CN108715497B - Treatment method and treatment device for isooctyl thioglycolate production wastewater - Google Patents

Treatment method and treatment device for isooctyl thioglycolate production wastewater Download PDF

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CN108715497B
CN108715497B CN201810577845.5A CN201810577845A CN108715497B CN 108715497 B CN108715497 B CN 108715497B CN 201810577845 A CN201810577845 A CN 201810577845A CN 108715497 B CN108715497 B CN 108715497B
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wastewater
isooctyl thioglycolate
production
waste water
storage tank
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CN108715497A (en
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王景华
张广俊
崔洪友
杨明刚
刘勤学
张远
王勇
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Shandong Jianlong Chemical Co ltd
Shandong Zhanhua Jinjiali Chemical Technology Co ltd
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Shandong Zhanhua Jinjiali Chemical Technology Co ltd
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    • C02F1/02Treatment of water, waste water, or sewage by heating
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    • C02F1/06Flash evaporation
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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. The treatment method comprises the steps of mixing a catalytic oxidation auxiliary agent into the isooctyl thioglycolate production wastewater in advance, preheating the mixture, introducing the mixture into a bubbling reactor, and carrying out oxidation reaction with an oxidant, so as to oxidize organic matters in the wastewater into H2O、CO2And SO4 2‑Desalting the reaction solution after reaction by flash evaporation and evaporation concentration; the invention also provides a processing device thereof. The invention uses soluble cobalt salt and MoO3/TiO2The combination fully exerts the synergistic effect between the two, thereby quickly and deeply oxidizing and removing the organic matters in the wastewater; greatly reduces the content of COD in the wastewater, can effectively separate water and solid salt, has low content of organic matters in the water and the solid salt, can recycle the separated water, and can use the solid salt as a byproduct.

Description

Treatment method and treatment device for isooctyl thioglycolate production wastewater
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
Sodium hydrosulfide method is adopted to produce isooctyl thioglycolate because of its advantages such as simple production process, low cost, etc., but often will be accompanied by a large amount of organic waste water in the production process, the content of sodium chloride in these organic waste water is up to more than 20%, still contain organic matters such as thioglycolic acid, isooctyl alcohol, isooctyl thioglycolate, etc..
Nighong et al used Fenton reagent to oxidize the isooctyl thioglycolate production wastewater, distilled the wastewater first, and then oxidized the distilled water, the removal rate of COD was 87.0%. On the one hand, the method has higher treatment cost, and on the other hand, the treatment of salt is not mentioned; in addition, salt and a part of organic matters are remained in the distillation kettle residue in the distillation process, which brings difficulty to the subsequent solid waste treatment.
Chinese patent CN101318750A discloses a method for treating waste water produced by isooctyl thioglycolate. The patent firstly extracts and recovers partial organic matters, and then carries out the processes of neutralization, oxidation, air flotation purification, activated carbon adsorption, distillation and the like. The patent has complex treatment process, high treatment cost and solid waste generation, and the direction of solid salt is not mentioned.
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 organic pollutants in the high-salinity wastewater can be oxidized and degraded. After the oxidation reaction is finished, the pH value of the reaction solution is adjusted to 2.0-4.0 by acid, then alkali is added for neutralization and precipitation to recover the catalyst, 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 H2O2Has catalytic decomposition effect, so that H2O2The consumption of (A) is usually much higher than the theoretical amount; in addition, the patent adopts a method of firstly neutralizing, precipitating and then dissolving to realize the circulation of the catalystThe use of the ring not only consumes a large amount of hydrochloric acid and sodium hydroxide, but also generates an inorganic salt to increase the treatment cost.
Longhui of Zhejiang university uses simulation components such as n-butyl alcohol, n-butyl alcohol-o-chlorophenol and the like as research objects in homogeneous catalysis wet air oxidation continuous treatment high-salt-content high-concentration organic wastewater of Master academic paper of Longhui university, and adopts a homogeneous catalyst Cu2+And Fe2+The removal rate of COD in the wastewater reaches 90%, but the concentration of the catalyst metal ions is higher in the process of treating the organic wastewater, and the concentration of the catalyst metal ions is as high as 0.833mmol/L, so that on one hand, the treatment cost is high, and on the other hand, the quality index of the recovered salt is poor.
Therefore, the best treatment method for the isooctyl thioglycolate production wastewater is to remove organic matters firstly and then carry out salt and water separation, so that not only can the water be recycled, but also the solid salt with higher purity can be obtained, and zero emission is realized. In the existing method for treating the waste water produced by the isooctyl thioglycolate, because the organic matters cannot be completely oxidized and degraded, the separated water often contains a certain amount of organic matters, the discharge requirement is difficult to meet, and a certain amount of organic matters are always doped in the separated solid salt, so that the separated inorganic salt is polluted. In addition, in the oxidation reaction process, how to realize sufficient gas-liquid two-phase contact and improve mass transfer, heat transfer and reaction efficiency is also a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a method for treating isooctyl thioglycolate production wastewater, which can greatly reduce the content of COD in the wastewater, can effectively separate water and solid salt, has low content of organic matters in the water and the solid salt, can repeatedly use the separated water, and can also use the solid salt as a byproduct; the invention also provides a device for treating the production wastewater of the isooctyl thioglycolate.
The method for treating the waste water produced by the isooctyl thioglycolate comprises the steps of mixing a catalytic oxidation auxiliary agent into the waste water produced by the isooctyl thioglycolate in advance, preheating the mixture, introducing the mixture into a bubbling reactor, and carrying out oxidation reaction with an oxidant so as to enable the mixture to be subjected to the reactionOxidation of organic matter in wastewater to H2O、CO2And SO4 2-Desalting the reaction solution after reaction by flash evaporation and evaporation concentration; the catalytic oxidation auxiliary agent is soluble cobalt salt; the bubbling reactor is filled with TiO2Supported MoO3Porous solid catalysts, i.e. porous solid catalysts MoO3/TiO2
Wherein:
mixing soluble cobalt salt into isooctyl thioglycolate production wastewater, and adding Co2+The molar concentration in the isooctyl thioglycolate production wastewater is 0.1-0.4 mmol/L. The soluble cobalt salt is preferably anhydrous cobalt chloride.
The TiO is2Supported MoO3The porous solid catalyst was in the form of particles having a porosity of 30%.
The oxidant is oxygen or air.
The oxidation reaction temperature is 150-250 ℃, the oxidation reaction time is 10-120min, and the oxidation reaction pressure is 2.0-10.0 MPa; the oxidation reaction time is the residence time in the bubble reactor.
The preheating temperature is 150-250 ℃.
The salt in the isooctyl thioglycolate production wastewater is NaCl, the salt content is 17.0-22.0wt.%, the COD content is 15000-20000mg/L, and the pH value is 0.5-5.0.
The invention relates to a device for treating isooctyl thioglycolate production wastewater, which comprises the following steps: the system comprises a wastewater storage tank, wherein the wastewater storage tank is sequentially connected with a filtering device, a preheating device, a bubbling reactor, a flash evaporation device, an evaporation device and a desalting filter; the bubbling reactor is also sequentially connected with a primary gas-liquid separator and a distilled water storage tank, and the bottom of the bubbling reactor is connected with an air compressor; the evaporation device is connected with the distilled water storage tank.
Preferably, the primary gas-liquid separator is also sequentially connected with the distilled water storage tank through a first condenser and a secondary gas-liquid separator; the evaporation device is connected with the distilled water storage tank through a second condenser; the flash evaporation device is also connected to a pipeline between the bubbling reactor and the primary gas-liquid separator; the desalting filter is also connected with a filtering device.
Preferably, a porous solid catalyst bed layer is arranged in the middle of the bubbling reactor, a catalyst support plate is arranged at the bottom of the porous solid catalyst bed layer, and a gas distributor is arranged at the lower part of the bubbling reactor; the top of the bubbling reactor is provided with a safety valve. The porous solid catalyst MoO is arranged on the porous solid catalyst bed layer3/TiO2
Preferably, the wastewater storage tank is connected with the filtering device through a first pressure delivery pump; a liquid phase pressure reduction regulating valve is arranged on a pipeline between the bubbling reactor and the flash evaporation device; a vapor phase pressure reduction regulating valve is arranged on the pipeline between the bubbling reactor and the primary gas-liquid separator and at one end close to the bubbling reactor; the desalting filter is also connected with the filtering device through a second pressurizing and conveying pump; and the top of the secondary gas-liquid separator is provided with an emptying valve.
The invention has the following beneficial effects:
(1) the invention uses Co as catalytic oxidation auxiliary agent2+And a porous solid catalyst MoO3/TiO2The combination fully exerts the synergistic effect between the two, thereby realizing the rapid deep oxidative degradation of organic matters in the wastewater. Namely, the catalytic oxidation auxiliary agent Co is fully utilized2+The organic matter is quickly oxidized into micromolecular intermediate products such as carboxylic acid and the like, and then the porous solid catalyst MoO is utilized3/TiO2Rapid oxidation of these intermediates to CO2、H2O and SO4 2-And the like in the final product. Catalytic oxidation assistant Co2+And a porous solid catalyst MoO3/TiO2The synergistic effect of (A) can also inhibit the MoO of the porous solid catalyst3/TiO2Coking on the surface, thereby prolonging the MoO of the porous solid catalyst3/TiO2The service life of (2).
(2) Compared with the prior art, the catalytic oxidation auxiliary agent Co in the wastewater treatment process2+Has a low concentration, and in the crystallization process, the catalytic oxidation auxiliary agent Co2+Still dissolved in the crystallization mother liquor, avoids the catalytic oxidation auxiliary agent Co2+The precipitation in the evaporation, concentration and crystallization process improves the quality of solid salt;in addition, the mother liquor after crystallization and desalination is mechanically applied to realize the catalytic oxidation auxiliary agent Co2+Can be recycled.
(3) The invention adopts air or oxygen as oxidant, has the advantages of low price and easy obtaining, and has low treatment cost compared with oxidants such as hydrogen peroxide, ozone and the like; compared with oxidants such as hypochlorite, chlorate and the like, other species are not introduced in the treatment process, and new salt species are not generated, so that the purity of the solid salt is improved.
(4) The bubbling reactor of the invention is filled with a porous solid catalyst MoO3/TiO2Soaking in liquid phase, setting high efficiency gas disperser below the catalyst bed layer, introducing gas from the lower part of the bubbling reactor through the gas disperser to make the gas phase highly dispersed in the liquid phase, moving upwards in the form of bubbles and fully contacting with wastewater, and adding Co as catalytic oxidation assistant2+With a porous solid catalyst MoO3/TiO2Under the combined action of the two phases, the oxidation reaction is carried out, thus greatly improving the contact area of gas and liquid. In the bubbling reactor, bubbles contact with a liquid phase to react, and simultaneously, the effect of stirring the liquid to increase the mass transfer rate can be achieved, so that the method is relatively suitable for the oxidation exothermic reaction. The gas in the bubbling reactor is uniformly distributed in a small bubble form and continuously passes through the gas-liquid reaction layer, so that the gas-liquid contact surface is ensured, the gas and the liquid are fully mixed, and the reaction is good.
(5) The invention can fully utilize the heat generated by the oxidation of organic matters to maintain the operation of the system in the wastewater treatment process, reduces the energy consumption in the wastewater treatment process, not only ensures the heat balance of the system, but also can generate high-pressure steam to supply heat to the outside.
(6) The invention is in catalyzing and oxidizing the assistant Co2+And a porous solid catalyst MoO3/TiO2Under the combined action of the two components, the removal rate of COD is more than 97 percent, and TOC and Co in solid salt2+The content of (A) is very small, and the salt content in the solid salt is more than or equal to 98.5 wt.%; co2+Less than or equal to 4.0 mu g/g; TOC is less than or equal to 10.0 mu g/g. The invention greatly reduces the content of COD in the wastewater, can effectively separate water and solid salt, and can separate water and solidThe content of organic matters in the bulk salt is low, the separated water can be reused, and the solid salt can also be used as a byproduct.
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 pressure feed pump; 3. a filtration device; 4. a preheating device; 5. a bubble reactor; 6. a catalyst support plate; 7. a porous solid catalyst bed; 8. a safety valve; 9. an air compressor; 10. liquid phase decompression regulating valve; 11. a flash evaporation device; 12. an evaporation device; 13. a desalting filter; 14. a second pressurized delivery pump; 15. a second condenser; 16. evaporating water to a storage tank; 17. a vapor phase pressure reduction regulating valve; 18. a primary gas-liquid separator; 19. a first condenser; 20. a secondary gas-liquid separator; 21. an atmospheric valve; 22. a catalytic oxidation promoter; 23. a solid salt; 24. a gas distributor.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Adding isooctyl thioglycolate production wastewater (NaCl content of 17.0 wt.%, COD: 15000mg/L, pH value of 0.5) into a wastewater storage tank, adding catalytic oxidation assistant anhydrous cobalt chloride, stirring uniformly, and adding Co in organic wastewater2+The molar concentration of (A) is 0.4 mmol/L;
(2) preheating to 200 ℃, and introducing into a reactor filled with a porous solid catalyst MoO3/TiO2Reacting with oxygen in the bubbling reactor; controlling the reaction temperature at 200 ℃, the reaction pressure at 7.0MPa, the retention time at 15min and the flow rate of the wastewater at 66.7 ml/min;
(3) sampling and analyzing at the outlet of the bubbling reactor, then entering a flash evaporation device, cooling, centrifugally separating solid salt NaCl through a desalting filter, returning the centrifuged concentrated solution to a filtering device, then entering a preheating device, and applying the concentrated solution to the process to realize the cyclic utilization of the catalytic oxidation auxiliary agent.
Through detection, the removal rate of COD in the treated organic wastewater is 98.12%, and the pH value is 6.8; NaCThe recovery rate of l is 99.1%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.5 wt.%, Co2+:4.0μg/g,TOC:10.0μg/g,SO4 2-:0.02wt.%。
Example 2
(1) Adding isooctyl thioglycolate production wastewater (NaCl content of 17.0 wt.%, COD: 15000mg/L, pH value of 5.0) into a wastewater storage tank, adding catalytic oxidation assistant anhydrous cobalt chloride, stirring uniformly, and adding Co in organic wastewater2+The molar concentration of (A) is 0.3 mmol/L;
(2) preheating to 150 ℃, and introducing into a reactor filled with a porous solid catalyst MoO3/TiO2Reacting with oxygen in the bubbling reactor; controlling the reaction temperature at 150 ℃, the reaction pressure at 4.0MPa, the retention time at 90min and the flow rate of the wastewater at 11.1 ml/min;
(3) sampling and analyzing at the outlet of the bubbling reactor, then entering a flash evaporation device, cooling, centrifugally separating solid salt NaCl through a desalting filter, returning the centrifuged concentrated solution to a filtering device, then entering a preheating device, and applying the concentrated solution to the process to realize the cyclic utilization of the catalytic oxidation auxiliary agent.
Through detection, the removal rate of COD in the treated organic wastewater is 97.95%, and the pH value is 6.6; the recovery rate of NaCl is 99.3%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.7 wt.%, Co2+:3.1μg/g,TOC:9.8μg/g,SO4 2-:0.03wt.%。
Example 3
(1) Adding isooctyl thioglycolate production wastewater (NaCl content 20.0 wt.%, COD: 20000mg/L, pH value 3.0) into a wastewater storage tank, adding catalytic oxidation assistant anhydrous cobalt chloride, stirring uniformly, and adding Co in organic wastewater2+The molar concentration of (A) is 0.1 mmol/L;
(2) preheating to 250 ℃, and introducing into a reactor filled with a porous solid catalyst MoO3/TiO2Reacting with oxygen in the bubbling reactor; controlling the reaction temperature to be 250 ℃, the reaction pressure to be 10.0MPa, the retention time to be 10min and the flow rate of the wastewater to be 100 ml/min;
(3) sampling and analyzing at the outlet of the bubbling reactor, then entering a flash evaporation device, cooling, centrifugally separating solid salt NaCl through a desalting filter, returning the centrifuged concentrated solution to a filtering device, then entering a preheating device, and applying the concentrated solution to the process to realize the cyclic utilization of the catalytic oxidation auxiliary agent.
Through detection, the removal rate of COD in the treated organic wastewater is 97.88 percent, and the pH value is 7.0; the recovery rate of NaCl is 99.2%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.8 wt.%, Co2+:1.2μg/g,TOC:8.3μg/g,SO4 2-:0.02wt.%。
Example 4
(1) Adding isooctyl thioglycolate production wastewater (NaCl content of 17.0 wt.%, COD: 15000mg/L, pH value of 3.0) into a wastewater storage tank, adding catalytic oxidation assistant anhydrous cobalt chloride, stirring uniformly, and adding Co in organic wastewater2+The molar concentration of (A) is 0.2 mmol/L;
(2) preheating to 250 ℃, and introducing into a reactor filled with a porous solid catalyst MoO3/TiO2Reacting with oxygen in the bubbling reactor; controlling the reaction temperature to be 250 ℃, the reaction pressure to be 7.5MPa, the retention time to be 15min and the flow rate of the wastewater to be 66.7 ml/min;
(3) sampling and analyzing at the outlet of the bubbling reactor, then entering a flash evaporation device, cooling, centrifugally separating solid salt NaCl through a desalting filter, returning the centrifuged concentrated solution to a filtering device, then entering a preheating device, and applying the concentrated solution to the process to realize the cyclic utilization of the catalytic oxidation auxiliary agent.
Through detection, the removal rate of COD in the treated organic wastewater is 99.32%, and the pH value is 6.9; the recovery rate of NaCl is 99.4%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.7 wt.%, Co2+:2.1μg/g,TOC:8.7μg/g,SO4 2-:0.03wt.%。
Example 5
(1) Adding isooctyl thioglycolate production wastewater (NaCl content 22.0wt.%, COD: 20000mg/L, pH value 3.0) into a wastewater storage tank, adding catalytic oxidation assistant anhydrous cobalt chloride, stirring uniformly, and adding Co in organic wastewater2+In a molar concentration of0.3mmol/L;
(2) Preheating to 150 ℃, and introducing into a reactor filled with a porous solid catalyst MoO3/TiO2Reacting with oxygen in the bubbling reactor; controlling the reaction temperature at 150 ℃, the reaction pressure at 2.0MPa, the retention time at 120min and the flow rate of the wastewater at 8.33 ml/min;
(3) sampling and analyzing at the outlet of the bubbling reactor, then entering a flash evaporation device, cooling, centrifugally separating solid salt NaCl through a desalting filter, returning the centrifuged concentrated solution to a filtering device, then entering a preheating device, and applying the concentrated solution to the process to realize the cyclic utilization of the catalytic oxidation auxiliary agent.
Through detection, the removal rate of COD in the treated organic wastewater is 97.28%, and the pH value is 6.7; the recovery rate of NaCl is 99.2%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.6 wt.%, Co2+:2.3μg/g,TOC:9.2μg/g,SO4 2-:0.03wt.%。
Example 6
(1) Adding isooctyl thioglycolate production wastewater (NaCl content 22.0wt.%, COD: 15000mg/L, pH value 2.0) into a wastewater storage tank, adding catalytic oxidation assistant anhydrous cobalt chloride, stirring uniformly, and adding Co in organic wastewater2+The molar concentration of (A) is 0.3 mmol/L;
(2) preheating to 250 ℃, and introducing into a reactor filled with a porous solid catalyst MoO3/TiO2Reacting with oxygen in the bubbling reactor; controlling the reaction temperature to be 250 ℃, the reaction pressure to be 8.0MPa, the retention time to be 20min and the flow rate of the wastewater to be 50 ml/min;
(3) sampling and analyzing at the outlet of the bubbling reactor, then entering a flash evaporation device, cooling, centrifugally separating solid salt NaCl through a desalting filter, returning the centrifuged concentrated solution to a filtering device, then entering a preheating device, and applying the concentrated solution to the process to realize the cyclic utilization of the catalytic oxidation auxiliary agent.
Through detection, the removal rate of COD in the treated organic wastewater is 98.10%, and the pH value is 6.8; the recovery rate of NaCl is 99.3%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.9 wt.%, Co2+:3.2μg/g,TOC:8.9μg/g,SO4 2-:0.03wt.%。
Example 7
(1) Adding isooctyl thioglycolate production wastewater (NaCl content of 17.0 wt.%, COD: 20000mg/L, pH value of 3.0) into a wastewater storage tank, adding catalytic oxidation assistant anhydrous cobalt chloride, stirring uniformly, and adding Co in organic wastewater2+The molar concentration of (A) is 0.4 mmol/L;
(2) preheating to 220 ℃, and introducing into a reactor filled with a porous solid catalyst MoO3/TiO2Reacting with oxygen in the bubbling reactor; controlling the reaction temperature at 220 ℃, the reaction pressure at 8.0MPa, the retention time at 20min and the flow rate of the wastewater at 50 ml/min;
(3) sampling and analyzing at the outlet of the bubbling reactor, then entering a flash evaporation device, cooling, centrifugally separating solid salt NaCl through a desalting filter, returning the centrifuged concentrated solution to a filtering device, then entering a preheating device, and applying the concentrated solution to the process to realize the cyclic utilization of the catalytic oxidation auxiliary agent.
Through detection, the removal rate of COD in the treated organic wastewater is 99.23%, and the pH value is 7.0; the recovery rate of NaCl is 99.2%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.7 wt.%, Co2+:2.1μg/g,TOC:8.5μg/g,SO4 2-:0.03wt.%。
Example 8
(1) Adding isooctyl thioglycolate production wastewater (NaCl content 20.0 wt.%, COD: 17000mg/L, pH value 5.0) into a wastewater storage tank, adding catalytic oxidation assistant anhydrous cobalt chloride, stirring uniformly, and adding Co in organic wastewater2+The molar concentration of (A) is 0.2 mmol/L;
(2) preheating to 200 ℃, and introducing into a reactor filled with a porous solid catalyst MoO3/TiO2Reacting with oxygen in the bubbling reactor; controlling the reaction temperature at 200 ℃, the reaction pressure at 7.5MPa, the retention time at 30min and the flow rate of the wastewater at 33.3 ml/min;
(3) sampling and analyzing at the outlet of the bubbling reactor, then entering a flash evaporation device, cooling, centrifugally separating solid salt NaCl through a desalting filter, returning the centrifuged concentrated solution to a filtering device, then entering a preheating device, and applying the concentrated solution to the process to realize the cyclic utilization of the catalytic oxidation auxiliary agent.
Through detection, the removal rate of COD in the treated organic wastewater is 98.24%, and the pH value is 6.7; the recovery rate of NaCl is 99.4%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.5 wt.%, Co2+:2.5μg/g,TOC:9.4μg/g,SO4 2-:0.03wt.%。
The effective volume of the bubble reactor in examples 1-8 was 1000 ml.
Comparative example 1
The catalyst does not contain catalytic oxidation auxiliary agent, anhydrous cobalt chloride and porous solid catalyst MoO3/TiO2The rest of the procedure was the same as in example 1.
Through detection, the removal rate of COD in the treated organic wastewater is 28.90%, and the pH value is 3.2; shows that no catalytic oxidation auxiliary agent is added, no porous solid catalyst MoO is used3/TiO2The organic wastewater is not completely oxidized. The recovery rate of NaCl is 98.4%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.0 wt.%, Co2+: not detected, TOC: 61.2. mu.g/g, SO4 2-:0.01wt.%。
Comparative example 2
MoO without porous solid catalyst3/TiO2The rest of the procedure was the same as in example 1.
Through detection, the removal rate of COD in the treated organic wastewater is 41.80%, and the pH value is 4.0; indicating that the porous solid catalyst MoO is not used3/TiO2The organic wastewater is not completely oxidized. The recovery rate of NaCl is 98.0%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.1 wt.%, Co2+:2.7μg/g,TOC:55.4μg/g,SO4 2-:0.01wt.%。
Comparative example 3
The procedure of example 1 was repeated except that the catalytic oxidation assistant anhydrous cobalt chloride was not added.
Through detection, the removal rate of COD in the treated organic wastewater is 39.22%, and the pH value is 4.3; indicating no addition ofThe catalytic oxidation assistant is anhydrous cobalt chloride, and the organic wastewater is not completely oxidized. The recovery rate of NaCl is 98.2%, and the solid salt is dried and then analyzed, wherein the quality indexes are as follows: NaCl: 98.0 wt.%, Co2+: not detected, TOC: 58.6. mu.g/g, SO4 2-:0.01wt.%。
The data for examples 1-8 and comparative examples 1-3 are shown in Table 1.
TABLE 1 data sheet
Figure BDA0001687580160000081
Figure BDA0001687580160000091
As can be seen from Table 1, the catalyst of the present invention is used in the catalytic oxidation of Co2+And a porous solid catalyst MoO3/TiO2Under the combined action of the two components, the removal rate of COD is more than 97 percent, and TOC and Co in solid salt2+The content of (A) is very small, and the salt content in the solid salt is more than or equal to 98.5 wt.%; co2+≤4.0μg/g;TOC≤10.0μg/g。
As shown in fig. 1, the device for treating isooctyl thioglycolate production wastewater used in examples 1 to 8 comprises a wastewater storage tank 1, wherein the wastewater storage tank 1 is sequentially connected with a filtering device 3, a preheating device 4, a bubbling reactor 5, a flash evaporation device 11, an evaporation device 12 and a desalting filter 13; the bubbling reactor 5 is also sequentially connected with a primary gas-liquid separator 18 and a distilled water storage tank 16, and the bottom of the bubbling reactor 5 is connected with an air compressor 9; the evaporation apparatus 12 is connected to a distilled water storage tank 16.
Wherein:
the primary gas-liquid separator 18 is also connected with the distilled water storage tank 16 in sequence through a first condenser 19 and a secondary gas-liquid separator 20; the evaporation device 12 is connected with a distilled water storage tank 16 through a second condenser 15; the flash evaporation device 11 is also connected to a pipeline between the bubble reactor 5 and the primary gas-liquid separator 18; the desalting filter 13 is also connected with the filtering device 3 through a second pressure delivery pump 14;
a porous solid catalyst bed layer 7 is arranged in the middle of the bubbling reactor 5, and a porous solid catalyst is arranged on the porous solid catalyst bed layer 7; the bottom of the porous solid catalyst bed layer 7 is provided with a catalyst support plate 6, and the lower part in the bubbling reactor 5 is provided with a gas distributor 24; the top of the bubble reactor 5 is provided with a safety valve 8.
Preferably, the wastewater storage tank 1 is connected to the filtering device 3 by means of a first pressurized delivery pump 2; a liquid phase pressure reduction regulating valve 10 is arranged on a pipeline between the bubbling reactor 5 and the flash evaporation device 11; a vapor phase decompression regulating valve 17 is arranged on one end of the pipeline between the bubbling reactor 5 and the primary gas-liquid separator 18 and close to the bubbling reactor 5; the desalting filter 13 is also connected with the filtering device 3 through a second pressure delivery pump 14; the top of the secondary gas-liquid separator 20 is provided with a blow-down valve 21.
When the device is used for treating the waste water produced by isooctyl thioglycolate, the catalytic oxidation auxiliary agent 22 is firstly added into the waste water in the waste water storage tank 1, the waste water is pressurized by the first pressurizing delivery pump 2 and then enters the filtering device 3, the filtered organic waste water enters the bubbling reactor 5 through the preheating device 4, the oxidant is pressed from the bottom of the bubbling reactor 5 through the air compressor 9, the oxidant is uniformly dispersed in the waste water through the gas distributor 24, the oxidation reaction is carried out by utilizing the combined action of the catalytic oxidation auxiliary agent 22 and the porous solid catalyst, and the organic matters in the waste water are quickly oxidized into H2O、CO2And SO4 2-And the like, non-toxic compounds;
the liquid generated by the oxidation reaction is decompressed by a liquid phase decompression regulating valve 10 and then enters a flash evaporation device 11, the liquid after flash evaporation is further concentrated by an evaporation device 12, the generated liquid is separated by a desalting filter 13 to obtain solid salt 23 and concentrated liquid, the concentrated liquid contains a catalytic oxidation auxiliary agent 22, the catalytic oxidation auxiliary agent is pressurized by a second pressurization conveying pump 14 and then returns to a filtering device 3, and then the catalytic oxidation auxiliary agent enters a preheating device 4 and is applied to the process, so that the cyclic utilization of the catalytic oxidation auxiliary agent 22 is realized; the gas generated by the evaporation device 12 is condensed into water by a second condenser 15 and enters a distilled water storage tank 16;
the gas generated by the oxidation reaction is decompressed by a vapor phase decompression regulating valve 17 and then enters a primary gas-liquid separator 18 together with the gas generated by flash evaporation for separation, the liquid enters a distilled water storage tank 16, the gas enters a secondary gas-liquid separator 20 through a first condenser 19 for re-separation, and the obtained liquid enters the distilled water storage tank 16 again; through the device, the high-efficiency degradation of the isooctyl thioglycolate production wastewater is realized, and the high-efficiency recycling of the solid salt is realized.

Claims (8)

1. A treatment method of isooctyl thioglycolate production wastewater is characterized by comprising the following steps: mixing catalytic oxidation auxiliary agent into isooctyl thioglycolate production wastewater in advance, preheating the mixture, introducing the mixture into a bubbling reactor, and carrying out oxidation reaction with oxidant so as to oxidize organic matters in the wastewater into H2O、CO2And SO4 2-Desalting the reaction solution after reaction by flash evaporation and evaporation concentration; the catalytic oxidation auxiliary agent is soluble cobalt salt, and the bubbling reactor is filled with TiO2Supported MoO3A porous solid catalyst;
mixing soluble cobalt salt into isooctyl thioglycolate production wastewater, and adding Co2+The molar concentration in the isooctyl thioglycolate production wastewater is 0.1-0.4 mmol/L;
the salt in the waste water from the production of isooctyl thioglycolate is NaCl, the salt content is 17.0-22.0wt.%, the COD content is 15000-20000mg/L, and the pH value is 0.5-5.0.
2. The method for treating waste water from the production of isooctyl thioglycolate according to claim 1, wherein the method comprises the following steps: TiO 22Supported MoO3The porous solid catalyst was in the form of particles having a porosity of 30%.
3. The method for treating waste water from the production of isooctyl thioglycolate according to claim 1, wherein the method comprises the following steps: the oxidant is oxygen or air.
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 oxidation reaction temperature is 150 ℃ and 250 ℃, the oxidation reaction time is 10-120min, and the oxidation reaction pressure is 2.0-10.0 MPa.
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 preheating temperature is 150 ℃ and 250 ℃.
6. An apparatus for treating waste water from the production of isooctyl thioglycolate by using the method of any one of claims 1 to 5, comprising a waste water storage tank (1), characterized in that: the waste water storage tank (1) is sequentially connected with the filtering device (3), the preheating device (4), the bubbling reactor (5), the flash evaporation device (11), the evaporation device (12) and the desalting filter (13); the bubbling reactor (5) is also sequentially connected with a primary gas-liquid separator (18) and a distilled water storage tank (16), and the bottom of the bubbling reactor (5) is connected with an air compressor (9); the evaporation device (12) is connected with a distilled water storage tank (16).
7. The apparatus for treating waste water from the production of isooctyl thioglycolate according to claim 6, wherein: the primary gas-liquid separator (18) is also connected with a distilled water storage tank (16) in sequence through a first condenser (19) and a secondary gas-liquid separator (20); the evaporation device (12) is connected with a distilled water storage tank (16) through a second condenser (15); the flash evaporation device (11) is also connected to a pipeline between the bubble reactor (5) and the primary gas-liquid separator (18); the desalting filter (13) is also connected with a filtering device (3).
8. The apparatus for treating waste water from the production of isooctyl thioglycolate according to claim 6, wherein: the middle part in the bubbling reactor (5) is provided with a porous solid catalyst bed layer (7), the bottom of the porous solid catalyst bed layer (7) is provided with a catalyst support plate (6), and the lower part in the bubbling reactor (5) is provided with a gas distributor (24).
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