CN106927606B - Method for treating sulfide in alkaline residue sewage - Google Patents

Method for treating sulfide in alkaline residue sewage Download PDF

Info

Publication number
CN106927606B
CN106927606B CN201511029166.7A CN201511029166A CN106927606B CN 106927606 B CN106927606 B CN 106927606B CN 201511029166 A CN201511029166 A CN 201511029166A CN 106927606 B CN106927606 B CN 106927606B
Authority
CN
China
Prior art keywords
alkaline residue
sewage
sulfide
treatment
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201511029166.7A
Other languages
Chinese (zh)
Other versions
CN106927606A (en
Inventor
李刘柱
黄太彪
高嵩
李本高
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201511029166.7A priority Critical patent/CN106927606B/en
Publication of CN106927606A publication Critical patent/CN106927606A/en
Application granted granted Critical
Publication of CN106927606B publication Critical patent/CN106927606B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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

Abstract

The invention relates to the field of sewage treatment, and discloses a method for treating sulfide in alkaline residue sewage, which comprises the following steps: (1) performing electric flocculation treatment on the alkaline residue sewage, and then performing solid-liquid separation; (2) and (2) carrying out electrocatalytic oxidation on the liquid phase obtained by the solid-liquid separation in the step (1) in the presence of a catalyst and an oxidant. The method for treating the sulfide in the alkaline residue sewage has simple equipment, and saves fixed investment and occupied area; the utilization rate of the catalyst is greatly improved; the treatment effect on sulfides in the alkaline residue sewage is good, and the biodegradability of the alkaline residue sewage can be greatly improved; the utilization rate of the oxidant is high, and the treatment cost is low; the method is environment-friendly, simple and easy to control, and good in repeatability; no special production equipment requirement is required, and industrialization is facilitated; the method can treat the alkaline residue sewage containing sulfides with different concentrations, and has good popularization and application prospects in the petrochemical industry.

Description

Method for treating sulfide in alkaline residue sewage
Technical Field
The invention relates to the field of sewage treatment, in particular to a method for treating sulfide in alkaline residue sewage.
Background
A large amount of alkaline residue sewage is generated in petrochemical processes such as petroleum refining, ethylene production and the like, and the main pollutants of the alkaline residue sewage have high sulfide content and high COD concentration. The sulfide not only seriously pollutes the surrounding environment, but also generates hydrogen sulfide when the pH value of water is reduced, and the hydrogen sulfide is easy to overflow from the water and endangers the health of people. In addition, the alkali residue sulfide can corrode metal equipment, and the subsequent process is seriously influenced.
At present, the high-temperature wet oxidation process is adopted in industry to treat the alkaline residue sulfide, the effect is good, but the energy consumption is high, the efficiency is low, high-temperature, high-pressure or expensive equipment is often needed, the treatment cost is high, and potential safety hazards exist. Patent CN103408097A discloses a method for removing sulfides in coking wastewater, but the types of sulfides in coking wastewater are greatly different from those in caustic sludge wastewater, and the technology also has the problems of difficult preparation of activated carbon-like materials, high temperature required for reaction, excessive use of oxidant, and the like. Patent CN103184068A discloses a hydrogen peroxide-hydrochloric acid oxidation desulfurization method, which uses hydrogen peroxide to oxidize sulfides in fuel oil into strongly polar sulfones or sulfoxides in an acidic medium, and then uses an extraction method to remove sulfides.
In recent years, in the field of sewage treatment, the application of the electric flocculation technology is more and more extensive, because the electric flocculation process comprises a plurality of reactions such as electrolytic reduction, electrolytic air flotation, adsorption flocculation and the like and the synergistic effect thereof, the waste water can be quickly and efficiently treated, the operation is simple, secondary pollution is not generated or is rarely generated, and the like, but the single electric flocculation technology has poor treatment effect on the alkaline residue sewage containing sulfides with the concentration of less than 20 weight percent of sulfide, and has large power consumption and high cost.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the method for treating the sulfide in the alkaline residue sewage, which can treat the alkaline residue sewage containing sulfides with different concentrations, and has the advantages of simple operation, low treatment cost, high oxidant utilization rate and good treatment effect.
The inventor of the invention discovers in research that the method can treat the alkaline residue sewage containing sulfides with different concentrations, has simple operation, low treatment cost and high oxidant utilization rate, and has good treatment effect on the sulfides in the alkaline residue sewage by performing the electric flocculation pretreatment on the alkaline residue sewage and then performing the electrocatalytic oxidation on the electric flocculation effluent in the presence of a catalyst and an oxidant.
Therefore, in order to achieve the above object, the present invention provides a method for treating sulfide in alkaline residue wastewater, the method comprising:
(1) performing electric flocculation treatment on the alkaline residue sewage, and then performing solid-liquid separation;
(2) and (2) carrying out electrocatalytic oxidation on the liquid phase obtained by the solid-liquid separation in the step (1) in the presence of a catalyst and an oxidant.
Preferably, in step (1), the conditions of the electroflocculation process include: the electrode plate is made of at least one of copper, iron and aluminum, has voltage of 15-36V and current density of 8-20mA/cm2The electrode spacing is 10-30mm, and the treatment time is 15-40 min.
Preferably, in the electric flocculation treatment, iron salt is added to the alkaline residue sewage.
Preferably, the adding amount of the iron salt is 20-200mg/L, and more preferably 50-150mg/L, relative to the caustic sludge sewage.
Preferably, the iron salt is at least one of ferrous sulfate, ferric trichloride, polymeric ferric sulfate and polymeric ferric chloride, more preferably, the iron salt is ferric trichloride, polymeric ferric sulfate and polymeric ferric chloride, and the weight ratio of ferric trichloride, polymeric ferric sulfate and polymeric ferric chloride is 1: 3-8: 3-10.
Preferably, in the step (2), the amount of the catalyst is 100-5000mg/L, and more preferably 500-2000mg/L, relative to the caustic sludge wastewater.
Preferably, the catalyst is at least one of manganese dioxide, titanium silicalite, titanium dioxide and copper oxide, more preferably a titanium silicalite, and even more preferably a hollow titanium silicalite HTS.
Preferably, in the step (2), the amount of the oxidant is 0.04-0.18mg/L, and more preferably 0.08-0.12mg/L, relative to the caustic sludge sewage.
Preferably, the oxidant is at least one of ozone, hydrogen peroxide, molecular oxygen and sodium hypochlorite.
Preferably, in step (2), the conditions of the electrocatalytic oxidation include: the electrode is DSA electrode with voltage of 20-40V and current density of 10-25mA/cm2The electrode spacing is 5-20mm, and the treatment time is 5-20 min.
According to the method for treating sulfide in alkaline residue sewage, the electrocatalytic oxidation and the catalytic oxidation of the oxidant are simultaneously carried out in the same reactor, the equipment is simple, the fixed investment and the occupied area are saved, and the utilization rate of the catalyst is greatly improved by sharing the catalyst; firstly, the electrocoagulation precipitation is carried out, and then the electrocatalytic oxidation and the oxidant catalytic oxidation have synergistic effect, so that the treatment effect on sulfides in the alkaline residue sewage is good, the biodegradability of the alkaline residue sewage can be greatly improved, the consumption of the oxidant is small, the utilization rate of the oxidant is high, and the treatment cost is low; the method is environment-friendly, simple and easy to control, and good in repeatability; the method has no special production equipment requirement, and is beneficial to industrialization; the method can treat the alkaline residue sewage containing sulfides with different concentrations, and has good popularization and application prospects in the petrochemical industry.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for treating sulfide in alkaline residue sewage, which comprises the following steps:
(1) performing electric flocculation treatment on the alkaline residue sewage, and then performing solid-liquid separation;
(2) and (2) carrying out electrocatalytic oxidation on the liquid phase obtained by the solid-liquid separation in the step (1) in the presence of a catalyst and an oxidant.
In step (1) of the method of the present invention, the conditions for the electrocoagulation treatment preferably include: the electrode plate is made of at least one of copper, iron and aluminum, has voltage of 15-36V and current density of 8-20mA/cm2The electrode spacing is 10-30mm, and the treatment time is 15-40 min.
In the present invention, in the electrocoagulation treatment, it is preferable to add an iron salt to the alkaline residue wastewater, and in this preferable case, the flocculation effect can be further improved, and the removal rate of sulfides in the wastewater can be further improved. The adding amount of the iron salt is preferably 20-200mg/L, and more preferably 50-150mg/L relative to the alkaline residue sewage. It will be appreciated by those skilled in the art that in order for the iron salt to better promote flocculation, the iron salt may be added at the beginning of the electroflocculation.
In the present invention, the iron salt may be an iron salt commonly used in the art, for example, the iron salt may be at least one of ferrous sulfate, ferric chloride, polymeric ferric sulfate and polymeric ferric chloride. However, the inventor of the present invention has unexpectedly found in research that when the ferric salt is ferric trichloride, polyferric sulfate and polyferric chloride, that is, when the ferric trichloride, the polyferric sulfate and the polyferric chloride are used in combination, the flocculation effect can be greatly improved, and the removal rate of sulfides in sewage can be greatly improved, therefore, the ferric salt is preferably ferric trichloride, polyferric sulfate and polyferric chloride, and the weight ratio of ferric trichloride, polyferric sulfate and polyferric chloride is preferably 1: 3-8: 3-10.
In the present invention, polymeric ferric sulfate and polymeric ferric chloride are not particularly required, and polymeric ferric sulfate and polymeric ferric chloride which are commonly used in the art can be used. For the polyferric sulfate and the polyferric chloride, they are commercially available.
As will be understood by those skilled in the art, when the alkaline residue sewage is subjected to the electric flocculation treatment, part of the sulfides in the sewage will flocculate to form precipitates, and therefore, the solid-liquid separation is performed, that is, part of the sulfides is removed from the sewage. There is no special requirement for solid-liquid separation, and various methods commonly used in the art can be adopted, as long as the solid phase and the liquid phase are separated, which is well known to those skilled in the art and will not be described herein.
In the step (2) of the invention, in the presence of a catalyst and an oxidant, the liquid phase obtained by the solid-liquid separation in the step (1) is subjected to electrocatalytic oxidation, namely the electrocatalytic oxidation and the oxidant catalytic oxidation share the same catalyst and are carried out together.
In the step (2) of the invention, the amount of the catalyst is preferably 100-5000mg/L, and more preferably 500-2000mg/L, relative to the alkali residue wastewater.
In the step (2) of the present invention, there is no particular requirement for the catalyst, as long as it can be used as both a catalyst for electrocatalytic oxidation and a catalyst for catalytic oxidation with an oxidant, and for example, the catalyst can be at least one of manganese dioxide, titanium silicalite, titanium dioxide and copper oxide. However, the inventors of the present invention have found in their research that when the catalyst is a titanium silicalite, more preferably a hollow titanium silicalite HTS, the removal rate of sulfides in the caustic sludge wastewater can be greatly improved, and therefore, the catalyst is preferably a titanium silicalite, more preferably a hollow titanium silicalite HTS.
The method can greatly reduce the dosage of the oxidant and improve the utilization rate of the oxidant, and in the step (2), the dosage of the oxidant is preferably 0.04-0.18mg/L, more preferably 0.08-0.12mg/L relative to the caustic sludge sewage.
In the present invention, the oxidizing agent is not particularly limited, and various oxidizing agents commonly used in the art may be used, and for example, the oxidizing agent may be at least one of ozone, hydrogen peroxide, molecular oxygen, and sodium hypochlorite. When ozone is used as the oxidizing agent, in order to make the ozone contact with the sulfide in the alkaline residue sewage better, the contact can be carried out by ozone aeration at the bottom of the reactor. It will be appreciated by those skilled in the art that hydrogen peroxide may be employed as an aqueous solution thereof, i.e., hydrogen peroxide. The concentration of hydrogen peroxide is not particularly limited, and a conventional concentration may be used, for example, 20 to 80 wt% hydrogen peroxide, such as 30 wt%, 50 wt%, or 70 wt% hydrogen peroxide commercially available.
In step (2) of the present invention, the conditions for the electrocatalytic oxidation preferably include: the electrode is DSA electrode with voltage of 20-40V and current density of 10-25mA/cm2The electrode spacing is 5-20mm, and the treatment time is 5-20 min.
In the present invention, the dsa (dimensional Stable anode) electrode is a size-Stable and shape-Stable electrode. The DSA electrode has a catalytic effect and can be used for carrying out electrocatalytic oxidation on sulfides in the alkaline residue sewage. DSA electrodes are commercially available.
In the present invention, since the reaction conditions are mild and high temperature and high pressure are not required, there is no special requirement for the reaction equipment, for example, the step (1) of electrocoagulation can be performed in a conventional electrocoagulation reactor, and the step (2) of electrocatalytic oxidation and catalytic oxidation of an oxidant can be performed in various reactors as will occur to those skilled in the art, for example, fixed bed reactors, suspension bed reactors and other equipment, the catalyst is filled in the bed layer of the reactor, and the caustic sludge wastewater flows into the catalyst bed layer from the lower end of the fixed bed or suspension bed reactor to perform electrocatalytic oxidation and catalytic oxidation of the oxidant.
In the invention, because the titanium silicalite molecular sieve catalyst has long service life and can be recycled, 2g of the titanium silicalite molecular sieve catalyst is filled in the fixed bed reactor, the alkali residue sewage is treated according to the method of the invention, and the treated alkali residue sewage reaching the standard can reach 150L after the catalyst is completely inactivated, so that the treatment cost can be further reduced, and when the titanium silicalite molecular sieve catalyst is inactivated, the titanium silicalite molecular sieve catalyst can be regenerated and can be recycled after regeneration. No special requirement is imposed on the regeneration method of the titanium silicalite molecular sieve, and the regeneration can be carried out by adopting the conventional method in the field, for example, the titanium silicalite molecular sieve can be calcined at the temperature of 400 ℃ and 600 ℃ for 2-4 h.
In the present invention, the caustic sludge wastewater refers to the conventional caustic sludge wastewater in the petrochemical field, for example, caustic sludge wastewater generated in petrochemical processes such as petroleum refining and ethylene production. The sulfide in the alkaline residue sewage is reductive sulfide, and generally comprises sodium sulfide, sodium methyl mercaptide, sodium ethyl mercaptide, sodium thiophenolate, ethyl sulfide and the like.
Examples
The following examples further illustrate the invention but are not intended to limit the invention thereto.
In the following examples and comparative examples:
hollow titanium silicalite HTS: purchased from the institute of petrochemical science.
DSA electrode: purchased from Baoji Zhiming Special metals, Inc.
And (3) measuring the sulfide content in the sewage: iodometry (HJ/T60-2000).
Determination of COD: dichromate method (GB 11914-89).
Sulfide removal rate (sulfide content in sewage before treatment-sulfide content in sewage after treatment)/sulfide content in sewage before treatment x 100%
COD removal rate (COD of the sewage before treatment-COD of the sewage after treatment)/COD of the sewage before treatment x 100%
Example 1
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
(1) Performing electric flocculation treatment on the alkaline residue sewage (the sulfide content is 28.5 wt%, and the COD is 359000mg/L), wherein the electrode plate is a copper electrode plate, the voltage is 20V, and the current density is 15mA/cm2The electrode spacing is 20mm, the treatment time is 30min, ferric salt is added into the alkaline residue sewage at the beginning of the electric flocculation, the adding amount of the ferric salt is 100mg/L relative to the alkaline residue sewage, the ferric salt is ferric chloride, polymeric ferric sulfate (purchased from Shandong Sanfeng group Co., Ltd.) and polymeric ferric chloride (purchased from Shandong Wan Jie environmental protection science and technology Co., Ltd.), and the weight ratio of the ferric chloride, the polymeric ferric sulfate and the polymeric ferric chloride is 1: 4: 5. and carrying out solid-liquid separation after treatment.
(2) Carrying out electrocatalytic oxidation on a liquid phase obtained by the solid-liquid separation in the step (1) in the presence of a hollow titanium silicalite HTS and an ozone-containing gas (30 volume percent, and the balance of air), wherein the dosage of the hollow titanium silicalite HTS is 1000mg/L relative to the caustic sludge sewage, the dosage of the ozone-containing gas is 0.1mg/L relative to the caustic sludge sewage in terms of ozone, the electrode is a DSA electrode, the voltage is 30V, and the current density is 15mA/cm2The electrode spacing was 10mm, and the treatment time was 15 min. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 2
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
(1) Performing electric flocculation treatment on the alkaline residue sewage (the sulfide content is 16.9 wt%, and the COD is 250980mg/L), wherein the electrode plate is an iron electrode plate, the voltage is 15V, and the current density is 8mA/cm2The electrode spacing is 10mm, the treatment time is 40min, when the electrocoagulation is started, ferric salt is added into the alkaline residue sewage, the adding amount of the ferric salt is 50mg/L relative to the alkaline residue sewage, the ferric salt is ferric chloride, polymeric ferric sulfate (purchased from Beijing Runji environmental improvement and development Limited company) and polymeric ferric chloride (purchased from Yangxin Water purification materials factory, Guijing), and the weight ratio of the ferric chloride, the polymeric ferric sulfate and the polymeric ferric chloride is 1: 3: 10. after treatmentAnd carrying out solid-liquid separation.
(2) Carrying out electrocatalytic oxidation on a liquid phase obtained by solid-liquid separation in the step (1) in the presence of hollow titanium silicalite HTS and hydrogen peroxide (with the concentration of 50 weight percent), wherein the dosage of the hollow titanium silicalite HTS is 500mg/L relative to the alkaline residue sewage, the dosage of the hydrogen peroxide is 0.08mg/L relative to the alkaline residue sewage, the electrode is a DSA electrode, the voltage is 20V, and the current density is 10mA/cm2The electrode spacing was 5mm, and the treatment time was 20 min. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 3
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
(1) Performing electric flocculation treatment on the alkaline residue sewage (the sulfide content is 23.4 wt%, and the COD is 286020mg/L), wherein the electrode plate is an aluminum electrode plate, the voltage is 36V, and the current density is 20mA/cm2The electrode spacing is 30mm, the treatment time is 15min, ferric salt is added into the alkaline residue sewage at the beginning of the electric flocculation, the adding amount of the ferric salt is 150mg/L relative to the alkaline residue sewage, the ferric salt is ferric trichloride, polymeric ferric sulfate (purchased from Yueyang Tianhe environmental protection science and technology Co., Ltd.) and polymeric ferric chloride (purchased from Zhengzhou Hua Sheng chemical products Co., Ltd.), and the weight ratio of the ferric trichloride, the polymeric ferric sulfate and the polymeric ferric chloride is 1: 8: 3. and carrying out solid-liquid separation after treatment.
(2) Carrying out electrocatalytic oxidation on a liquid phase obtained by the solid-liquid separation in the step (1) in the presence of a hollow titanium silicalite HTS and an ozone-containing gas (40 volume percent, and the balance being air), wherein the dosage of the hollow titanium silicalite HTS is 2000mg/L relative to the caustic sludge sewage, the dosage of the ozone-containing gas is 0.12mg/L relative to the caustic sludge sewage in terms of ozone, the electrode is a DSA electrode, the voltage is 40V, and the current density is 25mA/cm2The electrode spacing was 20mm, and the treatment time was 5 min. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 4
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
The alkaline residue wastewater was treated by the method of example 2, except that, in the step (1), the weight ratio of ferric trichloride, polyferric sulfate and polyferric chloride was 1: 1: 1. after treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 5
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
The alkaline residue wastewater was treated by the method of example 2, except that, in the step (1), the weight ratio of ferric trichloride, polyferric sulfate and polyferric chloride was 1: 9: 11. after treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 6
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
The alkaline residue wastewater was treated in the same manner as in example 2, except that in the step (1), ferric salt was added as ferric trichloride. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 7
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
The alkaline residue wastewater was treated according to the method of example 2, except that, in the step (1), ferric salt was added as ferric trichloride and polyferric sulfate (available from Beijing environmental improvement and environmental protection, Inc., Ruiki, Inc.), and the weight ratio of ferric trichloride to polyferric sulfate was 1: 3. after treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 8
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
The alkaline residue wastewater was treated in the same manner as in example 2, except that in the step (1), no iron salt was added. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 9
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
The caustic sludge wastewater was treated by the method of example 1, except that in the step (2), the hollow titanium silicalite HTS was replaced with titanium silicalite TS-1. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Example 10
This example is for explaining the method of treating sulfide in alkaline residue wastewater according to the present invention.
The caustic sludge wastewater was treated by the method of example 1, except that in the step (2), the hollow titanium silicalite HTS was replaced with titanium dioxide. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Comparative example 1
The caustic sludge sewage was treated in the same manner as in example 1 except that no catalyst was used in the step (2). After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Comparative example 2
The caustic sludge wastewater was treated in the same manner as in example 1, except that no oxidizing agent was used in the step (2). After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Comparative example 3
The caustic sludge sewage was treated by the method of example 1, except that in the step (2), only the oxidizing agent catalytic oxidation was performed, and the electrocatalytic oxidation was not performed, that is, the step (2) was: and (2) carrying out catalytic oxidation on the liquid phase obtained by the solid-liquid separation in the step (1) in the presence of a hollow titanium silicalite HTS and ozone-containing gas (30 volume percent, and the balance of air), wherein the dosage of the hollow titanium silicalite HTS is 1000mg/L relative to the caustic sludge sewage, and the dosage of the ozone-containing gas is 0.1mg/L relative to the caustic sludge sewage in terms of ozone, and reacting for 15 min. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Comparative example 4
Carrying out catalytic oxidation on the caustic sludge sewage (the sulfide content is 28.5 wt%, and the COD is 359000mg/L) in the presence of hollow titanium silicalite HTS and ozone-containing gas (30 vol%, and the balance is air), wherein the dosage of the hollow titanium silicalite HTS is 1000mg/L relative to the caustic sludge sewage, and the dosage of the ozone-containing gas is 1mg/L relative to the caustic sludge sewage in terms of ozone, and reacting for 60 min. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Comparative example 5
The alkaline residue wastewater was treated in the same manner as in example 1, except that the step (1) was not conducted, and only the step (2) was conducted. Namely, the alkaline residue sewage (sulfide content of 28.5 wt%, COD of 359000mg/L) was subjected to electrocatalytic oxidation in the presence of a hollow titanium silicalite HTS and an ozone-containing gas (30 vol%, the remainder being air), the amount of the hollow titanium silicalite HTS used was 1000mg/L relative to the alkaline residue sewage, the amount of the ozone-containing gas used was 1mg/L in terms of ozone relative to the alkaline residue sewage, the electrode was a DSA electrode, voltage was 30V, and current density was 15mA/cm2The distance between the electrodes is 10mm,
the treatment time was 60 min. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
Comparative example 6
The alkaline residue wastewater was treated in the same manner as in example 8, except that only the step (1) was carried out and the step (2) was not carried out. Namely, the alkaline residue sewage (the sulfide content is 16.9 weight percent, the COD is 250980mg/L) is subjected to electric flocculation treatment, an electrode plate is an iron electrode plate, the voltage is 15V, and the current density is 8mA/cm2The electrode spacing was 10mm and the treatment time was 90 min. After treatment, the sulfide content and COD in the sewage were measured, and the sulfide removal rate and COD removal rate were calculated, and the results are shown in Table 1.
TABLE 1
Figure BDA0000897733410000121
Figure BDA0000897733410000131
Comparing the example 1 with the comparative examples 1-5, respectively, it can be seen that the method for treating sulfides in alkaline residue sewage of the present invention, which comprises the steps of performing electrocoagulation precipitation, then performing electrocatalytic oxidation and oxidant catalytic oxidation in a synergistic manner, can greatly improve the sulfide removal rate and the COD removal rate, and has the advantages of low oxidant consumption, high oxidant utilization rate, and good treatment effect. Comparing example 8 with comparative example 6, it can be seen that the treatment effect on the low sulfide content alkaline residue sewage is not good when the electrocoagulation is used alone, but the sulfide treatment method in the alkaline residue sewage of the invention is not only suitable for the high sulfide content alkaline residue sewage, but also has good treatment effect on the low sulfide content alkaline residue sewage, which shows that the method of the invention has good removal effect on the alkaline residue sewage containing sulfides with different concentrations.
Comparing the example 2 with the example 8, it can be seen that the addition of the iron salt to the alkaline residue sewage during the electrocoagulation treatment can further improve the sulfide removal rate and the COD removal rate, and further improve the sewage treatment effect; comparing the example 2 with the examples 6 to 7 respectively, it can be seen that the ferric salts added during the electrocoagulation are ferric trichloride, polymeric ferric sulfate and polymeric ferric chloride, which can further improve the removal rate of sulfide and COD, and further improve the sewage treatment effect; comparing example 2 with examples 4-5, respectively, it can be seen that the weight ratio of ferric trichloride, polyferric sulfate and polyferric chloride added when performing the electrocoagulation is 1: 3-8: 3-10 hours, the sulfide removal rate and the COD removal rate can be further improved, and the sewage treatment effect is further improved; comparing example 1 with examples 9-10, respectively, it can be seen that the catalyst is a titanium silicalite molecular sieve, more preferably a hollow titanium silicalite molecular sieve HTS, which can further improve the sulfide removal rate and the COD removal rate, and further improve the sewage treatment effect.
Test examples
The caustic sludge sewage is treated according to the method of the example 1, the hollow titanium silicalite HTS is reused for 5 times after the reaction, the total use time is 6 times, the treatment conditions are the same as the example 1, the sulfide content and COD in the sewage are measured after each treatment, and the sulfide removal rate and the COD removal rate are calculated, and the results are shown in the table 2. The hollow titanium silicon molecular sieve HTS is continuously used until the hollow titanium silicon molecular sieve HTS is inactivated (when the sulfide removal rate is lower than 87 percent, the hollow titanium silicon molecular sieve HTS is judged to be inactivated), then the hollow titanium silicon molecular sieve HTS is roasted in a temperature programming furnace at 500 ℃ for 3 hours for regeneration, then the hollow titanium silicon molecular sieve HTS is naturally cooled and participates in the reaction again under the same conditions as the example 1, the sulfide content and the COD in the sewage are measured after the reaction, and the sulfide removal rate and the COD removal rate are calculated, and the results are shown.
TABLE 2
Sulfide removal rate (%) COD removal Rate (%)
1 st time 98.3 92.4
2 nd time 97.4 91.3
3 rd time 96.3 90.4
4 th time 95.2 90.3
5 th time 94.5 88.6
6 th time 93.7 88.1
Is used after regeneration 97.9 92.1
The test examples show that the titanium silicalite molecular sieve catalyst can be recycled, has long service life and can be regenerated and recycled in the method for treating the sulfide in the alkaline residue sewage.
According to the method for treating sulfide in alkaline residue sewage, the electrocatalytic oxidation and the catalytic oxidation of the oxidant are simultaneously carried out in the same reactor, the equipment is simple, the fixed investment and the occupied area are saved, and the utilization rate of the catalyst is greatly improved by sharing the catalyst; firstly, the electrocoagulation precipitation is carried out, and then the electrocatalytic oxidation and the oxidant catalytic oxidation have synergistic effect, so that the treatment effect on sulfides in the alkaline residue sewage is good, the biodegradability of the alkaline residue sewage can be greatly improved, the consumption of the oxidant is small, the utilization rate of the oxidant is high, and the treatment cost is low; the method is environment-friendly, simple and easy to control, and good in repeatability; the method has no special production equipment requirement, and is beneficial to industrialization; the method can treat the alkaline residue sewage containing sulfides with different concentrations, and has good popularization and application prospects in the petrochemical industry.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A method for treating sulfide in alkaline residue sewage is characterized by comprising the following steps:
(1) performing electric flocculation treatment on the alkaline residue sewage, and then performing solid-liquid separation;
(2) carrying out electrocatalytic oxidation on a liquid phase obtained by the solid-liquid separation in the step (1) in the presence of a catalyst and an oxidant; the catalyst is a hollow titanium silicalite molecular sieve HTS;
wherein, during the electric flocculation treatment, ferric salt is added into the alkaline residue sewage; the adding amount of the ferric salt is 50-150mg/L relative to the alkaline residue sewage; the ferric salt is ferric trichloride, polyferric sulfate and polyferric chloride, and the weight ratio of the ferric trichloride to the polyferric sulfate to the polyferric chloride is 1: 3-8: 3-10;
the content of sulfide in the alkaline residue sewage is 16.9-28.5 wt%, and the COD is 250980-359000 mg/L.
2. The method of claim 1, wherein in step (1), the conditions of the electroflocculation process comprise: the electrode plate is made of at least one of copper, iron and aluminum, has voltage of 15-36V and current density of 8-20mA/cm2The electrode spacing is 10-30mm, and the treatment time is 15-40 min.
3. The method as claimed in claim 1, wherein in the step (2), the amount of the catalyst is 100-5000mg/L relative to the caustic sludge wastewater.
4. The method as claimed in claim 1, wherein in the step (2), the amount of the catalyst is 500-2000mg/L relative to the alkaline residue wastewater.
5. The method according to claim 1, wherein in the step (2), the amount of the oxidizing agent is 0.04-0.18mg/L relative to the caustic sludge wastewater.
6. The method according to claim 1, wherein in the step (2), the amount of the oxidizing agent is 0.08-0.12mg/L relative to the caustic sludge wastewater.
7. The method of any one of claims 1-6, wherein the oxidizing agent is at least one of ozone, hydrogen peroxide, molecular oxygen, sodium hypochlorite.
8. The method of claim 1, wherein in step (2), the conditions of the electrocatalytic oxidation comprise: the electrode is DSA electrode with voltage of 20-40V and current density of 10-25mA/cm2The electrode spacing is 5-20mm, and the treatment time is 5-20 min.
9. The method of claim 1, wherein the caustic sludge wastewater comprises caustic sludge wastewater produced in a petrochemical process.
10. The method of claim 9, wherein the sulfide in the caustic sludge wastewater is a reducing sulfide comprising at least one of sodium sulfide, sodium methyl mercaptide, sodium ethyl mercaptide, sodium thiophenolate, and ethyl sulfide.
CN201511029166.7A 2015-12-31 2015-12-31 Method for treating sulfide in alkaline residue sewage Active CN106927606B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201511029166.7A CN106927606B (en) 2015-12-31 2015-12-31 Method for treating sulfide in alkaline residue sewage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511029166.7A CN106927606B (en) 2015-12-31 2015-12-31 Method for treating sulfide in alkaline residue sewage

Publications (2)

Publication Number Publication Date
CN106927606A CN106927606A (en) 2017-07-07
CN106927606B true CN106927606B (en) 2020-10-27

Family

ID=59442226

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201511029166.7A Active CN106927606B (en) 2015-12-31 2015-12-31 Method for treating sulfide in alkaline residue sewage

Country Status (1)

Country Link
CN (1) CN106927606B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107601732B (en) * 2017-09-19 2021-01-26 中国石油天然气集团公司 Ternary combination flooding and polymer flooding oily sewage or fracturing flowback fluid treatment equipment and process
CN110092538A (en) * 2019-04-28 2019-08-06 上海大学 Refinery basic sewage waste water classification processing combined technical method
CN110563221A (en) * 2019-09-27 2019-12-13 北京帝力伟业科技开发有限公司 Treatment system and method for high-saline-alkali slag wastewater

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101434443B (en) * 2007-11-15 2011-07-20 中国石油化工股份有限公司 Method and apparatus for treating oil refining sewerage
CN101723533B (en) * 2009-12-10 2012-03-28 上海宝钢化工有限公司 Method for treating concentrated water produced by coking wastewater recycling process
CN101985379B (en) * 2010-08-02 2012-02-22 惠州Tcl环境科技有限公司 Treatment method for high-concentration sulfur-containing caustic sludge wastewater from oil refinery
CN103979646B (en) * 2014-06-04 2015-07-15 江苏科技大学 Continuous electric flocculation water treatment method for dosing along process
CN104671378B (en) * 2015-02-12 2016-08-17 凯天环保科技股份有限公司 A kind of electro-catalysis waste water processes special coagulant/conduction complex salt

Also Published As

Publication number Publication date
CN106927606A (en) 2017-07-07

Similar Documents

Publication Publication Date Title
US8273249B2 (en) Method integrating electrochemical oxidation and flocculation processes for pre-treatment of coking wastewater
CN101723485B (en) Method for processing reverse osmosis concentrated water
CN105461135B (en) A kind of organic petrochemical industry wastewater preprocessing process of high-concentration hardly-degradable
Asaithambi et al. Performance evaluation of hybrid electrocoagulation process parameters for the treatment of distillery industrial effluent
CN108529714B (en) Photoelectrochemical reaction tank and method for treating hydrogen sulfide waste gas and waste water by using same
CN106927606B (en) Method for treating sulfide in alkaline residue sewage
CN104787853A (en) Electrochemical method cooperated with active carbon for activating persulfate for treating organic wastewater
CN104556533B (en) Treatment method for reverse osmosis concentrated water
CN107298490B (en) Electrochemical reactor, method for removing chloride ions in wastewater through electric flocculation, precipitated product and application
KR101834438B1 (en) Apparatus and method for treating desulfurization waste water
US10710906B2 (en) Method for treatment of petrochemical spent caustic wastewater
CN111422954A (en) Advanced wastewater treatment method and system for realizing sludge source reduction
CN108409003B (en) Treatment method and system for salt-containing organic wastewater after PCB wastewater copper recovery
CN113582439A (en) Iron-carbon Fenton pretreatment method for acidic high-salt high-concentration organic wastewater
CN111087047A (en) Treatment method of bromine-containing organic wastewater
BR102015030975A2 (en) effluent treatment from biodiesel washing using electroflotation / electrooxidation and coupled fenton
CN217202372U (en) Coking wastewater advanced treatment equipment
Khoshbin et al. Removal of acid red 1 dye pollutant from contaminated waters by electrocoagulation method using a recirculating tubular reactor
CN210559900U (en) Chemical nickel waste water electrocatalytic oxidation treatment system
CN209815912U (en) Electrocatalytic oxidation treatment system for cyanide-containing wastewater
CN113371895A (en) Process method and system for resourceful treatment of oil and gas field produced water
CN105668915A (en) Treatment method for degradation-resistant petrochemical engineering wastewater
CN111087049A (en) Method for treating organic nitrogen wastewater
KR20130116244A (en) Method and device for anaerobically treating wastewater containing terephthalic acid
CN204490573U (en) A kind of dry coke quenching coking dense salt waste water after-treatment system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant