carry out the mixed solution that ammonia absorption obtains, described one-level deamination absorbing liquid
Ammonia absorption is carried out for recirculation spray after being carried out ammonia absorption by two grades of deamination absorbing liquids in first order deamination absorption processes step
The mixed solution obtained.
The desulfurization deamination processing method of the waste water that oil refining hydrogenation technique the most according to claim 1 produces, it is characterised in that:
It is provided with after described step b2 and the one-level deamination absorbing liquid of recovery is evaporated successively concentration, decrease temperature crystalline and centrifuge dehydration
Step, obtains solid ammonium sulfide product.
The desulfurization deamination processing method of the waste water that oil refining hydrogenation technique the most according to claim 1 produces, it is characterised in that:
In step a1, described air stripping desulfurization processing procedure, air is (3000-5000) with the gas liquid ratio of waste water: 1, the sky of air
Tower flow velocity is 1.0-2.0m/s.
The desulfurization deamination processing method of the waste water that oil refining hydrogenation technique the most according to claim 1 produces, it is characterised in that:
In step a2, described first order desulfurization absorption processes step, and gas is (30-100) with the gas liquid ratio of first grade desulfurizing absorbing liquid: 1；
The desulfurization absorption of the described second level processes step, and gas is (30-100) with the gas liquid ratio of two-grade desulfurizing absorbing liquid: 1.
The desulfurization deamination processing method of the waste water that oil refining hydrogenation technique the most according to claim 1 produces, it is characterised in that:
In step b1, described air stripping deamination is processed as two-stage air stripping deamination and processes, every grade of air stripping deamination processing procedure
In, air is (3000-5000) with the gas liquid ratio of waste water: 1, and the void tower flow velocity of air is 1.0-2.0m/s.
The desulfurization deamination processing method of the waste water that oil refining hydrogenation technique the most according to claim 1 produces, it is characterised in that:
In step b2, described first order deamination absorbs processing procedure, and gas is (30-100) with the gas liquid ratio of one-level deamination absorbing liquid: 1；
Described second level deamination absorbs processing procedure, and the gas liquid ratio of gas and two grades of deamination absorbing liquids is (30-100): 1.
7. refine oil the desulfurization deamination processing means of waste water that hydrogenation technique produces for one kind, it is characterised in that: include desulfurization datatron
Structure and be connected to the deamination processing mechanism in desulfurization processing mechanism downstream；
Described desulfurization processing mechanism includes the first pipe-line mixer, and connecting via acid adding dosing pump on the first pipe-line mixer has
First acid solution tank, also includes the desulfurization stripping tower being connected to the first pipe-line mixer downstream, the liquid outlet of described desulfurization stripping tower
Connecting deamination processing mechanism, the gas outlet of described desulfurization stripping tower connects sulfur recovery unit, and described sulfur recovery unit includes
Concatenate mutually is respectively provided with reservoir and the first sulfur tail gas absorber and second of spray head being connected via circulating pump with reservoir
Sulfur tail gas absorber, the reservoir of the first sulfur tail gas absorber and the second sulfur tail gas absorber is connected, and inhales at the second sulfur tail gas
Receive tower to be provided with and supplement spray head, at the liquid storage of the first sulfur tail gas absorber via adding the alkali liquor that alkali pump and the first alkali liquid tank be connected
Connect at groove and have overfall；
Second pipe blender that described deamination processing mechanism includes being sequentially connected in series, the first deamination stripping tower, the 3rd line-blending
Device and the second deamination stripping tower, on second pipe blender and the 3rd pipe-line mixer respectively via first add alkali dosing pump and
Second adds the connection of alkali dosing pump has the second alkali liquid tank, in the gas outlet parallel connection phase of the first deamination stripping tower and the second deamination stripping tower
It is connected to ammonia recovery unit, and described ammonia recovery unit includes that concatenate mutually is respectively provided with reservoir and via circulating pump and reservoir phase
First ammonia tail gas absorber of spray head even and the second ammonia tail gas absorber, the first ammonia tail gas absorber and the second ammonia tail gas are inhaled
The reservoir receiving tower is connected, and is provided with the acid solution being connected via acid adding pump and the second acid solution tank and mends on the second ammonia tail gas absorber
Filling spray head, connecting at the reservoir of the first ammonia tail gas absorber has overfall；
Liquid outlet at described desulfurization stripping tower is provided with a PH detector, and described acid adding dosing pump controls to be connected in a PH inspection
Survey instrument, the overfall at described first sulfur tail gas absorber is provided with the 2nd PH detector, described in add alkali pump control be connected in second
PH detector, the liquid outlet at described first deamination stripping tower and the second deamination stripping tower is respectively equipped with the 3rd PH detector and
Four PH detectors, described 3rd PH detector and first adds alkali dosing pump and controls to couple, and described 4th PH detector and second adds
Alkali pump controls to couple, and the overfall at the first ammonia tail gas absorber connects the 5th PH detector, and described acid adding pump controls to couple
In the 5th PH detector.
The desulfurization deamination processing means of the waste water that oil refining hydrogenation technique the most according to claim 7 produces, it is characterised in that:
It is serially connected with homogenizing tank in the upstream of the first pipe-line mixer.
The desulfurization deamination processing means of the waste water that oil refining hydrogenation technique the most according to claim 7 produces, it is characterised in that:
Connect in the downstream of described first ammonia tail gas absorber overfall and have collecting tank, and be sequentially connected in series in collecting tank via delivery pump
On evaporation concentrator, crystallizer and centrifuge.
The desulfurization deamination processing means of the waste water that oil refining hydrogenation technique the most according to claim 7 produces, its feature exists
In: described in the second sulfur tail gas absorber, alkali liquor supplements spray head and is placed on spray head；In the second ammonia tail gas absorber
Described acid solution is supplemented spray head and is placed on spray head.
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| CN114768487B (en) * | 2022-05-07 | 2023-11-21 | 江苏凯美酷碳科技有限公司 | Circulating system for solvent recovery gas-liquid separation and wastewater reuse and operation method thereof |
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| CN106277455B (en) | 2023-09-26 |
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