CN106277455B - Desulfurization and deamination treatment method and treatment device for wastewater generated in oil refining hydrogenation process - Google Patents

Desulfurization and deamination treatment method and treatment device for wastewater generated in oil refining hydrogenation process Download PDF

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CN106277455B
CN106277455B CN201610770991.0A CN201610770991A CN106277455B CN 106277455 B CN106277455 B CN 106277455B CN 201610770991 A CN201610770991 A CN 201610770991A CN 106277455 B CN106277455 B CN 106277455B
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deamination
absorption
treatment
desulfurization
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CN106277455A (en
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孟琳
王海波
刘国才
殷召锋
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Hebei Yuanqing Environmental Protection Technology Co ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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)
    • 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
    • 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

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Abstract

The invention relates to a desulfurization and deamination treatment method for wastewater generated by an oil refining hydrogenation process, which comprises the steps of desulfurization and sulfur recovery treatment and deamination and ammonia recovery treatment for wastewater in sequence. The desulfurization and deamination treatment method for the wastewater generated by the oil refining hydrogenation process, which is disclosed by the invention, takes the pH value as a key regulation factor, realizes the organic combination of all treatment links, efficiently removes sulfur and ammonia nitrogen pollution in the wastewater, ensures that the content of sulfur and ammonia nitrogen in the treated wastewater meets the requirement of a secondary discharge standard in GB8978-1996 integrated wastewater discharge standard, converts the removed sulfur and ammonia nitrogen into reusable chemical products, has obvious benefits in the aspects of economic value and environmental protection, and realizes green chemical industry. In addition, the treatment device provided by the invention is more beneficial to the operation and operation control of the treatment method, and can conveniently and efficiently realize the desulfurization, ammonia nitrogen removal treatment and recovery of wastewater.

Description

Desulfurization and deamination treatment method and treatment device for wastewater generated in oil refining hydrogenation process
Technical Field
The invention relates to the technical field of desulfurization and deamination of wastewater, in particular to a desulfurization and deamination treatment method of wastewater generated in an oil refining hydrogenation process and a treatment device for the treatment method.
Background
Because of the improvement of the quality of the fuel oil and the lubricating oil for vehicles in China, a hydrogenation process is added in the oil refining process by an oil refinery to remove mercapto (-SH) and amino (-NH) contained in the fuel oil and the lubricating oil 2 ) Nitro (-NO) 2 ) Hydrophilic groups such as alcohol, aldehyde and ketone, the content of sulfur dioxide and nitrogen oxides in the combustion emission of the oil product of the engine is reduced, the risk of lubricating oil emulsification is reduced, and the quality of the oil product is improved.
After the fuel oil and the lubricating oil are hydrogenated, mercapto (-SH) and amino (-NH) 2 ) Nitro (-NO) 2 ) Hydrophilic groups such as alcohols, aldehydes, ketones and the like are converted into water, (NH) 4 ) 2 S and NH 4 NO 3 Separating from oil to form aqueous solution, wherein sulfur ions (S 2- ) The concentration is up to 9000mg/L, and ammonia Nitrogen (NH) 4 -N) concentration is up to 15000mg/L, and the desulfurization and ammonia nitrogen removal treatment is necessary for the ultra-high concentration sulfur-containing and ammonia nitrogen-containing wastewater.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a desulfurization and deamination treatment method for wastewater generated by an oil refining hydrogenation process, which is used for removing high-content sulfur and ammonia nitrogen pollution in the wastewater, so that the content of sulfur and ammonia nitrogen in the treated wastewater meets the requirement of a secondary emission standard in GB8978-1996 integrated wastewater emission standard, and can be used for recycling sulfur to obtain sodium sulfide and recycling ammonia nitrogen to obtain ammonium sulfate.
In order to achieve the above object, the present invention provides a desulfurization and deamination treatment method for wastewater generated in a refinery hydrogenation process, comprising the steps of:
a. desulfurizing and sulfur recovery treatment:
a1, desulfurization treatment: adding dilute sulfuric acid solution I into the wastewater generated in the oil refining hydrogenation process, regulating the pH value, spraying, reversely contacting with air to perform air stripping desulfurization treatment, and conveying the desulfurized wastewater to a deamination treatment step; the pH value of the desulfurized wastewater is controlled to be 0.8-1.2; h in the dilute sulfuric acid solution I 2 SO 4 The mass content of (2) is 30% -50%;
a2, sulfur recovery treatment: the gas escaping from the desulfurization treatment step is discharged after two-stage desulfurization absorption treatment, wherein the two-stage desulfurization absorption treatment comprises a first-stage desulfurization absorption treatment step of circularly spraying a first-stage desulfurization absorption liquid on the gas escaping from the desulfurization treatment step, and a second-stage desulfurization absorption treatment step of circularly spraying a second-stage desulfurization absorption liquid and a supplemental spraying NaOH solution I on the gas escaping from the first-stage desulfurization absorption treatment step; controlling the pH value of the primary desulfurization absorption liquid to be 10.7-11.3, and recovering the primary desulfurization absorption liquid; the mass content of NaOH in the NaOH solution I is 20% -22%, the second-stage desulfurization absorption liquid is a mixed solution obtained by performing sulfur absorption on the NaOH solution I in the second-stage desulfurization absorption treatment step and then performing recirculation spraying on the NaOH solution I, and the first-stage desulfurization absorption liquid is a mixed solution obtained by performing sulfur absorption on the second-stage desulfurization absorption liquid in the first-stage desulfurization absorption treatment step and then performing recirculation spraying on the NaOH solution I;
b. deamination and ammonia recovery treatment steps:
b1, deamination treatment: adding NaOH solution II into the desulfurized wastewater, regulating the pH value, spraying, reversely contacting with air to perform air stripping deamination treatment, and discharging the deaminated wastewater; the pH value of the wastewater after deamination is controlled to be 10.5-11.5; the mass content of NaOH in the NaOH solution II is 20-30%;
b2, ammonia recovery treatment: the gas escaping from the deamination treatment step is discharged after two-stage deamination absorption treatment, wherein the two-stage deamination absorption treatment comprises a first-stage deamination absorption treatment step of circularly spraying a first-stage deamination absorption liquid on the gas escaping from the deamination treatment step, and a second-stage deamination absorption treatment step of circularly spraying a second-stage deamination absorption liquid and a diluted sulfuric acid solution II which is sprayed in a complementary manner on the gas escaping from the first-stage deamination absorption treatment step; controlling the pH value of the primary deamination absorption liquid to be 4.5-6.5, and recovering the primary deamination absorption liquid; h in the dilute sulfuric acid solution II 2 SO 4 The mass content of the (B) is 30%, and the secondary deamination absorption liquidThe ammonia absorption treatment method comprises the steps of carrying out ammonia absorption by a dilute sulfuric acid solution II in a second-stage ammonia absorption treatment step, and then carrying out recycling spraying to carry out ammonia absorption, wherein the first-stage ammonia absorption liquid is a mixed solution obtained by carrying out ammonia absorption by a second-stage ammonia absorption liquid in a first-stage ammonia absorption treatment step, and then carrying out recycling spraying to carry out ammonia absorption.
The wastewater treatment method of the invention aims at the characteristics of high sulfur content and high ammonia nitrogen content of wastewater generated by an oil refining hydrogenation process, adopts a mode of sequentially carrying out desulfurization and sulfur recovery treatment and deamination and ammonia recovery treatment, and efficiently removes sulfur and ammonia nitrogen pollution in the wastewater, so that the sulfur and ammonia nitrogen content in the treated wastewater reaches the requirement of a secondary emission standard in a table 4 of GB8978-1996 integrated wastewater emission standard, and the sulfur is recovered to obtain sodium sulfide, the ammonia nitrogen is recovered to obtain ammonium sulfate, and pollutants are converted into available valuable chemical products, thereby realizing green chemical industry.
Firstly desulfurizing the wastewater in the treatment method, regulating the pH value of the wastewater by adding dilute sulfuric acid into the wastewater, realizing the desulfurization treatment by blowing the wastewater by air on one hand, and utilizing sulfuric acid as regulating acid to avoid the escape of impurity pollutants except hydrogen sulfide pollutants in the air blowing-off process so as to ensure the sulfur recovery effect and the air treatment effect of the subsequent steps; on the other hand, the pH value of the wastewater after desulfurization is controlled to ensure the desulfurization effect of the wastewater, so that the sulfur content in the wastewater is lower than 1mg/L, and the requirement of the secondary discharge standard in the table 4 of GB8978-1996 comprehensive wastewater discharge standard is met. The amount of dilute sulfuric acid added into the wastewater is regulated and controlled by taking the pH value of the wastewater after desulfurization as a standard, so that the pH value of the wastewater after desulfurization is maintained at 0.8-1.2. The removed sulfur pollutants enter the sulfur recovery process along with air in the form of hydrogen sulfide to be recovered, and the primary desulfurization absorption liquid is sequentially used for carrying out primary circulating spray absorption on most of hydrogen sulfide to form a concentrated solution circulation mainly comprising sodium sulfide, and the secondary desulfurization absorption liquid and the supplemental NaOH solution are used for carrying out secondary circulating spray absorption on the rest small amount of hydrogen sulfide to form a lean solution circulation mainly comprising sodium sulfide; the NaOH solution needs to be supplemented in a spraying mode, and the pH value of the primary desulfurization absorption liquid is controlled to be maintained in the range of 10.7-11.3, so that the supplementing spraying quantity of the NaOH solution is regulated, the thorough absorption of hydrogen sulfide in the removed air is realized, and the gas after the absorption treatment reaches the malodorous pollutant emission standard (GB 14554-93); in addition, the mass content (20% -22%) of the NaOH solution which is sprayed in a supplementing way and the pH value range (10.7-11.3) of the recovered primary desulfurization absorption liquid are limited, so that the recovered primary desulfurization absorption liquid reaches the standard that the mass content of sodium hydrosulfide meets 28%, and the recovered primary desulfurization absorption liquid can be directly used as a chemical product, such as unhairing of peltry in the tanning industry, tanning treatment and the like.
The wastewater after desulfurization is subjected to deamination treatment, and NaOH solution is added into the wastewater to adjust the pH value of the wastewater, so that deamination treatment by air sweeping the wastewater is realized on one hand, naOH is used as adjusting alkali to avoid impurity pollutants except ammonia pollutants from escaping in the air stripping process, and the ammonia recovery effect and the air treatment effect of the subsequent steps are ensured; on the other hand, the pH value of the wastewater after deamination is controlled to ensure the deamination effect of the wastewater, so that the ammonia nitrogen content in the wastewater is less than 25mg/L, and the requirement of the secondary emission standard in Table 4 of GB8978-1996 integrated wastewater emission standard is met. The pH value of the wastewater after deamination is maintained at 10.5-11.5 by regulating and controlling the amount of NaOH solution added into the wastewater with the pH value of the wastewater after deamination as a standard. The removed ammonia nitrogen pollutants are recycled along with air in an ammonia recycling process, and most ammonia is subjected to first-stage circulating spray absorption sequentially through a first-stage deamination absorption liquid to form a circulating absorption liquid mainly containing ammonium sulfate, and the rest ammonia is subjected to second-stage circulating spray absorption through a second-stage deamination absorption liquid and a supplemented dilute sulfuric acid solution to form a circulating absorption liquid mainly containing ammonium bisulfate; the pH value of the primary deamination absorption liquid is controlled to be maintained in the range of 4.5-6.5, and the supplementary spraying amount of the dilute sulfuric acid solution is regulated and controlled, so that the ammonia in the removed air is thoroughly absorbed, and the absorbed gas reaches the standard of malodorous pollutant emission standard (GB 14554-93); in addition, the mass content (30%) of the diluted sulfuric acid solution which is sprayed in a supplementing way and the pH value range (4.5-6.5) of the recovered primary deamination absorption liquid are limited, so that the recovered primary deamination absorption liquid reaches the ammonium sulfate concentration of 40%, namely the nearly saturated ammonium sulfate solution, thereby meeting the standard of directly preparing solid ammonium sulfate and simultaneously avoiding the problem of crystal precipitation in an absorption tower.
The treatment method of the invention takes the pH value as a key regulation factor, realizes the organic combination of each treatment link, further completes the high-efficiency desulfurization and ammonia nitrogen removal treatment of high-sulfur and high-ammonia nitrogen wastewater generated in the oil refining hydrogenation process, limits the mass content of NaOH solution which is complementarily sprayed in sulfur recovery and the mass content of dilute sulfuric acid solution which is complementarily sprayed in ammonia recovery, realizes the direct conversion of the removed sulfur and ammonia nitrogen into reusable chemical products, and has obvious benefits in economic value and environmental protection.
As a further limitation to the above manner, the step b2 is followed by a step of sequentially evaporating, concentrating, cooling, crystallizing and centrifugally dehydrating the recovered primary deamination absorption liquid to obtain a solid ammonium sulfide product.
The first-stage deamination absorption liquid recovered in the treatment method can obtain a solid ammonium sulfide product meeting the sales product standard only by evaporating concentration, cooling crystallization and centrifugal dehydration treatment, and the recovered first-stage deamination absorption liquid reaches a nearly saturated ammonium sulfate solution, so that energy can be greatly saved in the evaporating concentration process, and the method has higher economic value.
As a further limitation to the above mode, in the step a1, the air-to-liquid ratio of air to wastewater in the air stripping desulfurization treatment process is (3000-5000) 1, and the superficial flow rate of air is 1.0-2.0m/s.
As a further limitation to the above mode, in the step a2, the gas-liquid ratio of the gas to the primary desulfurization absorbing liquid in the primary desulfurization absorbing treatment step is (30-100): 1; the gas-liquid ratio of the gas and the secondary desulfurization absorption liquid in the second desulfurization absorption treatment step is (30-100): 1.
As a further limitation to the above mode, in the step b1, the air stripping and deamination treatment is two-stage air stripping and deamination treatment, in each stage of air stripping and deamination treatment, the air-liquid ratio of air to wastewater is (3000-5000): 1, and the air tower flow rates of the air are 1.0-2.0m/s.
As a further limitation to the above mode, in the step b2, the gas-liquid ratio of the gas to the primary deamination absorption liquid is (30-100): 1; in the second-stage deamination absorption treatment process, the gas-liquid ratio of the gas to the second-stage deamination absorption liquid is (30-100): 1.
Further limiting the operation parameters such as the gas-liquid ratio, the air tower flow rate, the gas-liquid ratio, the air tower flow rate and the gas-liquid ratio of the air stripping and desulfurizing treatment process, the gas-liquid ratio, the air tower flow rate, the gas-liquid ratio of the deamination and absorbing treatment process and the like in the treatment method, so that the desulfurization and deamination treatment reaches the optimal operation process, and further the treatment effect, the treatment cost and the like are excellent.
Meanwhile, the invention also provides a desulfurization and deamination treatment device for wastewater generated by the oil refining hydrogenation process, which comprises a desulfurization treatment mechanism and a deamination treatment mechanism connected to the downstream of the desulfurization treatment mechanism;
the desulfurization treatment mechanism comprises a first pipeline mixer, a first acid liquid tank is connected to the first pipeline mixer through an acid adding metering pump, the desulfurization treatment mechanism further comprises a desulfurization blowing-off tower connected to the downstream of the first pipeline mixer, a liquid outlet of the desulfurization blowing-off tower is connected with a deamination treatment mechanism, a gas outlet of the desulfurization blowing-off tower is connected with a sulfur recovery unit, the sulfur recovery unit comprises a first sulfur tail gas absorption tower and a second sulfur tail gas absorption tower which are connected in series and are respectively provided with a liquid storage tank and a spray header connected with the liquid storage tank through a circulating pump, the liquid storage tanks of the first sulfur tail gas absorption tower and the second sulfur tail gas absorption tower are communicated, an alkali liquor supplementing spray header connected with the first alkali liquid tank through an alkali adding pump is arranged on the second sulfur tail gas absorption tower, and an overflow port is connected to the liquid storage tank of the first sulfur tail gas absorption tower;
the deamination treatment mechanism comprises a second pipeline mixer, a first deamination blowing-off tower, a third pipeline mixer and a second deamination blowing-off tower which are sequentially connected in series, wherein the second pipeline mixer and the third pipeline mixer are respectively connected with a second alkali liquid tank through a first alkali adding metering pump and a second alkali adding metering pump, the air outlets of the first deamination blowing-off tower and the second deamination blowing-off tower are connected with an ammonia recovery unit in parallel, the ammonia recovery unit comprises a first ammonia tail gas absorption tower and a second ammonia tail gas absorption tower which are connected in series and are respectively provided with a liquid storage tank and a spray header connected with the liquid storage tank through a circulating pump, the liquid storage tanks of the first ammonia tail gas absorption tower and the second ammonia tail gas absorption tower are communicated, an acid liquid supplementing spray header connected with the second acid liquid tank through an acid adding pump is arranged on the second ammonia tail gas absorption tower, and an overflow port is connected at the liquid storage tank of the first ammonia tail gas absorption tower;
the liquid outlet of desulfurization stripping tower is equipped with first PH detector, add sour measuring pump control and link in first PH detector the overflow mouth of first sulfur tail gas absorption tower is equipped with the second PH detector, add alkali pump control and link in the second PH detector first deamination stripping tower and second deamination stripping tower's liquid outlet is equipped with third PH detector and fourth PH detector respectively, third PH detector and first alkali adding measuring pump control link, fourth PH detector and second alkali adding pump control link, be connected with the fifth PH detector at the overflow mouth of first ammonia tail gas absorption tower, add sour pump control and link in the fifth PH detector.
As a further limitation of the above, a homogenizing tank is connected in series upstream of the first pipe mixer.
As a further limitation to the above manner, a liquid collecting tank is connected downstream of the overflow port of the first ammonia tail gas absorbing tower, and an evaporation concentrator, a crystallizer and a centrifuge are sequentially connected in series on the liquid collecting tank via a delivery pump.
As a further limitation to the above manner, the lye replenishment showerhead is disposed above the showerhead in the second sulfur tail gas absorber; and the acid liquor supplementing spray header is arranged above the spray header in the second ammonia tail gas absorption tower.
The treatment device provided by the invention is more beneficial to the operation and operation control of the treatment method, can conveniently and efficiently realize the desulfurization and ammonia nitrogen removal treatment of the wastewater, ensures that the treated wastewater meets the secondary discharge standard in the table 4 of GB8978-1996 integrated wastewater discharge standard, and is more beneficial to converting the removed sulfur and ammonia nitrogen into reusable chemical products so as to realize recovery.
In summary, the technical scheme of the invention is adopted to obtain the desulfurization and deamination treatment method for wastewater generated in the oil refining hydrogenation process, the method of sequentially carrying out desulfurization and sulfur recovery treatment and deamination and ammonia recovery treatment on the wastewater is adopted, the pH value is used as a key regulation factor, the organic combination of all treatment links is realized, the sulfur and ammonia nitrogen pollution in the wastewater is effectively removed, the sulfur and ammonia nitrogen content in the treated wastewater meets the requirement of the secondary emission standard in the table 4 of GB8978-1996 comprehensive wastewater emission standard, the removed sulfur and ammonia nitrogen are converted into reusable chemical products, and the method has remarkable benefits in the aspects of economic value and environmental protection, and realizes green chemical industry. In addition, the treatment device provided by the invention is more beneficial to the operation and operation control of the treatment method, and can conveniently and efficiently realize the desulfurization, ammonia nitrogen removal treatment and recovery of wastewater.
Drawings
The invention will be described in more detail below with reference to the attached drawings and detailed description:
FIG. 1 is a schematic diagram of a desulfurization treatment mechanism and a deamination treatment mechanism according to an embodiment of the present invention;
FIG. 2 is a schematic view of a sulfur recovery unit according to an embodiment of the present invention;
FIG. 3 is a schematic view of an ammonia recovery unit according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a concentrating crystallization and centrifugation portion of a deaminated absorption liquid according to an embodiment of the present invention;
FIG. 5 is a schematic view showing the structure of a desulfurization stripping column according to an embodiment of the present invention;
FIG. 6 is a schematic diagram of a second sulfur tail gas absorber according to an embodiment of the present invention;
in the figure: 1. a first pipe mixer; 2. a first acid tank; 3. an acid metering pump is added; 4. a desulfurization stripping tower; 5. a first pH detector; 6. a first sulfur tail gas absorber; 7. a second sulfur tail gas absorption tower; 8. adding an alkali pump; 9. a first alkali liquid tank; 10. a second pH detector; 11. a second pipe mixer; 12. a first deamination blow-off column; 13. a third pipe mixer; 14. a second deamination blow-off column; 15. a second alkali liquid tank; 16. a first alkali adding metering pump; 17. a second alkali adding metering pump; 18. a third PH detector; 19. a fourth PH detector; 20. a first ammonia tail gas absorption tower; 21. a second ammonia tail gas absorption tower; 22. adding an acid pump; 23. a second acid tank; 24. a fifth PH detector; 25. a homogenizing tank; 26. overflow port, 27, chimney, 28, overflow port, 29, chimney, 30, tower body, 31, liquid inlet, 32, stripping tower spray header, 33, packing, 34, liquid outlet, 35, gas outlet, 36, blower, 37, tower body, 38, packing, 39, gas inlet, 40, liquid storage tank, 41, circulating spray header, 42, alkali liquor supplementing spray header, 43, gas outlet, 44, liquid collecting tank, 45, heat exchanger, 46, delivery pump, 47, evaporation concentrator, 48, crystallizer, 49, centrifuge.
Detailed Description
Examples
This example relates to the desulfurization and deamination of wastewater produced by refinery hydrogenation processes.
The desulfurization and deamination treatment device for wastewater produced by the refinery hydrogenation process of this embodiment, as shown in fig. 1 to 4, comprises a desulfurization treatment mechanism and a deamination treatment mechanism connected downstream of the desulfurization treatment mechanism.
The desulfurization treatment mechanism comprises a first pipeline mixer 1, a first acid liquid tank 2 is connected to the upstream of the first pipeline mixer 1, and dilute acid stored in the first acid liquid tank 2 is quantitatively added into the first pipeline mixer 1 through an acid adding metering pump 3 arranged between the first pipeline mixer 1 and the first acid liquid tank 2 to regulate and control the pH value of wastewater in the first pipeline mixer 1. The downstream of the first pipeline mixer 1 is connected with a desulfurization stripping tower 4 with a blower, a liquid outlet of the desulfurization stripping tower 4 is connected to a deamination treatment mechanism through a lifting pump, a first PH detector 5 is additionally arranged at the liquid outlet of the desulfurization stripping tower 4, and the first PH detector 5 is connected with a control acid adding metering pump 3 so as to regulate and control the acid adding metering pump 3 according to the pH value of wastewater at the liquid outlet of the desulfurization stripping tower 4, and further regulate and control the acid adding amount in the first pipeline mixer 1.
The gas outlet of the desulfurization stripping tower 4 is connected with a sulfur recovery unit, and the sulfur recovery unit comprises a first sulfur tail gas absorption tower 6 and a second sulfur tail gas absorption tower 7 which are connected in series. The first sulfur tail gas absorption tower 6 and the second sulfur tail gas absorption tower 7 are respectively internally provided with a liquid storage tank and a circulating spray header connected with the liquid storage tank through a circulating pump arranged outside the tower, and the liquid storage tanks in the first sulfur tail gas absorption tower 6 and the second sulfur tail gas absorption tower 7 are also communicated. An alkali liquor supplementing spray header is further arranged in the second sulfur tail gas absorption tower 7 and is connected to the first alkali liquor tank 9 through an alkali adding pump 8 arranged outside the tower so as to be used for supplementing and spraying NaOH solution stored in the first alkali liquor tank 9 into the second sulfur tail gas absorption tower 7.
In order to fully exert the supplementary absorption effect of the NaOH solution, the alkali liquor supplementary spray header is arranged above the circulating spray header in the second sulfur tail gas absorption tower 7. An overflow port is connected to the liquid storage tank of the first sulfur tail gas absorption tower 6 for discharging the absorption liquid in the first sulfur tail gas absorption tower 6, and the gas outlet of the second sulfur tail gas absorption tower 7 is communicated with a chimney 27 for discharging the absorbed gas. The overflow port of the liquid storage tank of the first sulfur tail gas absorption tower 6 is also additionally provided with a second PH detector 10, and the second PH detector 10 is connected with and controls the alkali adding pump 8 so as to regulate and control the alkali adding pump 8 according to the pH value of the primary desulfurization absorption liquid in the liquid storage tank of the first sulfur tail gas absorption tower 6, thereby regulating and controlling the alkali adding amount of the supplementary spray in the second sulfur tail gas absorption tower 7.
The deamination processing mechanism of this embodiment includes a second pipeline mixer 11, a first deamination blow-off tower 12 with a blower, and a third pipeline mixer 13 and a second deamination blow-off tower 14 with a blower, which are connected in series in sequence, and a lift pump is also connected in series between the third pipeline mixer 13 and the first deamination blow-off tower 12. The second pipeline mixer 11 and the third pipeline mixer 13 are respectively connected with a second alkali liquid tank 15 through a first alkali adding metering pump 16 and a second alkali adding metering pump 17, and alkali liquid stored in the second alkali liquid tank 15 is respectively quantitatively added into the second pipeline mixer 11 and the third pipeline mixer 13 through the first alkali adding metering pump 16 and the second alkali adding metering pump 17 so as to regulate and control the pH value of waste water in the second pipeline mixer 11 and the third pipeline mixer 13. After the wastewater is treated by the first ammonia removal blowing tower 12 and the second ammonia removal blowing tower 14 in sequence, the wastewater is discharged from an overflow port connected to the bottom of the second ammonia removal blowing tower 14 to be sent to a sewage treatment station or municipal sewage pipe network.
A third PH detector 18 is additionally arranged at the liquid outlet of the first deamination blow-off tower 12, and the third PH detector 18 is connected with and controls the first alkali adding metering pump 16 so as to regulate and control the first alkali adding metering pump 16 according to the pH value of the wastewater at the liquid outlet of the first deamination blow-off tower 12, and further regulate and control the alkali adding amount into the second pipeline mixer 11. A fourth PH detector 19 is additionally arranged at the liquid outlet of the second deamination blow-off tower 14, and the fourth PH detector 19 is connected with and controls the second alkali adding metering pump 17 so as to regulate and control the second alkali adding metering pump 17 according to the pH value of the wastewater at the liquid outlet of the second deamination blow-off tower 14, thereby regulating and controlling the alkali adding amount into the third pipeline mixer 13.
The air outlets of the first ammonia removal blowing tower 12 and the second ammonia removal blowing tower 14 are connected in parallel to an ammonia recovery unit, the ammonia recovery unit comprises a first ammonia tail gas absorption tower 20 and a second ammonia tail gas absorption tower 21 which are connected in series, and a chimney 29 is connected to the air outlet of the second ammonia tail gas absorption tower 21. The first ammonia tail gas absorption tower 20 and the second ammonia tail gas absorption tower 21 are respectively provided with a liquid storage tank, and a circulating spray header connected with the liquid storage tank through a circulating pump arranged outside the tower, and the liquid storage tanks in the first ammonia tail gas absorption tower 20 and the second ammonia tail gas absorption tower 21 are also communicated. An acid liquor supplementing spray header is also arranged in the second ammonia tail gas absorption tower 21 and is connected to a second acid liquid tank 23 through an acid adding pump 22 arranged outside the tower so as to be used for supplementing and spraying the dilute sulfuric acid solution stored in the second acid liquid tank 23 into the second ammonia tail gas absorption tower 21.
In order to fully exert the supplemental absorption effect of the dilute sulfuric acid solution, an acid liquid supplemental spray header is arranged above the circulating spray header in the second ammonia tail gas absorption tower 21. An overflow port 28 is connected to the reservoir of the first ammonia tail gas absorbing tower 21 for discharging the absorbing solution in the first ammonia tail gas absorbing tower 21. A fifth PH detector 24 is additionally arranged at the overflow port 28, and the fifth PH detector 24 is connected with and controls the acid adding pump 22 so as to regulate and control the acid adding pump 22 according to the pH value of the primary deamination absorption liquid in the liquid storage tank of the first ammonia tail gas absorption tower 21, and further regulate and control the acid adding amount of the supplementary spray in the second ammonia tail gas absorption tower 21.
A liquid collecting tank 44 is connected to the downstream of the overflow port 28 of the first ammonia tail gas absorbing tower 21, a delivery pump 46 is connected to the outlet of the liquid collecting tank 44, a container with a hollow interior is used for collecting the absorbing solution discharged from the first ammonia tail gas absorbing tower 21 in the liquid collecting tank 44, and a centrifugal pump is used for the delivery pump 46. The outlet of the centrifugal pump 46 is connected in series with a heat exchanger 45, an evaporation concentrator 47, a crystallizer 48 and a centrifuge 49 in order, as shown in fig. 4, the heat exchanger 45 can be used for reutilizing the steam discharged from the evaporation concentrator 47, so as to make full use of the steam to avoid waste of the steam by emptying, however, the heat exchanger 45 can also be removed in the embodiment. The evaporator-concentrator 47 is an existing double-effect evaporator-concentrator or triple-effect evaporator-concentrator, the crystallizer is an existing cooling crystallizer for cooling crystallization, and the centrifuge is an existing industrial centrifuge. Wherein the centrate discharged by the centrifuge 49 may be transferred to the sump 44 for further processing.
In this embodiment, in order to facilitate the treatment of the wastewater, a homogenizing tank 25 is further connected in series upstream of the first pipeline mixer 1, so that the wastewater generated in the oil refining hydrogenation process is input into the homogenizing tank 25, and the quality of the wastewater is stable, and the homogenizing tank adopts the existing structure. Fig. 5 in this embodiment shows the structure of the desulfurization stripping tower 4, and the structures of the first deamination stripping tower 12 and the second deamination stripping tower 14 are substantially the same as the structure of the desulfurization stripping tower 4, and will not be described in detail herein. As shown in fig. 5, the desulfurization stripping tower 4 comprises a tower body 30, a blower 36 is connected to the bottom of the tower body 30, a liquid outlet 34 is formed, an air outlet 35 is formed in the top of the tower body 30, a filler 33 is arranged in the tower body 30, a stripping tower spray head 32 is arranged above the filler 33, the stripping tower spray head 32 is connected with a liquid inlet 31 formed in the top of the tower body 30, and the liquid inlet 31 is communicated with the liquid outlet of the homogenizing tank 25 through a lifting pump.
Fig. 6 in this embodiment shows the structure of the second sulfur tail gas absorbing tower 7, which includes a tower body 37, a liquid storage tank 40 is arranged at the bottom in the tower body 37, an air inlet 39 is arranged above the liquid storage tank 40, a filler 38 is arranged above the air inlet 39, a circulation spray header 41 and an alkali liquor supplementing spray header 42 are arranged above the filler 38, the alkali liquor supplementing spray header 42 is higher than the circulation spray header 41, the circulation spray header 41 is connected to the liquid storage tank 40 through a circulation pump, the alkali liquor supplementing spray header 42 is connected to the first alkali liquor tank 9, and an air outlet 43 is further arranged at the top of the tower body 37. In this embodiment, the structure of the second ammonia tail gas absorbing tower 21 is substantially the same as that of the second sulfur tail gas absorbing tower 7, and the structures of the first sulfur tail gas absorbing tower 6 and the first ammonia tail gas absorbing tower 20 are also substantially the same as that of the second sulfur tail gas absorbing tower 7 except that the alkali liquor supplementing spray header and the acid liquor supplementing spray header are not provided.
Example 1
Desulfurization and deamination treatment of the wastewater produced by the oil refining hydrogenation process is performed in the treatment device, and the wastewater produced by the oil refining hydrogenation process (the pollutant content is S 2- ：9837mg/L；NH 3 -N:15329 mg/L) was input into a homogenization tank, followed by the following treatments:
a. desulfurizing and sulfur recovery treatment:
a1, desulfurization treatment: the pH value of the wastewater output from the homogenizing tank is regulated by adding dilute sulfuric acid solution I (the mass content is 30% -50%) into a first pipeline mixer, the wastewater is uniformly mixed and then is input into a desulfurization blowing tower for spraying, the sprayed wastewater reversely contacts with air blown out from a blower in the tower for air blowing desulfurization treatment, and the wastewater after desulfurization is conveyed to a deamination treatment mechanism from a liquid outlet of the desulfurization blowing tower for deamination treatment; controlling an acid adding metering pump according to the numerical value detected by the first PH detector in the treatment process to control the adding amount of dilute sulfuric acid, and further controlling the pH value of the desulfurized wastewater (namely the numerical value detected by the first PH detector) to be maintained at 0.8-1.2;
a2, sulfur recovery treatment: the gas escaping from the gas outlet of the desulfurization stripping tower is input into a sulfur recovery unit for two-stage desulfurization absorption treatment, the gas firstly enters a first sulfur tail gas absorption tower and is subjected to the first-stage desulfurization absorption treatment by a circulating sprayed first-stage desulfurization absorption liquid, then enters a second sulfur tail gas absorption tower and is subjected to the second-stage desulfurization absorption treatment by a circulating sprayed second-stage desulfurization absorption liquid and a complementarily sprayed NaOH solution I (the mass content is 21+/-1 percent), and the gas escaping from the gas outlet of the second sulfur tail gas absorption tower (GB 14554-93) can be directly discharged to the atmosphere; the treatment process controls the spraying amount of the alkaline solution in the second sulfur tail gas absorption tower to spray the NaOH solution I according to the pH value of the first sulfur tail gas absorption liquid detected by the second PH detector, controls the pH value of the first sulfur tail gas absorption liquid to be 10.7-11.3, and recovers the first sulfur tail gas absorption liquid through an overflow port of the first sulfur tail gas absorption tower, wherein the recovered first sulfur tail gas absorption liquid is hydrogen sulfide solution, can meet the standard requirement of liquid L-3 in the table 1 of GB23937-2009 industrial sodium hydrosulfide, and can be used for sales; the secondary desulfurization absorption liquid is a mixed solution which is mainly composed of sodium sulfide and sodium hydroxide and is obtained by performing sulfur absorption by NaOH solution I in a second sulfur tail gas absorption tower and then performing recirculation spraying, and the primary desulfurization absorption liquid is a mixed solution which is mainly composed of sodium hydrosulfide and is obtained by performing sulfur absorption by the secondary desulfurization absorption liquid in a first sulfur tail gas absorption tower and then performing recirculation spraying;
b. deamination and ammonia recovery treatment steps:
b1, deamination treatment: aiming at the characteristic of ammonia nitrogen content in wastewater, the wastewater output from a liquid outlet of a desulfurization stripping tower can be subjected to two-stage air stripping and deamination treatment to completely remove ammonia nitrogen pollution, the wastewater is firstly subjected to pH value adjustment by adding NaOH solution II (the mass content is 20% -30%) in a second pipeline mixer, the wastewater is uniformly mixed and then is input into a first ammonia stripping and deamination tower for spraying, the sprayed wastewater is reversely contacted with air blown from a blower in the tower to be subjected to first-stage air stripping and deamination treatment, then is conveyed to a third pipeline mixer from the liquid outlet of the first ammonia stripping and deamination tower to be subjected to pH value adjustment by adding NaOH solution II, the wastewater is input into the second ammonia stripping and deamination tower for spraying after being uniformly mixed, the sprayed wastewater is reversely contacted with air blown from the blower in the tower to be subjected to second-stage air stripping and deamination treatment, and the wastewater reaches the second-stage discharge standard in a table 4 of GB8978-1996 comprehensive wastewater discharge standard for finishing treatment, and can be discharged to municipal wastewater pipe networks; the treatment process controls the first alkali adding metering pump according to the numerical value detected by the third PH detector to control the adding amount of the NaOH solution II in the second pipeline mixer, controls the second alkali adding metering pump according to the numerical value detected by the fourth PH detector to control the adding amount of the NaOH solution II in the third pipeline mixer, and further controls the pH value of the wastewater after deamination (namely the numerical values detected by the third PH detector and the fourth PH detector) to be maintained at 10.5-11.5;
b2, ammonia recovery treatment: the gas escaping from the gas outlet of the first deamination blowing tower and the gas outlet of the second deamination blowing tower is jointly input into an ammonia recovery unit for two-stage deamination absorption treatment, the gas firstly enters the first ammonia tail gas absorption tower and is subjected to the first-stage deamination absorption treatment by the circulating sprayed first-stage deamination absorption liquid, then enters the second ammonia tail gas absorption tower and is subjected to the second-stage deamination absorption treatment by the circulating sprayed second-stage deamination absorption liquid and the supplemented sprayed dilute sulfuric acid solution II (the mass content is 30 percent), and the gas escaping from the gas outlet of the second ammonia tail gas absorption tower reaches the malodorous pollutant emission standard (GB 14554-93) and can be directly discharged into the atmosphere; the treatment process comprises the steps of controlling the spraying quantity of an acid liquid in a second ammonia tail gas absorption tower to be supplemented with a spraying head to spray a dilute sulfuric acid solution II according to the pH value of the first ammonia tail gas absorption liquid detected by a fifth pH detector, controlling the pH value of the first ammonia tail gas absorption liquid to be 4.5-6.5, recycling the first ammonia tail gas absorption liquid through an overflow port of the first ammonia tail gas absorption tower, wherein the recycled first ammonia tail gas absorption liquid is a nearly saturated solution of ammonium sulfate, the mass content of the ammonium sulfate is 40%, the problem of crystal precipitation in the absorption tower is avoided, further treating the recycled first ammonia tail gas absorption liquid, carrying out evaporation concentration on the first ammonia tail gas absorption liquid collected in a liquid collecting tank through a concentration evaporation crystallizer, then carrying out cooling crystallization in a cooling crystallizer, and finally carrying out centrifugal dehydration on the first ammonia tail gas absorption liquid to obtain solid ammonium sulfate which can meet the standards of ammonium sulfate sales products, recycling ammonia from a centrifugal machine to a liquid collecting tank, concentrating and crystallizing again, and recycling ammonia; the secondary deamination absorption liquid is a mixed solution which is mainly composed of sulfuric acid and ammonium bisulfate and is obtained by ammonia absorption of dilute sulfuric acid solution II in a second ammonia tail gas absorption tower and then recycling spraying, and the primary deamination absorption liquid is a mixed solution which is mainly composed of ammonium sulfate and is obtained by ammonia absorption of the secondary deamination absorption liquid in a first ammonia tail gas absorption tower and then recycling spraying.
In the treatment method, in the step a1, the gas-liquid ratio of the air in the desulfurization stripping tower to the wastewater is (3000-5000) 1 (m 3 /m 3 ) The air flow rate of the air tower is 1.0-2.0m/s; in the step a2, the gas-liquid ratio (i.e. the ratio of the gas which escapes after the desulfurization treatment step to the primary desulfurization absorption liquid) in the first sulfur tail gas absorption tower is (30-100) 1 (m 3 /m 3 ) The gas-liquid ratio (i.e. the ratio of the gas which escapes after the first-stage desulfurization absorption treatment step and the second-stage desulfurization absorption liquid) in the second sulfur tail gas absorption tower is (30-100) 1 (m 3 /m 3 ) The method comprises the steps of carrying out a first treatment on the surface of the In the step b1, the air-to-liquid ratio of the air in the first deamination blowing tower and the air in the second deamination blowing tower (i.e. the ratio of the air to the desulfurized wastewater) is (3000-5000) 1 (m 3 /m 3 ) The air flow rate of the air tower is 1.0-2.0m/s; in the step b2, the gas-liquid ratio of the first ammonia tail gas absorption tower (i.e. the ratio of the gas which escapes after the deamination treatment step to the primary deamination absorption liquid) is (30-100): 1 (m 3 /m 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The gas-liquid ratio of the second ammonia tail gas absorption tower (i.e. the ratio of the gas which escapes after the first-stage deamination absorption treatment step to the second-stage deamination absorption liquid) is (30-100) 1 (m 3 /m 3 )。
After detection, the COD of the treated wastewater<120，NH 3 -N<25mg/L sulfide<1mg/L. Meets the secondary discharge standard of Table 4 of GB8978-1996 comprehensive discharge Standard for Sewage
Contaminant content H in gas 2 S<1mg/m 3 Ammonia, ammonia<100mg/m 3 Meets the emission standard of malodorous pollutants (GB 14554-93).
Example 2
This example relates to the effect of different control conditions on wastewater and gas treatment results in the treatment process of example 1.
Example 2.1
The same treatment apparatus and the same treatment method as in example 1 were used, and the influence of the pH control conditions on the wastewater and gas treatment results was examined under the same other operating conditions, and the experiment was conducted as shown in the following table:
the results of the above experiments are shown in the following table:
as can be seen from the table, in the desulfurization and deamination treatment method for wastewater generated by the oil refining hydrogenation process, the pH value control of five links is important for the desulfurization and deamination treatment, and the optimal control conditions for the wastewater are as follows: the pH of the desulfurization wastewater is controlled to be 0.8-1.2, the pH of the overflow liquid of the first sulfur tail gas absorption tower (i.e. the recovered primary desulfurization absorption liquid) is controlled to be 10.7-11.3, the pH of the deamination wastewater is controlled to be 10.5-11.5, the pH control range of the overflow liquid of the first ammonia tail gas absorption tower (i.e. the recovered primary deamination absorption liquid) is 4.5-6.5, the sulfur pollution and ammonia nitrogen pollution in the wastewater can be thoroughly treated, the secondary emission standard and the malodorous pollutant emission standard (GB 14554-93) in the table 4 of GB8978-1996 integrated wastewater emission standard are achieved, and the removed sulfur and ammonia nitrogen are converted into reusable chemical products, so that the efficient recovery is realized.
Example 2.2
The same treatment apparatus and the same treatment method as in example 1 were used to examine the effect of control conditions such as air flow rate and gas-liquid ratio on the results of wastewater and gas treatment under the same other operating conditions, and the experiments were conducted as shown in the following table:
the results of the above experiments are shown in the following table:
as can be seen from the table, in the desulfurization and deamination treatment method for wastewater generated by the oil refining hydrogenation process, conditions such as air flow rate and gas-liquid ratio can influence the desulfurization and deamination treatment result for wastewater.
Example 3
This example relates to the effect on the outcome of the sequence of treatments for desulphurisation and deamination in the treatment process of the present invention.
The wastewater from the refinery hydrogenation process was first deaminated, i.e., the wastewater was first deaminated and ammonia recovered as described in example 1, with the results shown in the following table:
as can be seen from the table, when the wastewater generated in the oil refining hydrogenation process is deaminated, because sodium bisulfide is alkaline, hydrogen sulfide is easier to blow off, so that the content of hydrogen sulfide in the deaminated gas exceeds the standard, and the hydrogen sulfide is removed for discharging. In addition, the pH value of the desulfurized wastewater can be raised and then alkali is regulated, so that the treatment cost is saved.

Claims (2)

1. A desulfurization and deamination treatment method of wastewater generated by an oil refining hydrogenation process is characterized by comprising the following steps:
a. desulfurizing and sulfur recovery treatment:
a1, desulfurization treatment: adding dilute sulfuric acid solution I into the wastewater generated in the oil refining hydrogenation process, regulating the pH value, spraying, reversely contacting with air to perform air stripping desulfurization treatment, and conveying the desulfurized wastewater to a deamination treatment step; the pH value of the desulfurized wastewater is controlled to be 0.8-1.2; h in the dilute sulfuric acid solution I 2 SO 4 The mass content of (1)The amount is 30% -50%;
in the step a1, in the air stripping desulfurization treatment process, the gas-liquid ratio of air to wastewater is (3000-5000) 1, and the air tower flow rate of air is (1.0-2.0) m/s;
a2, sulfur recovery treatment: the gas escaping from the desulfurization treatment step is discharged after two-stage desulfurization absorption treatment, wherein the two-stage desulfurization absorption treatment comprises a first-stage desulfurization absorption treatment step of circularly spraying a first-stage desulfurization absorption liquid on the gas escaping from the desulfurization treatment step, and a second-stage desulfurization absorption treatment step of circularly spraying a second-stage desulfurization absorption liquid and a supplemental spraying NaOH solution I on the gas escaping from the first-stage desulfurization absorption treatment step;
the removed sulfur pollutants enter a sulfur recovery treatment process along with air in the form of hydrogen sulfide, and the sulfur pollutants are subjected to primary circulating spray absorption on most of hydrogen sulfide through primary desulfurization absorption liquid in sequence to form concentrated liquid circulation mainly comprising sodium sulfide, and then subjected to secondary circulating spray absorption on the rest small amount of hydrogen sulfide through secondary desulfurization absorption liquid and supplemental NaOH solution I to form lean liquid circulation mainly comprising sodium sulfide; the NaOH solution I is required to be supplemented in a spraying mode, and the supplementing spraying quantity of the NaOH solution I is regulated and controlled by controlling the pH value of the primary desulfurization absorption liquid;
controlling the pH value of the primary desulfurization absorption liquid to be 10.7-11.3, and recycling the primary desulfurization absorption liquid; the mass content of NaOH in the NaOH solution I is 20% -22%, the second-stage desulfurization absorption liquid is a mixed solution obtained by performing sulfur absorption by the NaOH solution I in the second-stage desulfurization absorption treatment step and then performing recirculation spraying, and the first-stage desulfurization absorption liquid is a mixed solution obtained by performing sulfur absorption by the second-stage desulfurization absorption liquid in the first-stage desulfurization absorption treatment step and then performing recirculation spraying;
in the step a2, in the first-stage desulfurization absorption treatment step, the gas-liquid ratio of the gas to the first-stage desulfurization absorption liquid is (30-100): 1; the second-stage desulfurization absorption treatment step is that the gas-liquid ratio of the gas to the second-stage desulfurization absorption liquid is (30-100) 1; the recycled primary desulfurization absorption liquid reaches the standard that the mass content of sodium hydrosulfide meets 28%;
b. deamination and ammonia recovery treatment steps:
b1, deamination treatment: adding NaOH solution II into the desulfurized wastewater, regulating the pH value, spraying, reversely contacting with air to perform air stripping deamination treatment, and discharging the deaminated wastewater; the pH value of the deaminated wastewater is controlled to be 10.5-11.5; the mass content of NaOH in the NaOH solution II is 20-30%;
in the step b1, the air stripping and deamination treatment is two-stage air stripping and deamination treatment, wherein in each stage of air stripping and deamination treatment process, the air-liquid ratio of air to wastewater is (3000-5000): 1, and the air tower flow rates of the air are (1.0-2.0) m/s;
b2, ammonia recovery treatment: the gas escaping from the deamination treatment step is discharged after two-stage deamination absorption treatment, wherein the two-stage deamination absorption treatment comprises a first-stage deamination absorption treatment step of circularly spraying a first-stage deamination absorption liquid on the gas escaping from the deamination treatment step, and a second-stage deamination absorption treatment step of circularly spraying a second-stage deamination absorption liquid and a diluted sulfuric acid solution II which is sprayed in a complementary manner on the gas escaping from the first-stage deamination absorption treatment step;
the removed ammonia nitrogen pollutants enter an ammonia recovery treatment process along with air in the form of ammonia gas, and the ammonia gas is subjected to primary circulating spray absorption on most ammonia gas sequentially through primary deamination absorption liquid to form circulating absorption liquid mainly containing ammonium sulfate, and then the residual ammonia gas is subjected to secondary circulating spray absorption on the rest small amount of ammonia gas through secondary deamination absorption liquid and supplemented dilute sulfuric acid solution II to form circulating absorption liquid mainly containing ammonium bisulfate; and the pH value of the primary deamination absorption liquid is controlled to regulate and control the supplementary spraying amount of the dilute sulfuric acid solution II,
controlling the pH value of the primary deamination absorption liquid to be 4.5-6.5, and recovering the primary deamination absorption liquid; h in the dilute sulfuric acid solution II 2 SO 4 The mass content of the ammonia absorption liquid is 30%, the secondary deamination absorption liquid is a mixed solution obtained by ammonia absorption by recycling spraying after ammonia absorption is carried out on the dilute sulfuric acid solution II in the secondary deamination absorption treatment step, and the ammonia absorption liquid is prepared byThe primary deamination absorption liquid is a mixed solution obtained by recycling and spraying ammonia absorption after ammonia absorption is carried out on the secondary deamination absorption liquid in the primary deamination absorption treatment step;
in the step b2, in the first-stage deamination absorption treatment process, the gas-liquid ratio of the gas to the first-stage deamination absorption liquid is (30-100): 1; in the second-stage deamination absorption treatment process, the gas-liquid ratio of the gas to the second-stage deamination absorption liquid is (30-100): 1; the recovered first-stage deamination absorption liquid reaches the concentration of ammonium sulfate of 40 percent, and meets the standard of directly preparing solid ammonium sulfide.
2. The desulfurization and deamination treatment method of wastewater generated in a refinery hydrogenation process according to claim 1, wherein: and b2, sequentially carrying out evaporation concentration, cooling crystallization and centrifugal dehydration on the recovered primary deamination absorption liquid to obtain a solid ammonium sulfide product.
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