Method for efficiently treating diacetylmonoxime production wastewater

Abstract

The invention relates to a method for efficiently treating diacetylmonoxime production wastewater, and belongs to the technical field of diacetylmonoxime production wastewater treatment. The method comprises the following steps: reacting diacetylmonoxime wastewater, an iron-carbon material, an H2O2 solution and a coagulant, precipitating and filtering; taking the filtered clear liquid, and carrying out air stripping by using nitrogen; adding activated sludge, mechanically stirring to keep the sludge in a uniform fluidized state in the clear liquid, and carrying out anaerobic treatment and aerobic treatment; the coagulant is prepared by the following steps: carrying out click chemical reaction on ferrocenyl hexanethiol, benzofuryl-containing acrylamide, toluene and a photoinitiator under the irradiation of ultraviolet light with the absorption wavelength of 365 nm, and distilling to remove toluene after the reaction is ended. The acrylamide containing the benzofuran group is prepared from 2, 3-dihydro-1-benzofuran-5-yl isocyanate, hydroxymethyl acrylamide, organic tin and DMF (Dimethyl Formamide), and the acrylamide containing the benzofuran group is prepared from the 2, 3-dihydro-1-benzofuran-5-yl isocyanate, the hydroxymethyl acrylamide, the organic tin and the DMF; the coagulant prepared by the invention can effectively remove various impurities such as COD (Chemical Oxygen Demand), ammonia nitrogen, TP (Total Phosphorus) and the like in diacetylmonoxime wastewater.

Description

Technical Field

[0001] The invention relates to the technical field of butanone oxime production wastewater treatment, in particular to a method for efficiently treating butanone oxime production wastewater. Background Art

[0002] Butanone oxime is a colorless or light yellow oily transparent liquid antioxidant, mainly used as boiler deoxidizer, and also as an anti-skinning agent in coatings, paints, inks and other materials. It is the raw material for the production of neutral crosslinking agents such as methyl tributylanoxime silane and vinyl tributylanoxime silane. Butanone oxime production wastewater is a type of organic chemical wastewater with high toxicity, low pH value, unbalanced carbon-nitrogen ratio, and difficult to directly treat biochemically.

[0003] Chinese patent CN215480382U: provides a biological treatment device for butanone oxime wastewater, including a container, in which an acid washing tank, an alkali washing tank and a biochemical tank are arranged; the acid washing tank is connected to a water inlet pipe and an acid inlet pipe, and is connected to the alkali washing tank through a first pipeline; the alkali washing tank is connected to an alkali inlet pipe, and is connected to the biochemical tank through a second pipeline; a membrane assembly and a filter are arranged in the biochemical tank, and the part of the biochemical tank located at the filter is connected to a bacteria inlet pipe, and is connected to the part below the filter through a circulation pipe; the membrane assembly is located above the filter, and is connected to the outside through a water outlet pipe; the acid inlet pipe, the alkali inlet pipe and the bacteria inlet pipe are all connected to a feeding pump, the first pipeline and the second pipeline are both connected to a suction pump, the circulation pipe is connected to a circulation pump, and the water outlet pipe is connected to a water pump.

[0004] Chinese patent CN107739129A: relates to a method for treating oxime-containing wastewater. Oxime-containing wastewater refers to wastewater generated by the production and use of oxime chemical products, which cannot be directly discharged into the sewage network without treatment. The method for treating oxime-containing wastewater of the present invention has the following specific steps: the first step: adding dilute acid to the oxime-containing wastewater, adjusting the pH to between 5 and 6, and stirring at the same time; the second step: adding hydrogen peroxide, 2000 to 3000 mg per liter of water; the third step: injecting the wastewater with adjusted pH into the evaporator, passing the recovered heat source, and stirring; the fourth step: biochemical treatment.

[0005] Chinese patent CN203144233U: discloses a treatment system for wastewater containing COD and ammonia nitrogen, which is characterized by: including a water inlet, a water outlet, a COD, ammonia nitrogen regulating tank, a pH adjustment tank, an anaerobic baffle regulating tank, an intermittent sewage treatment tank, and a clean water tank, wherein the wastewater is connected to the COD and ammonia nitrogen regulating tank through the water inlet, one end of the pH adjustment tank is connected to the COD and ammonia nitrogen regulating tank, and the other end is connected to the anaerobic baffle regulating tank; one end of the intermittent sewage treatment tank is connected to the anaerobic baffle regulating tank, and the other end is connected to the clean water tank; the water outlet is connected to the clean water tank.

[0006] The butanone oxime wastewater treated by the existing technology has high COD, ammonia nitrogen and TP, poor biodegradability and high operating cost. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a method for efficiently treating butanone oxime production wastewater, and the operating steps are as follows: S1: Take 80-100 parts of butanone oxime wastewater and 35-45 parts of iron-carbon material, react for 60-120 minutes, and control the pH value during the reaction; S2: After the reaction is complete, add 0.1-0.5 parts of H 2 O 2 The solution was reacted for 5-10 minutes, and the pH value was controlled during the reaction; S3: Add 0.001-0.01 parts of coagulant, react for 1-3 minutes, let stand and settle, and filter; S4: Take 80-100 parts of the filtered clear liquid, blow it off with nitrogen, and control the DO mass concentration; add 1-5 parts of activated sludge, use mechanical stirring to keep the sludge in a uniform fluidized state in the clear liquid, and perform anaerobic treatment and aerobic treatment; The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0008] The pH value of S1 is 2-3.

[0009] The H 2 O 2 The mass concentration of the solution is 20-30%.

[0010] The pH value of S2 is 8-9.

[0011] The DO mass concentration is 0.1-0.2 mg / L.

[0012] The anaerobic treatment time is 120-180 minutes.

[0013] The aerobic treatment time is 8-12 hours.

[0014] The preparation method of the coagulant is: According to weight, 7-15 parts of ferrocenyl hexanethiol, 50-80 parts of benzofuranyl acrylamide and 300-500 parts of toluene are added into a stirring kettle, 0.05-0.5 parts of a photoinitiator are added after mixing, and a click chemistry reaction is carried out under ultraviolet light with a maximum absorption wavelength of 365 nm. The reaction time is 30-100 minutes. After the reaction is completed, the toluene is removed by distillation to obtain a coagulant.

[0015] The photoinitiator is one of photoinitiator 1173, photoinitiator TPO, photoinitiator 819, photoinitiator benzophenone, and photoinitiator ITX.

[0016] The preparation method of the benzofuranyl-containing acrylamide is as follows: According to weight, 20-30 parts of 2,3-dihydro-1-benzofuran-5-yl isocyanate, 60-120 parts of hydroxymethyl acrylamide, 2-6 parts of organotin and 300-400 parts of DMF are added into a stirring kettle, reacted at 60-70° C. for 60-100 minutes, and DMF is removed by distillation to obtain benzofuranyl-containing acrylamide.

[0017] Reaction mechanism 1. Ferrocenyl hexanethiol: This is an organic compound containing iron, usually used as a catalyst or ligand in synthesis.

[0018] 2. Acrylamide containing benzofuranyl: This compound may participate in click chemistry reactions.

[0019] 3. Basic principles of click chemistry reaction Under 365nm ultraviolet light, the double bond in the benzofuranyl acrylamide reacts with the thiol group (-SH) in ferrocenyl hexanethiol to undergo a thiol-ene click chemistry reaction. This reaction generally includes the following steps: Photoinduced free radical generation: Photoinitiators decompose after absorbing ultraviolet light to produce free radicals.

[0020] Free Radical Attack: The free radical generated attacks the double bond in the benzofuranyl acrylamide, forming a new carbon-carbon bond.

[0021] Reaction of Thiol Group: Simultaneously, the thiol group attacks the double bond of another molecule to form a new thioether bond.

[0022] In general, the click chemistry reaction of ferrocenyl hexanethiol and benzofuranyl acrylamide under ultraviolet light is an efficient, environmentally friendly and widely applicable synthetic method. The coagulant obtained by this synthetic method can be used for the preparation of butanone oxime, demonstrating its practical application potential in organic synthesis.

[0023] Technical Effects The present invention discloses a method for efficiently treating butanone oxime production wastewater. Compared with the prior art, the present invention has the following significant effects: In the production of butanone oxime, the use of polyacrylamide containing ferrocene and benzofuran as a coagulant can significantly improve the coagulation effect; the following are the detailed technical effects: 1. Enhanced flocculation ability: Polyacrylamide containing ferrocene and benzofuran groups has a stronger charge density and a higher molecular weight, which enables it to adsorb suspended particles more effectively. This enhanced flocculation ability makes it easier for suspended particles to aggregate into larger flocs, making them easier to separate from the solution.

[0024] 2. Improve coagulation efficiency: Due to the particularity of its molecular structure, this polyacrylamide can form stable flocs more quickly. This means that under the same reaction conditions, the coagulation process can be completed faster using this coagulant, thereby improving production efficiency.

[0025] 3. Improve removal rate: Polyacrylamide containing ferrocene and benzofuran has better adsorption capacity for various pollutants. This means that it can more effectively remove various impurities generated in the production process of butanone oxime from the solution, thereby improving product quality.

[0026] 4. Reduce dosage: Due to its efficient coagulation performance, the use of this coagulant can reduce the required dosage, thereby reducing production costs. At the same time, this also reduces the impurities that may be generated during the treatment process. In summary, polyacrylamide containing ferrocene and benzofuran groups can be used as a coagulant in the production of butanone oxime to improve the technical effect by enhancing flocculation ability, improving coagulation efficiency, increasing removal rate, reducing dosage, reducing environmental impact and simplifying operation procedures. DETAILED DESCRIPTION

[0027] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with the embodiments and comparative examples. The specific test results are shown in Table 1: COD was determined by the dichromate method; ammonia nitrogen was determined by the Nessler reagent spectrophotometry; TP was determined by the ammonium molybdate spectrophotometry.

[0028] Example 1 A method for efficiently treating butanone oxime production wastewater, the operating steps are: S1: Take 80g of butanone oxime wastewater and 35g of iron-carbon material, react for 60min, and control the pH value during the reaction; S2: After the reaction is complete, add 0.1gH 2 O 2 The solution was reacted for 5 min, and the pH value was controlled during the reaction; S3: Add 0.001g coagulant, react for 1min, let stand to settle, and filter; S4: Take 80g of the filtered clear liquid, blow it off with nitrogen, and control the DO mass concentration; add 1g of activated sludge, use mechanical stirring to keep the sludge in the clear liquid in a uniform fluidized state, and perform anaerobic treatment and aerobic treatment; The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0029] The pH value of S1 is 2.

[0030] The H 2O 2 The mass concentration of the solution is 20%.

[0031] The pH value of S2 is 8.

[0032] The DO mass concentration is 0.1 mg / L.

[0033] The anaerobic treatment time is 120 minutes.

[0034] The aerobic treatment time is 8 hours.

[0035] The preparation method of the coagulant is: 7 g of ferrocenyl hexanethiol, 50 g of benzofuranyl acrylamide and 300 g of toluene were added to a stirring kettle, 0.05 g of a photoinitiator was added after mixing, and a click chemistry reaction was carried out under ultraviolet light with a maximum absorption wavelength of 365 nm. The reaction time was 30 minutes. After the reaction was completed, the toluene was removed by distillation to obtain a coagulant.

[0036] The photoinitiator is photoinitiator 1173.

[0037] The preparation method of the benzofuranyl-containing acrylamide is as follows: 20 g of 2,3-dihydro-1-benzofuran-5-yl isocyanate, 60 g of hydroxymethyl acrylamide, 2 g of organotin and 300 g of DMF were added to a stirring kettle, and the mixture was reacted at 60° C. for 60 minutes. DMF was distilled off to obtain benzofuranyl-containing acrylamide.

[0038] Example 2 A method for efficiently treating butanone oxime production wastewater, the operating steps are: S1: Take 85g of butanone oxime wastewater and 38g of iron-carbon material, react for 80min, and control the pH value during the reaction; S2: After the reaction is complete, add 0.2gH 2 O 2 The solution was reacted for 6 min, and the pH value was controlled during the reaction; S3: Add 0.005 g of coagulant, react for 2 min, let stand to settle, and filter; S4: Take 85g of the filtered clear liquid, blow it off with nitrogen, and control the DO mass concentration; add 2g of activated sludge, use mechanical stirring to keep the sludge in the clear liquid in a uniform fluidized state, and perform anaerobic treatment and aerobic treatment; The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0039] The pH value of S1 is 2.

[0040] The H 2O 2 The mass concentration of the solution is 25%.

[0041] The pH value of S2 is 8.

[0042] The DO mass concentration is 0.15 mg / L.

[0043] The anaerobic treatment time is 140 minutes.

[0044] The aerobic treatment time is 9 hours.

[0045] The preparation method of the coagulant is: 9 g of ferrocenyl hexanethiol, 60 g of benzofuranyl acrylamide and 350 g of toluene were added to a stirring kettle, 0.2 g of a photoinitiator was added after mixing, and a click chemistry reaction was carried out under ultraviolet light with a maximum absorption wavelength of 365 nm. The reaction time was 50 minutes. After the reaction was completed, the toluene was removed by distillation to obtain a coagulant.

[0046] The photoinitiator is photoinitiator TPO.

[0047] The preparation method of the benzofuranyl-containing acrylamide is as follows: 23 g of 2,3-dihydro-1-benzofuran-5-yl isocyanate, 80 g of hydroxymethyl acrylamide, 3 g of organotin and 340 g of DMF were added to a stirring kettle, and the mixture was reacted at 65° C. for 70 minutes. DMF was distilled off to obtain benzofuranyl-containing acrylamide.

[0048] Example 3 A method for efficiently treating butanone oxime production wastewater, the operating steps are: S1: Take 95g of butanone oxime wastewater and 43g of iron-carbon material, react for 100min, and control the pH value during the reaction; S2: After the reaction is complete, add 0.4gH 2 O 2 The solution was reacted for 9 min, and the pH value was controlled during the reaction; S3: Add 0.008 g of coagulant, react for 2 min, let stand to settle, and filter; S4: Take 95g of the filtered clear liquid, blow it off with nitrogen, and control the DO mass concentration; add 4g of activated sludge, use mechanical stirring to keep the sludge in the clear liquid in a uniform fluidized state, and perform anaerobic treatment and aerobic treatment; The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0049] The pH value of S1 is 3.

[0050] The H 2O 2 The mass concentration of the solution is 25%.

[0051] The pH value of S2 is 9.

[0052] The DO mass concentration is 0.15 mg / L.

[0053] The anaerobic treatment time is 160 minutes.

[0054] The aerobic treatment time is 11 hours.

[0055] The preparation method of the coagulant is: 13 g of ferrocenyl hexanethiol, 70 g of benzofuranyl acrylamide and 450 g of toluene were added to a stirring kettle, 0.4 g of a photoinitiator was added after mixing, and a click chemistry reaction was carried out under ultraviolet light with a maximum absorption wavelength of 365 nm. The reaction time was 80 minutes. After the reaction, the toluene was removed by distillation to obtain a coagulant.

[0056] The photoinitiator is photoinitiator 819.

[0057] The preparation method of the benzofuranyl-containing acrylamide is as follows: 28 g of 2,3-dihydro-1-benzofuran-5-yl isocyanate, 100 g of hydroxymethyl acrylamide, 5 g of organotin and 380 g of DMF were added to a stirring kettle, and the mixture was reacted at 65° C. for 90 minutes. DMF was distilled off to obtain benzofuranyl-containing acrylamide.

[0058] Example 4 A method for efficiently treating butanone oxime production wastewater, the operating steps are: S1: Take 100g butanone oxime wastewater and 45g iron-carbon material, react for 120min, and control the pH value during the reaction; S2: After the reaction is complete, add 0.5gH 2 O 2 The solution was reacted for 10 min, and the pH value was controlled during the reaction; S3: Add 0.01 g of coagulant, react for 3 min, let stand to settle, and filter; S4: Take 100g of the filtered clear liquid, blow it off with nitrogen, and control the DO mass concentration; add 5g of activated sludge, use mechanical stirring to keep the sludge in the clear liquid in a uniform fluidized state, and perform anaerobic treatment and aerobic treatment; The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0059] The pH value of S1 is 3.

[0060] The H2 O 2 The mass concentration of the solution is 30%.

[0061] The pH value of S2 is 9.

[0062] The DO mass concentration is 0.2 mg / L.

[0063] The anaerobic treatment time is 180 minutes.

[0064] The aerobic treatment time is 12 hours.

[0065] The preparation method of the coagulant is: 15 g of ferrocenyl hexanethiol, 80 g of benzofuranyl acrylamide, and 500 g of toluene were added to a stirring kettle, 0.5 g of a photoinitiator was added after mixing, and a click chemistry reaction was carried out under ultraviolet light with a maximum absorption wavelength of 365 nm. The reaction time was 100 minutes. After the reaction was completed, the toluene was removed by distillation to obtain a coagulant.

[0066] The photoinitiator is photoinitiator benzophenone.

[0067] The preparation method of the benzofuranyl-containing acrylamide is as follows: 30 g of 2,3-dihydro-1-benzofuran-5-yl isocyanate, 120 g of hydroxymethyl acrylamide, 6 g of organotin and 400 g of DMF were added to a stirring kettle, and the mixture was reacted at 70° C. for 100 minutes. DMF was distilled off to obtain benzofuranyl-containing acrylamide.

[0068] Comparative Example 1 No coagulant was added, but polyacrylamide was added instead, and the rest was the same as in Example 1.

[0069] Comparative Example 2 The benzofuranyl-containing acrylamide was not added, and the other steps were the same as in Example 1.

[0070] Comparative Example 3 The other steps were the same as in Example 1 except that ferrocenyl hexanethiol was not added.

[0071] Table 1 COD / mg / L Ammonia nitrogen / mg / L TP / mg / L Wastewater 1836 73 51 Example 1 75 23 0 Example 2 66 20 0 Example 3 61 17 0 Example 4 55 15 0 Comparative Example 1 273 48 1.21 Comparative Example 2 222 37 0.88 Comparative Example 3 198 35 0.76 Through the data analysis of the above embodiments and comparative examples, the coagulant prepared by the present invention can effectively remove various impurities such as COD, ammonia nitrogen, TP, etc. in butanone oxime wastewater.

[0072] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for efficiently treating butanone oxime production wastewater, the operating steps are: S1: Take 80-100 parts of butanone oxime wastewater and 35-45 parts of iron-carbon material, react for 60-120 minutes, and control the pH value during the reaction; S2: After the reaction is completed, add 0.1-0.5 parts of H2O2 solution and continue the reaction for 5-10 minutes, and control the pH value during the reaction; S3: Add 0.001-0.01 parts of coagulant, react for 1-3 minutes, let stand and settle, and filter; S4: Take 80-100 parts of the filtered clear liquid, blow it off with nitrogen, and control the DO mass concentration; add 1-5 parts of activated sludge, use mechanical stirring to keep the sludge in a uniform fluidized state in the clear liquid, and perform anaerobic treatment and aerobic treatment; The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

2. A method for efficiently treating butanone oxime production wastewater according to claim 1, characterized in that: The pH value of the S1 is 2-3.

3. A method for efficiently treating butanone oxime production wastewater according to claim 1, characterized in that: The mass concentration of the H2O2 solution is 20-30%.

4. The method for efficiently treating butanone oxime production wastewater according to claim 1, characterized in that: The pH value of S2 is 8-9.

5. The method for efficiently treating butanone oxime production wastewater according to claim 1, characterized in that: The DO mass concentration is 0.1-0.2 mg / L.

6. The method for efficiently treating butanone oxime production wastewater according to claim 1, characterized in that: The anaerobic treatment time is 120-180 minutes.

7. The method for efficiently treating butanone oxime production wastewater according to claim 1, characterized in that: The aerobic treatment time is 8-12 hours.

8. The method for efficiently treating butanone oxime production wastewater according to claim 1, characterized in that: The preparation method of the coagulant is: According to weight, 7-15 parts of ferrocenyl hexanethiol, 50-80 parts of benzofuranyl acrylamide and 300-500 parts of toluene are added into a stirring kettle, 0.05-0.5 parts of a photoinitiator are added after mixing, and a click chemistry reaction is carried out under ultraviolet light with a maximum absorption wavelength of 365 nm. The reaction time is 30-100 minutes. After the reaction is completed, the toluene is removed by distillation to obtain a coagulant.

9. A method for efficiently treating butanone oxime production wastewater according to claim 8, characterized in that: The photoinitiator is one of photoinitiator 1173, photoinitiator TPO, photoinitiator 819, photoinitiator benzophenone, and photoinitiator ITX.

10. The method for efficiently treating butanone oxime production wastewater according to claim 8, characterized in that: The preparation method of the benzofuranyl-containing acrylamide is as follows: According to weight, 20-30 parts of 2,3-dihydro-1-benzofuran-5-yl isocyanate, 60-120 parts of hydroxymethyl acrylamide, 2-6 parts of organotin and 300-400 parts of DMF are added into a stirring kettle, reacted at 60-70° C. for 60-100 minutes, and DMF is removed by distillation to obtain benzofuranyl-containing acrylamide.