CN113816554A - Treatment method and treatment device for isooctyl thioglycolate production wastewater - Google Patents
Treatment method and treatment device for isooctyl thioglycolate production wastewater Download PDFInfo
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- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention belongs to the technical field of organic wastewater treatment, and particularly relates to a treatment method and a treatment device for isooctyl thioglycolate production wastewater. Filling a granular activated carbon-loaded Fe catalyst serving as an adsorbent into an adsorption tower in advance, allowing isooctyl thioglycolate production wastewater to flow through the adsorption tower, and fully adsorbing organic matters in the wastewater by the adsorbent to realize separation of the organic matters and salt in the wastewater; then desalting in an evaporation device, and condensing evaporated water to be recycled as reclaimed water; evaporating the mother liquor and filtering the mother liquor by a desalting filter to obtain solid salt which is sold as a byproduct. After the salt-containing organic wastewater is subjected to adsorption and desalination treatment, the removal rate of COD of distilled water is over 99 percent, and the TOC content in solid salt is very low. The treatment device provided by the invention has the advantages that the two adsorption towers A and B are alternately used, the adsorption tower A is heated after reaching adsorption saturation and is aerated for catalytic oxidation degradation, the wastewater enters the adsorption tower B for separation of organic matters and salts, and the device can continuously run.
Description
Technical Field
The invention belongs to the technical field of organic wastewater treatment, and particularly relates to a treatment method and a treatment device for isooctyl thioglycolate production wastewater.
Background
Currently, the sodium hydrosulfide process is the primary production method of isooctyl thioglycolate. The technology has the advantages of simple process, low cost and the like, but a large amount of high-salt high-concentration organic wastewater can be generated in the production process. The content of sodium chloride in the high-salt high-concentration organic wastewater reaches more than 20 wt%, and the high-salt high-concentration organic wastewater also contains organic matters such as thioglycolic acid, isooctyl alcohol, isooctyl thioglycolate and the like.
Chinese patent CN101318750A discloses a method for treating waste water produced by isooctyl thioglycolate. In the patent, part of organic matters are recovered by extraction, and then operations such as neutralization, oxidation, air flotation purification, activated carbon adsorption, distillation and the like are carried out on a water phase, so that the organic matters remained in the water phase are further removed. The patent has complex treatment process, high treatment cost and solid waste generation, and does not mention a solid waste treatment method.
Chinese patent CN104925997A discloses a method for recycling high-salinity wastewater with a recyclable catalyst. The pH value of the wastewater treated by the patent is 4.0-6.0 and is H2O2As an oxidizing agent, Cu2+The catalyst, the catalyst and the oxidant are added in batches, and the organic matters in the high-salinity wastewater can be catalytically, oxidatively and degraded. After the oxidation reaction is finished, the pH value of the reaction liquid is adjusted to 2.0-4.0, the catalyst is recovered in a precipitation form by adding alkali, and the recovered catalyst is added with hydrochloric acid for redissolution and then returned to the catalytic oxidation reactor for recycling. This patent employs H2O2Is an oxidizing agent, has high treatment cost, and is Cu2+To H2O2Having a catalytic decomposition effect, H2O2The consumption of (A) is usually much higher than the theoretical amount; in addition, this patent teachesThe method of firstly adding alkali for precipitation and then adding acid for dissolution is adopted to realize the recycling of the catalyst, so that a large amount of sodium hydroxide and hydrochloric acid are additionally consumed, and the additionally generated inorganic salt increases the treatment cost.
Chinese patent CN108715487A discloses a method for treating waste water produced by isooctyl thioglycolate. The patent catalytically oxidizes isooctyl thioglycolate production wastewater by a bubbling reactor at the temperature of 150 ℃ and the pressure of 2.0-10.0 MPa. Although the treatment method of the patent can realize lower organic content in treated water and salt, the operating conditions of high temperature and high pressure have special requirements on the reactor; particularly for the waste water produced by isooctyl thioglycolate with higher chloride content, the reactor needs to be made of Hastelloy materials, and the equipment investment is huge.
Chinese patent CN101333013A discloses a harmless treatment method and equipment for catalytic oxidation of wastewater by continuous microwave-ultraviolet light induction; the active carbon modified by magnetic transition metal and oxide thereof is used as an adsorbent, a microwave generator emits short pulse microwaves, an electrodeless ultraviolet light source is excited to generate ultraviolet light, and the ultraviolet light and oxygen brought by air react to generate O3And assist H2O2、ClO2Or NaClO as oxidant to decompose organic matter through microwave induced catalytic oxidation reaction. The technology needs to use microwave and ultraviolet light to induce and generate O3And additional consumption of H2O2、ClO2And oxidizing agents such as NaClO and the like, the equipment is complex to build and the operation cost is high.
In the prior method for treating the waste water produced by isooctyl thioglycolate, a large amount of H is consumed for low-temperature normal-pressure operation2O2For organic wastewater with high COD, the operation cost is expensive; although the high-temperature and high-pressure operation can use cheap air as the oxidant, the strict reaction conditions have special requirements on the material of the reactor, and the equipment investment is huge.
Therefore, based on the above technical defects, a new treatment method and a new treatment device for isooctyl thioglycolate production wastewater are needed to be explored.
Disclosure of Invention
The purpose of the invention is: provides a method for treating waste water produced by isooctyl thioglycolate. The method obviously reduces the content of COD in the wastewater, effectively separates water and solid salt, has low content of organic matters in the water and the solid salt, can repeatedly use the separated water, can use the solid salt as a byproduct, and can continuously carry out the treatment process; the invention also provides a processing device thereof.
The invention relates to a method for treating waste water produced by isooctyl thioglycolate, which comprises the following steps:
(1) enabling the isooctyl thioglycolate production wastewater to flow through an adsorption tower filled with Fe catalyst loaded by granular activated carbon as an adsorbent to perform adsorption reaction;
(2) after adsorption, the salt-containing wastewater flowing out of the adsorption tower enters an evaporation device for salt water separation, and evaporation mother liquor is filtered by a desalting filter to obtain solid salt;
(3) when the adsorbent in the adsorption tower reaches adsorption saturation, stopping injecting the isooctyl thioglycolate production wastewater, preheating the adsorption tower to a certain temperature, continuously introducing air to perform in-situ catalytic oxidation reaction, oxidizing and decomposing the adsorbed organic matters into gas, and discharging the gas through a pipeline, wherein the adsorbent is regenerated;
wherein: and (3) carrying out in-situ catalytic oxidation reaction according to the step (3) after the adsorption saturation of the adsorption tower A, and allowing the isooctyl thioglycolate production wastewater to enter the adsorption tower B for separation of organic matters and salts so as to realize continuous operation of wastewater treatment.
Wherein:
the salt in the isooctyl thioglycolate production wastewater in the step (1) is NaCl, the salt content is 17.0-22.0 wt.%, the COD content is 10000-20000mg/L, and the pH value is 0.5-6.0.
The adsorbent in the step (1) is a Fe catalyst (marked as Fe/AC) loaded by granular activated carbon, the porosity of the Fe catalyst is more than 30 percent, and the specific surface area of the Fe catalyst is more than 1000m2/g。
The granular active carbon loaded Fe catalyst in the step (1) is granular nitrogen-doped active carbon, and the nitrogen doping amount is more than 5 wt%; the supported Fe catalyst is a highly dispersed Fe nano-particle catalyst with the particle size of 5-50nm, and the loading capacity of the Fe nano-particle catalyst on the granular activated carbon is 10-20 wt.%.
The flow rate of the waste water produced by the isooctyl thioglycolate in the step (1) flowing through the adsorption tower A is 20-60 mL/min.
And (3) condensing the water evaporated by the evaporation device in the step (2) and then storing and recycling the water.
And (4) sampling and analyzing the salt-containing wastewater outlet at the bottom of the adsorption tower in real time in the step (3), and when the COD content of the effluent salt-containing wastewater is higher than 1000mg/L, determining that the adsorption tower is saturated.
The in-situ catalytic oxidation reaction temperature in the step (3) is 200-; the catalytic oxidation reaction time is the continuous air introduction time of air in the adsorption tower.
Preferably, the method for treating the isooctyl thioglycolate production wastewater comprises the following steps: filling a granular activated carbon-loaded Fe catalyst serving as an adsorbent into an adsorption tower in advance, enabling isooctyl thioglycolate production wastewater to flow through the adsorption tower, fully adsorbing organic matters in the wastewater by the adsorbent, and enabling effluent saline wastewater to enter an evaporation device for desalination to realize separation of the organic matters and salt in the isooctyl thioglycolate production wastewater; carrying out in-situ catalytic oxidation reaction after the adsorbent reaches adsorption saturation, preheating the adsorption tower to a certain temperature, continuously introducing air, and oxidatively decomposing the adsorbed saturated organic matter into H under the action of a catalyst2O、CO2、SO4 2-Meanwhile, the regeneration of the adsorbent is realized, and the tail gas is absorbed by the waste water produced by the isooctyl thioglycolate and then discharged; two adsorption towers A and B are used alternately, the adsorption tower A is heated after reaching adsorption saturation and is aerated for catalytic oxidation degradation, at the moment, wastewater enters the adsorption tower B for separation of organic matters and salt, and continuous operation of the device is realized.
The invention relates to a treatment device of isooctyl thioglycolate production wastewater, which comprises an evaporation device, a desalting filter, an adsorption tower and a wastewater storage tank; the waste water storage tank is sequentially connected with the filtering device, the adsorption tower, the buffer storage tank, the evaporation device and the desalting filter through pipelines, and the desalting filter is connected with the filtering device through a pipeline; the bottom of the adsorption tower is connected with an air compressor, and the top of the adsorption tower is connected with a wastewater storage tank through a pipeline.
Wherein:
the adsorption tower consists of an adsorption tower A and an adsorption tower B which are arranged in parallel.
Resistance wires are arranged outside the adsorption tower A and the adsorption tower B.
The middle parts in the adsorption tower A and the adsorption tower B are provided with a porous solid adsorbent bed layer, and the bottom of the porous solid adsorbent bed layer is provided with an adsorbent support plate; and the porous solid adsorbent bed layer is provided with a Fe catalyst loaded by granular activated carbon.
The evaporation device is connected with the condensing device and the distilled water storage tank in sequence through pipelines.
A first delivery pump is arranged on a pipeline connecting the wastewater storage tank and the filtering device; a second delivery pump is arranged on a pipeline connecting the buffer storage tank and the evaporation device; and a third delivery pump is arranged on a pipeline connecting the desalting filter and the filtering device.
A valve E is arranged on a wastewater inlet pipeline connected with the adsorption tower A, and a valve F is arranged on a wastewater outflow pipeline; and a valve A is arranged on a tail gas exhaust pipeline connected with the adsorption tower A, and a valve B is arranged on an air inlet pipeline connected with the adsorption tower A.
A valve G is arranged on a wastewater inlet pipeline connected with the adsorption tower B, and a valve H is arranged on a wastewater outflow pipeline; and a valve C is arranged on a tail gas exhaust pipeline connected with the adsorption tower B, and a valve D is arranged on an air inlet pipeline connected with the adsorption tower B.
The operation process of the device for treating the production wastewater of the isooctyl thioglycolate comprises the following steps:
(1) filling a granular activated carbon-loaded Fe catalyst into an adsorption tower A and an adsorption tower B in advance, enabling isooctyl thioglycolate production wastewater to flow through the adsorption tower A, enabling a valve E and a valve F to be in an open state, and enabling a valve G and a valve H to be in a closed state; and (3) desalting the salt-containing wastewater flowing out of the bottom of the adsorption tower A in an evaporation device, condensing evaporated water in a condensing device, then feeding the condensed evaporated water in an evaporated water storage tank, allowing the evaporated mother liquor to pass through a desalting filter to obtain solid salt, and allowing the filtrate to pass through a third conveying pump and be merged into a conveying pipeline of the wastewater storage tank.
(2) Sampling and analyzing a salt-containing wastewater outlet at the bottom of the adsorption tower A in real time, and when the COD content of the effluent salt-containing wastewater is higher than 1000mg/L, determining that the adsorption tower A is saturated in adsorption; at this time, the valves E and F are closed, the valves G and H are opened, and the adsorption tower B starts to adsorb organic matters; simultaneously, after preheating the adsorption tower A to 200-400 ℃, opening the valve A and the valve B, continuously introducing air into the adsorption tower A for 60-240min, and oxidatively decomposing the organic matters adsorbed by the catalyst into H2O、CO2、SO4 2-The regeneration of the adsorbent is realized, and the adsorption tower A and the adsorption tower B are alternately recycled.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a method for treating isooctyl thioglycolate production wastewater, which is characterized in that a Fe catalyst loaded by granular activated carbon is filled into an adsorption tower in advance as an adsorbent, the isooctyl thioglycolate production wastewater flows through the adsorption tower, and organic matters in the wastewater are fully adsorbed by the adsorbent, so that the separation of the organic matters and salt in the wastewater is realized; greatly reducing the COD content of the salt-containing wastewater flowing out of the adsorption tower, desalting the salt-containing wastewater in an evaporation device, and condensing the evaporated water to reuse the water as reclaimed water; the evaporated mother liquor is filtered by a desalting filter to obtain solid salt as a byproduct for sale, and the filtrate is merged into a conveying pipeline of a wastewater storage tank through a conveying pump. The invention skillfully avoids the problem of equipment corrosion when the traditional wet air catalytic oxidation method is used for treating the salt-containing organic wastewater, and obviously reduces the equipment investment cost.
(2) According to the method for treating the isooctyl thioglycolate production wastewater, granular activated carbon is used as an adsorbent and a catalyst carrier, and the activated carbon is large in specific surface area and strong in adsorption capacity; and a certain amount of hydroxyl, aldehyde group, carboxyl and other organic groups exist on the surface of the activated carbon, and the organic groups can interact with part of organic matters in the wastewater, so that the adsorption capacity of the activated carbon on the organic matters in the wastewater is further enhanced.
(3) After the salt-containing organic wastewater is subjected to adsorption and desalination treatment, the removal rate of COD (chemical oxygen demand) of the distilled water is over 99 percent, the TOC content in solid salt is very low, the salt content in the solid salt is more than or equal to 98.5 wt.%, and the TOC is less than or equal to 10.1 mu g/g; the distilled water can be reused as reclaimed water, and the solid salt can be sold as a byproduct.
(4) According to the method for treating the isooctyl thioglycolate production wastewater, organic matters and salts in the wastewater are separated in advance in an adsorption mode, and then the saturated organic matters are degraded and adsorbed by in-situ catalytic oxidation, so that the problem of corrosion of the wastewater containing the chlorine salt to equipment under the conditions of high temperature and high pressure is ingeniously avoided.
(5) The method for treating the waste water produced by the isooctyl thioglycolate adopts air as an oxidant, and has the advantages of low price and easy obtainment; and the in-situ catalytic oxidation treatment on the organic matter with saturated adsorption is a gas-solid reaction, so that the problem of metal dissolution in the catalyst is not involved.
(6) According to the method for treating the isooctyl thioglycolate production wastewater, the oxidation degree of organic matters can be improved in a mode of raising the reaction temperature in the in-situ catalytic oxidation treatment process of the organic matters with saturated adsorption, the reaction process is normal pressure, and the problem of pressure resistance of equipment is not required to be considered.
(7) The method for treating the isooctyl thioglycolate production wastewater can fully utilize the heat generated by the oxidation of the organic matters to maintain the operation of the system in the in-situ catalytic oxidation treatment process of the organic matters with saturated adsorption, reduce the energy consumption in the wastewater treatment process and ensure the heat balance of the system.
(8) The method for treating the waste water from the production of isooctyl thioglycolate has the advantages that after the in-situ catalytic oxidation treatment process is carried out on the organic matters with saturated adsorption, the organic matters are thoroughly oxidized and decomposed into H2O、CO2、SO4 2-The adsorbent can be recycled.
(9) The invention firstly proposes the idea of separating organic matters and salts in the isooctyl thioglycolate production wastewater in advance, and then respectively carrying out catalytic oxidative degradation and evaporative desalination on the organic matters and the salts, so that not only can the recovery and utilization of water and inorganic salts be realized, but also the organic matters can be deeply oxidatively degraded, thereby realizing zero emission.
(10) The treatment device for the production wastewater of isooctyl thioglycolate provided by the invention adopts two adsorption towers A and B to be alternately used, the adsorption tower A is heated after reaching adsorption saturation and is aerated for catalytic oxidation degradation, the wastewater enters the adsorption tower B for separation of organic matters and salts, and the device can continuously run.
Drawings
FIG. 1 is a schematic structural view of a wastewater treatment device for isooctyl thioglycolate production according to the present invention;
wherein: 1. a wastewater storage tank; 2. a first delivery pump; 3. a filtration device; 4. an adsorption tower A; 5. an adsorption tower B; 6. a buffer storage tank; 7. a second delivery pump; 8. an evaporation device; 9. a condensing unit; 10. evaporating water to a storage tank; 11. a desalting filter; 12. a third delivery pump; 13. an air compressor; 14. a porous solid adsorbent bed; 15. an adsorbent support plate; 16. a valve A; 17. a valve B; 18. a valve C; 19. a valve D; 20. a valve E; 21. a valve F; 22. a valve G; 23. and (7) a valve H.
Detailed Description
The present invention is further described below with reference to examples.
The method for treating the isooctyl thioglycolate production wastewater comprises the following steps:
(1) enabling the isooctyl thioglycolate production wastewater to flow through an adsorption tower filled with Fe catalyst loaded by granular activated carbon as an adsorbent to perform adsorption reaction;
(2) after adsorption, the salt-containing wastewater flowing out of the adsorption tower enters an evaporation device for salt water separation, and evaporation mother liquor is filtered by a desalting filter to obtain solid salt;
(3) when the adsorbent in the adsorption tower reaches adsorption saturation, stopping injecting the isooctyl thioglycolate production wastewater, preheating the adsorption tower to a certain temperature, continuously introducing air to perform in-situ catalytic oxidation reaction, oxidizing and decomposing the adsorbed organic matters into gas, and discharging the gas through a pipeline, wherein the adsorbent is regenerated;
wherein: and (3) carrying out in-situ catalytic oxidation reaction according to the step (3) after the adsorption saturation of the adsorption tower A, and allowing the isooctyl thioglycolate production wastewater to enter the adsorption tower B for separation of organic matters and salts so as to realize continuous operation of wastewater treatment.
Wherein:
the granular activated carbon-supported Fe catalyst (denoted as Fe/AC) described in the step (1) had a porosity of 35.2% and a specific surface area of 1263.5m2/g。
In the Fe catalyst loaded by the granular activated carbon in the step (1), the granular activated carbon is granular nitrogen-doped activated carbon, and the nitrogen doping amount is 5.3 wt%; the supported Fe catalyst is a highly dispersed Fe nano-particle catalyst with the particle size of 10-40 nm; the loading of the Fe nanoparticle catalyst on the granular activated carbon was 13.6 wt.%.
As shown in figure 1: the device for treating the isooctyl thioglycolate production wastewater comprises an evaporation device 8, a desalting filter 11, an adsorption tower and a wastewater storage tank 1; the wastewater storage tank 1 is sequentially connected with the filtering device 3, the adsorption tower, the buffer storage tank 6, the evaporation device 8 and the desalting filter 11 through pipelines, and the desalting filter 11 is connected with the filtering device 3 through a pipeline; the bottom of the adsorption tower is connected with an air compressor 13, and the top of the adsorption tower is connected with a wastewater storage tank 1 through a pipeline.
Wherein:
the adsorption tower consists of an adsorption tower A4 and an adsorption tower B5 which are arranged in parallel.
Resistance wires are arranged outside the adsorption tower A4 and the adsorption tower B5.
The middle parts in the adsorption tower A4 and the adsorption tower B5 are provided with a porous solid adsorbent bed layer 14, and the bottom of the porous solid adsorbent bed layer 14 is provided with an adsorbent support plate 15; the porous solid adsorbent bed 14 is provided with a Fe catalyst loaded by granular activated carbon.
The evaporation device 8 is connected to the condensation device 9 and the distilled water storage tank 10 in this order through a pipe.
A first delivery pump 2 is arranged on a pipeline connecting the wastewater storage tank 1 and the filtering device 3; a second delivery pump 7 is arranged on a pipeline connecting the buffer storage tank 6 with the evaporation device 8; a third delivery pump 12 is arranged on a pipeline of the desalting filter 11 connected with the filtering device 3.
A valve E20 is arranged on a wastewater inlet pipeline connected with the adsorption tower A4, and a valve F21 is arranged on a wastewater outflow pipeline; a valve a 16 is arranged on the tail gas exhaust pipeline connected with the adsorption tower A4, and a valve B17 is arranged on the air inlet pipeline connected with the adsorption tower A4.
A valve G22 is arranged on a wastewater inlet pipeline connected with the adsorption tower B5, and a valve H23 is arranged on a wastewater outflow pipeline; a valve C18 is arranged on a tail gas exhaust pipeline connected with the adsorption tower B5, and a valve D19 is arranged on an air inlet pipeline connected with the adsorption tower B5.
Example 1
The method for treating the isooctyl thioglycolate production wastewater, disclosed by the embodiment 1 of the invention, comprises the following steps of:
(1) filling a granular activated carbon-loaded Fe catalyst into an adsorption tower A and an adsorption tower B in advance, enabling isooctyl thioglycolate production wastewater (the salt in the isooctyl thioglycolate production wastewater is NaCl, the salt content is 20.0 wt.%, the COD content is 10000mg/L, and the pH value is 0.5) to flow through the adsorption tower A, enabling a valve E and a valve F to be in an open state, enabling a valve G and a valve H to be in a closed state, and controlling the flow rate of the wastewater to be 20 mL/min; and (3) desalting the salt-containing wastewater flowing out of the bottom of the adsorption tower A in an evaporation device, condensing evaporated water in a condensing device, then feeding the condensed evaporated water in an evaporated water storage tank, allowing the evaporated mother liquor to pass through a desalting filter to obtain solid salt, and allowing the filtrate to pass through a conveying pump and be merged into a conveying pipeline of the wastewater storage tank.
(2) Sampling and analyzing a salt-containing wastewater outlet at the bottom of the adsorption tower A in real time, and when the COD content of the effluent salt-containing wastewater is higher than 1000mg/L, determining that the adsorption tower A is saturated in adsorption; at this time, the valves E and F are closed, the valves G and H are opened, and the adsorption tower B starts to adsorb organic matters; simultaneously, after preheating the adsorption tower A to 200 ℃, opening the valve A and the valve B, continuously introducing air into the adsorption tower A, controlling the air flow rate to be 400mL/min, treating the air for 4h, controlling the catalytic oxidation reaction pressure to be 0.1MPa, and adsorbing the organic matters under the action of a catalystOxidative decomposition to H2O、CO2、SO4 2-And the regeneration of the adsorbent is realized. The adsorption tower A and the adsorption tower B are alternately recycled.
Through detection, the COD content of the effluent water at the bottom of the adsorption tower is between 600 and 1000mg/L during continuous operation, the removal rate of the COD of the effluent water is 99.52 percent, and the pH value is 6.8; the recovery rate of NaCl is 99.5%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.5 wt.%, TOC: 7.6. mu.g/g, SO4 2-：0.02wt.％。
Example 2
The method for treating the isooctyl thioglycolate production wastewater, disclosed by the embodiment 2 of the invention, comprises the following steps of:
(1) filling a granular activated carbon-loaded Fe catalyst into an adsorption tower A and an adsorption tower B in advance, enabling isooctyl thioglycolate production wastewater (the salt in the isooctyl thioglycolate production wastewater is NaCl, the salt content is 17.0 wt.%, the COD content is 15000mg/L, and the pH value is 2.0) to flow through the adsorption tower A, enabling a valve E and a valve F to be in an open state, enabling a valve G and a valve H to be in a closed state, and controlling the flow rate of the wastewater to be 40 mL/min; and (3) desalting the salt-containing wastewater flowing out of the bottom of the adsorption tower A in an evaporation device, condensing evaporated water in a condensing device, then feeding the condensed evaporated water in an evaporated water storage tank, allowing the evaporated mother liquor to pass through a desalting filter to obtain solid salt, and allowing the filtrate to pass through a conveying pump and be merged into a conveying pipeline of the wastewater storage tank.
(2) Sampling and analyzing a salt-containing wastewater outlet at the bottom of the adsorption tower A in real time, and when the COD content of the effluent salt-containing wastewater is higher than 1000mg/L, determining that the adsorption tower A is saturated in adsorption; at this time, the valves E and F are closed, the valves G and H are opened, and the adsorption tower B starts to adsorb organic matters; simultaneously, after preheating the adsorption tower A to 250 ℃, opening the valve A and the valve B, continuously introducing air into the adsorption tower A, controlling the air flow rate to be 500mL/min, the treatment time to be 2.5H, the catalytic oxidation reaction pressure to be 0.1MPa, and oxidatively decomposing the organic matters adsorbed by the action of the catalyst into H2O、CO2、SO4 2-And the regeneration of the adsorbent is realized. The adsorption tower A and the adsorption tower B are alternately recycled.
Through detection, the COD content of the bottom flow effluent of the adsorption tower is between 400-1000mg/L during continuous operationThe removal rate of COD in the distilled water is 99.17 percent, and the pH value is 6.6; the recovery rate of NaCl is 99.1%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 99.3 wt.%, TOC: 10.1. mu.g/g, SO4 2-：0.01wt.％。
Example 3
The method for treating the isooctyl thioglycolate production wastewater, disclosed by the embodiment 3 of the invention, comprises the following steps of:
(1) filling a granular activated carbon-loaded Fe catalyst into an adsorption tower A and an adsorption tower B in advance, enabling isooctyl thioglycolate production wastewater (the salt in the isooctyl thioglycolate production wastewater is NaCl, the salt content is 17.0 wt.%, the COD content is 20000mg/L, and the pH value is 4.5) to flow through the adsorption tower A, enabling a valve E and a valve F to be in an open state, enabling a valve G and a valve H to be in a closed state, and controlling the flow rate of the wastewater to be 60 mL/min; and (3) desalting the salt-containing wastewater flowing out of the bottom of the adsorption tower A in an evaporation device, condensing evaporated water in a condensing device, then feeding the condensed evaporated water in an evaporated water storage tank, allowing the evaporated mother liquor to pass through a desalting filter to obtain solid salt, and allowing the filtrate to pass through a conveying pump and be merged into a conveying pipeline of the wastewater storage tank.
(2) Sampling and analyzing a salt-containing wastewater outlet at the bottom of the adsorption tower A in real time, and when the COD content of the effluent salt-containing wastewater is higher than 1000mg/L, determining that the adsorption tower A is saturated in adsorption; at this time, the valves E and F are closed, the valves G and H are opened, and the adsorption tower B starts to adsorb organic matters; simultaneously, after preheating the adsorption tower A to 300 ℃, opening the valve A and the valve B, continuously introducing air into the adsorption tower A, controlling the air flow rate to be 600mL/min, treating the air for 1H, controlling the catalytic oxidation reaction pressure to be 0.1MPa, and oxidatively decomposing the organic matters adsorbed by the action of the catalyst into H2O、CO2、SO4 2-And the regeneration of the adsorbent is realized. The adsorption tower A and the adsorption tower B are alternately recycled.
Through detection, the COD content of the bottom flow water of the adsorption tower during continuous operation is between 200 and 1000mg/L, the removal rate of the COD of the distilled water is 99.25 percent, and the pH value is 7.1; the recovery rate of NaCl is 98.9%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 99.1 wt.%, TOC: 8.3. mu.g/g, SO4 2-：0.03wt.％。
The effective volume of the adsorption column in examples 1-3 was 1000 mL.
Comparative example 1
The Fe catalyst supported by the granular activated carbon in the adsorption tower was replaced with Fe catalyst supported by quartz sand, and the rest of the procedure was the same as in example 1.
Through detection, the COD content of the effluent of the tower bottom flow is 9796mg/L, which indicates that the quartz sand has no adsorption capacity; the wastewater treatment plant cannot be operated continuously.
Comparative example 2
The adsorbent in the adsorption column was replaced with granular activated carbon having no Fe catalyst supported thereon, and the remaining steps were the same as in example 1.
Through detection, the COD content of the tower bottom effluent water is 9142mg/L when the adsorbent is used for the second time; the granular active carbon without the supported Fe catalyst can not effectively catalyze, oxidize, decompose and adsorb organic matters; the wastewater treatment plant cannot be operated continuously.
Comparative example 3
In the catalytic oxidation treatment stage, the air used was replaced with nitrogen, and the rest of the procedure was the same as in example 2.
Through detection, the COD content of the bottom effluent water of the adsorbent when the adsorbent is used for the second time is 14976 mg/L; the oxygen in the air is the main component for catalyzing, oxidizing, desorbing and adsorbing the organic matters; the wastewater treatment plant cannot be operated continuously.
Comparative example 4
In the catalytic oxidation treatment stage, the adsorption column saturated with adsorption was heated to 100 ℃, and the rest of the procedure was the same as in example 3.
Through detection, the COD content of the tower bottom effluent water is 8675mg/L when the adsorbent is used for the second time; indicating that when the reaction temperature is not high enough, the adsorbed saturated organic matter is difficult to be completely catalyzed, oxidized and decomposed into H2O、CO2、SO4 2-(ii) a The wastewater treatment plant cannot be operated continuously.
The data for examples 1-3 and comparative examples 1-4 are shown in Table 1.
TABLE 1 Experimental results for examples 1-3 and comparative examples 1-4
As can be seen from Table 1, under the action of the Fe catalyst loaded by the granular activated carbon and simultaneously used as an adsorbent and a catalyst, the removal rate of COD in distilled water is more than 99%, the TOC content in solid salt is very low, the salt content in the solid salt is more than or equal to 98.5 wt%, and the TOC is less than or equal to 10.1 mu g/g.
Claims (10)
1. A treatment method of isooctyl thioglycolate production wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) enabling the isooctyl thioglycolate production wastewater to flow through an adsorption tower filled with Fe catalyst loaded by granular activated carbon as an adsorbent to perform adsorption reaction;
(2) after adsorption, the salt-containing wastewater flowing out of the adsorption tower enters an evaporation device for salt water separation, and evaporation mother liquor is filtered by a desalting filter to obtain solid salt;
(3) when the adsorbent in the adsorption tower reaches adsorption saturation, stopping injecting the isooctyl thioglycolate production wastewater, preheating the adsorption tower to a certain temperature, continuously introducing air to perform in-situ catalytic oxidation reaction, oxidizing and decomposing the adsorbed organic matters into gas, and discharging the gas through a pipeline, wherein the adsorbent is regenerated;
wherein: and (3) carrying out in-situ catalytic oxidation reaction according to the step (3) after the adsorption saturation of the adsorption tower A, and allowing the isooctyl thioglycolate production wastewater to enter the adsorption tower B for separation of organic matters and salts so as to realize continuous operation of wastewater treatment.
2. The method for treating waste water from the production of isooctyl thioglycolate according to claim 1, wherein the method comprises the following steps: the salt in the isooctyl thioglycolate production wastewater in the step (1) is NaCl, the salt content is 17.0-22.0 wt.%, the COD content is 10000-20000mg/L, and the pH value is 0.5-6.0.
3. Thioglycolic acid according to claim 1The treatment method of the isooctyl ester production wastewater is characterized by comprising the following steps: the granular activated carbon-loaded Fe catalyst in the step (1) has the porosity of more than 30 percent and the specific surface area of more than 1000m2/g。
4. The method for treating waste water from the production of isooctyl thioglycolate according to claim 1, wherein the method comprises the following steps: the granular active carbon loaded Fe catalyst in the step (1) is granular nitrogen-doped active carbon, and the nitrogen doping amount is more than 5 wt%; the supported Fe catalyst is Fe nano-particle catalyst with the particle size of 5-50nm, and the supported amount of the Fe nano-particle catalyst on the granular activated carbon is 10-20 wt.%.
5. The method for treating waste water from the production of isooctyl thioglycolate according to claim 1, wherein the method comprises the following steps: the flow rate of the isooctyl thioglycolate production wastewater flowing through the adsorption tower in the step (1) is 20-60 mL/min;
condensing and storing the water evaporated by the evaporation device in the step (2) for recycling;
and (4) sampling and analyzing the salt-containing wastewater outlet at the bottom of the adsorption tower in real time in the step (3), and when the COD content of the effluent salt-containing wastewater is higher than 1000mg/L, determining that the adsorbent in the adsorption tower is saturated.
6. The method for treating waste water from the production of isooctyl thioglycolate according to claim 1, wherein the method comprises the following steps: the in-situ catalytic oxidation reaction temperature in the step (3) is 200-; the catalytic oxidation reaction time is the continuous air introduction time of air in the adsorption tower.
7. The apparatus for treating waste water from the production of isooctyl thioglycolate according to claim 1, wherein: comprises an evaporation device (8), a desalting filter (11), an adsorption tower and a waste water storage tank (1); the wastewater storage tank (1) is sequentially connected with the filtering device (3), the adsorption tower, the buffer storage tank (6), the evaporation device (8) and the desalting filter (11) through pipelines, and the desalting filter (11) is connected with the filtering device (3) through pipelines; the bottom of the adsorption tower is connected with an air compressor (13), and the top of the adsorption tower is connected with a wastewater storage tank (1) through a pipeline.
8. The apparatus for treating waste water from the production of isooctyl thioglycolate according to claim 7, wherein:
the adsorption tower consists of an adsorption tower A (4) and an adsorption tower B (5) which are arranged in parallel;
resistance wires are arranged outside the adsorption tower A (4) and the adsorption tower B (5);
the middle parts in the adsorption tower A (4) and the adsorption tower B (5) are provided with a porous solid adsorbent bed layer (14), and the bottom of the porous solid adsorbent bed layer (14) is provided with an adsorbent support plate (15); and the porous solid adsorbent bed layer (14) is provided with a Fe catalyst loaded by granular activated carbon.
9. The apparatus for treating waste water from the production of isooctyl thioglycolate according to claim 7, wherein: the evaporation device (8) is connected with the condensing device (9) and the distilled water storage tank (10) in sequence through pipelines.
10. The apparatus for treating waste water from the production of isooctyl thioglycolate according to claim 8, wherein:
a valve E (20) is arranged on a wastewater inlet pipeline connected with the adsorption tower A (4), and a valve F (21) is arranged on a wastewater outlet pipeline; a tail gas discharge pipeline connected with the adsorption tower A (4) is provided with a valve A (16), and an air inlet pipeline connected with the adsorption tower A (4) is provided with a valve B (17);
a valve G (22) is arranged on a wastewater inlet pipeline connected with the adsorption tower B (5), and a valve H (23) is arranged on a wastewater outlet pipeline; a tail gas discharge pipeline connected with the adsorption tower B (5) is provided with a valve C (18), and an air inlet pipeline connected with the adsorption tower B (5) is provided with a valve D (19).
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| CN101522572A (en) * | 2006-06-27 | 2009-09-02 | 技术研究及发展基金有限公司 | Method for adsorption of fluid contaminants and regeneration of the adsorbent |
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| CN101318750A (en) * | 2008-07-22 | 2008-12-10 | 湖北犇星化工有限责任公司 | Method for treating waste water from acetic acid mercapto- isooctyl ester |
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