A method for efficiently treating the wastewater produced in the production of butanone oxime

Abstract

The present invention relates to a method for efficiently treating methyl ethyl ketoxime production wastewater, belonging to the technical field of methyl ethyl ketoxime production wastewater treatment. In the present invention, methyl ethyl ketoxime wastewater, iron-carbon material, H2O2 solution, and coagulant are reacted, precipitated, and filtered; the filtered clear liquid is taken, and after nitrogen stripping; activated sludge is added, and mechanical stirring is used to keep the sludge in a uniform fluidized state in the clear liquid for anaerobic treatment and aerobic treatment; the coagulant of the present invention is prepared by reacting ferrocenyl hexanethiol, benzofuran-based acrylamide, toluene, and a photoinitiator under ultraviolet light irradiation with an absorption wavelength of 365 nm, and after the reaction, toluene is removed by distillation; the benzofuran-based acrylamide of the present invention is prepared by 2,3-dihydro-1-benzofuran-5-yl isocyanate, hydroxymethyl acrylamide, organotin, and DMF; the coagulant prepared by the present invention can effectively remove various impurities such as COD, ammonia nitrogen, and TP in methyl ethyl ketoxime wastewater.

Description

Technical Field

[0001] The present invention relates to the technical field of methyl ethyl ketoxime production wastewater treatment, and particularly to a method for efficiently treating methyl ethyl ketoxime production wastewater. Background Art

[0002] Methyl ethyl ketoxime is a colorless or light yellow oily transparent liquid antioxidant, mainly used as a boiler deoxidizer, and also as an anti-skinning agent in materials such as coatings, paints, and inks. It is a raw material for the production of neutral crosslinking agents such as methyltris (ethyl methyl ketoxime) silane and vinyltris (ethyl methyl ketoxime) silane. Methyl ethyl ketoxime production wastewater is a type of organic chemical wastewater with high toxicity, low pH value, and unbalanced carbon-nitrogen ratio, which is difficult to directly treat by biochemical methods.

[0003] Chinese Patent CN215480382U: provides a biological treatment device for methyl ethyl ketoxime 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 with 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 with an alkali inlet pipe and is connected to the biochemical tank through a second pipeline; a membrane module and a filter screen are arranged in the biochemical tank, the part of the biochemical tank located under the filter screen is connected with a bacteria inlet pipe and is connected to the part below the filter screen through a circulation pipe; the membrane module is located above the filter screen 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 with a feeding pump, the first pipeline and the second pipeline are both connected with a suction pump, the circulation pipe is connected with a circulation pump, and the water outlet pipe is connected with a water extraction pump.

[0004] Chinese Patent CN107739129A: relates to a treatment method for wastewater containing oxime. The wastewater containing oxime refers to the wastewater generated in the production and use of oxime chemical products, which cannot be directly discharged into the sewage network without treatment. The treatment method for the wastewater containing oxime in the present invention specifically comprises the following steps: First step: adding dilute acid to the wastewater containing oxime, adjusting the pH to between 5 and 6, and stirring simultaneously; Second step: adding hydrogen peroxide, with 2000 - 3000 mg added per liter of water; Third step: pumping the wastewater with adjusted pH into an evaporator, introducing a recovery heat source, and stirring; Fourth step: biochemical treatment.

[0005] Chinese Patent CN203144233U: discloses a treatment system for wastewater containing COD and ammonia nitrogen, characterized in that it includes a water inlet, a water outlet, a COD and ammonia nitrogen adjustment tank, a pH callback tank, an anaerobic baffle adjustment tank, an intermittent sewage treatment tank, and a clear water tank. Among them, the wastewater is connected to the COD and ammonia nitrogen adjustment tank through the water inlet, one end of the pH callback tank is connected to the COD and ammonia nitrogen adjustment tank, and the other end is connected to the anaerobic baffle adjustment tank; one end of the intermittent sewage treatment tank is connected to the anaerobic baffle adjustment tank, and the other end is connected to the clear water tank; the water outlet is connected to the clear water tank.

[0006] The methyl ethyl ketoxime wastewater treated by the existing technology has high COD, ammonia nitrogen, and TP, poor biodegradability, and high operating costs. Summary of the Invention

[0007] To solve the above problems, the present invention provides a method for efficiently treating methyl ethyl ketoxime production wastewater, and its operating steps are as follows:

[0008] S1: Take 80 - 100 parts of methyl ethyl ketoxime wastewater and 35 - 45 parts of iron-carbon material, react for 60 - 120 min, and control the pH value during the reaction;

[0009] S2: After the reaction is completed, add 0.1 - 0.5 parts of H2O2 solution, continue to react for 5 - 10 min, and control the pH value during the reaction;

[0010] S3: Add 0.001 - 0.01 parts of coagulant, react for 1 - 3 min, stand for precipitation, and filter;

[0011] 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, and use mechanical stirring to keep the sludge in a uniform fluidization state in the clear liquid for anaerobic treatment and aerobic treatment;

[0012] The coagulant is prepared by reacting ferrocenyl hexanethiol and benzofuran-based acrylamide.

[0013] The pH value of S1 is 2 - 3.

[0014] The mass concentration of the H2O2 solution is 20 - 30%.

[0015] The pH value of S2 is 8 - 9.

[0016] The DO mass concentration is 0.1 - 0.2 mg / L.

[0017] The anaerobic treatment time is 120 - 180 min.

[0018] The aerobic treatment time is ⑧ - 12 h.

[0019] The preparation method of the coagulant is as follows:

[0020] By weight, add 7 - 15 parts of ferrocenyl hexanethiol, 50 - 80 parts of benzofuran-based acrylamide, and 300 - 500 parts of toluene into a stirring kettle. After mixing, add 0.05 - 0.5 parts of photoinitiator, and carry out a click chemical reaction under ultraviolet light irradiation with a maximum absorption wavelength of 365 nm. The reaction time is 30 - 100 minutes. After the reaction is completed, remove toluene by distillation to obtain the coagulant.

[0021] The photoinitiator is one of photoinitiator 1173, photoinitiator TPO, photoinitiator 819, photoinitiator benzophenone, and photoinitiator ITX.

[0022] The preparation method of the benzofuranyl acrylamide is as follows:

[0023] By weight, add 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 into a stirring kettle, react at 60 - 70 °C for 60 - 100 minutes, and distill off DMF to obtain benzofuranyl acrylamide.

[0024] Reaction mechanism

[0025] 1. Ferrocenyl hexanethiol: This is an organic compound containing iron element and is usually used as a catalyst or ligand in synthesis.

[0026] 2. Benzofuranyl acrylamide: This compound may participate in click chemical reactions.

[0027] 3. Basic principle of click chemical reaction

[0028] Under the irradiation of ultraviolet light at 365 nm, the double bond in benzofuranyl acrylamide reacts with the thiol group (-SH) in ferrocenyl hexanethiol through a thiol - ene click chemical reaction. This reaction generally includes the following steps:

[0029] Generation of photo - initiated free radicals: The photoinitiator absorbs ultraviolet light and decomposes to generate free radicals.

[0030] Attack of free radicals: The generated free radicals attack the double bond in benzofuranyl acrylamide to form a new carbon - carbon bond.

[0031] Reaction of thiol group: Meanwhile, the thiol group attacks the double bond of another molecule to form a new thioether bond.

[0032] Generally speaking, the click chemical reaction of ferrocenyl hexanethiol and benzofuranyl acrylamide under ultraviolet light irradiation is an efficient, environmentally friendly and widely applicable synthesis method. The coagulant obtained by this synthesis method can be used for the preparation of butanone oxime, demonstrating its practical application potential in organic synthesis.

[0033] Technical effects

[0034] A method for efficiently treating butanone oxime production wastewater in the present invention has the following remarkable effects compared with the prior art:

[0035] In the production of methyl ethyl ketoxime, using polyacrylamide containing ferrocene and benzofuranyl as a coagulant can significantly improve the coagulation effect; the following are the detailed technical effects:

[0036] 1. Enhance flocculation ability: Polyacrylamide containing ferrocene and benzofuranyl has a stronger charge density and a higher molecular weight, which enables it to more effectively adsorb suspended particles. This enhanced flocculation ability makes the suspended particles easier to aggregate into larger flocs, thus being more easily separated from the solution.

[0037] 2. Improve coagulation efficiency: Due to the special nature of its molecular structure, this polyacrylamide can form stable flocs more rapidly. This means that under the same reaction conditions, using this coagulant can complete the coagulation process faster, thereby improving production efficiency.

[0038] 3. Increase the removal rate: Polyacrylamide containing ferrocene and benzofuranyl has better adsorption ability for various pollutants. This means that it can more effectively remove various impurities generated during the production process of methyl ethyl ketoxime from the solution, thereby improving product quality.

[0039] 4. Reduce the dosage: Due to its high - efficiency coagulation performance, using 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.

[0040] In summary, polyacrylamide containing ferrocene and benzofuranyl as a coagulant in the production of methyl ethyl ketoxime can improve technical effects by enhancing flocculation ability, improving coagulation efficiency, increasing the removal rate, reducing the dosage, reducing environmental impact, and simplifying the operation process. Specific embodiments

[0041] To further elaborate on 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 examples and comparative examples. The specific test results are shown in Table 1:

[0042] COD is determined by the dichromate method; ammonia nitrogen is determined by the Nessler reagent spectrophotometric method; TP is determined by the ammonium molybdate spectrophotometric method.

[0043] Example 1

[0044] A method for efficiently treating methyl ethyl ketoxime production wastewater, the operation steps of which are as follows:

[0045] S1: Take 80 g of methyl ethyl ketoxime wastewater and 35 g of iron - carbon material, react for 60 min, and control the pH value during the reaction;

[0046] S2: After the reaction is completed, add 0.1 g of H2O2 solution and continue to react for 5 min, and control the pH value during the reaction;

[0047] S3: Add 0.001 g of coagulant, react for 1 min, let it stand for sedimentation, and then filter.

[0048] S4: Take 80 g of the filtered clear liquid, blow it off with nitrogen, and control the mass concentration of DO; add 1 g of activated sludge, and use mechanical stirring to keep the sludge in a uniform fluidized state in the clear liquid for anaerobic treatment and aerobic treatment.

[0049] The coagulant is prepared by the reaction between ferrocenylhexanethiol and benzofuran-based acrylamide.

[0050] The pH value of S1 is 2.

[0051] The mass concentration of the H2O2 solution is 20%.

[0052] The pH value of S2 is 8.

[0053] The mass concentration of DO is 0.1 mg / L.

[0054] The anaerobic treatment time is 120 min.

[0055] The aerobic treatment time is 8 h.

[0056] The preparation method of the coagulant is as follows:

[0057] Add 7 g of ferrocenylhexanethiol, 50 g of benzofuran-based acrylamide, and 300 g of toluene into a stirring kettle. After mixing, add 0.05 g of photoinitiator, and carry out a click chemical reaction under ultraviolet light irradiation with a maximum absorption wavelength of 365 nm for 30 minutes. After the reaction, remove toluene by distillation to obtain the coagulant.

[0058] The photoinitiator is photoinitiator 1173.

[0059] The preparation method of the benzofuran-based acrylamide is as follows:

[0060] Add 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 into a stirring kettle, react at 60 °C for 60 minutes, and distill off DMF to obtain benzofuran-based acrylamide.

[0061] Example 2

[0062] A method for efficiently treating methyl ethyl ketoxime production wastewater, and its operation steps are as follows:

[0063] S1: Take 85 g of methyl ethyl ketoxime wastewater and 38 g of iron-carbon material, react for 80 min, and control the pH value during the reaction.

[0064] S2: After the reaction is completed, add 0.2 g of H2O2 solution and continue the reaction for 6 min, controlling the pH value during the reaction;

[0065] S3: Add 0.005 g of coagulant, react for 2 min, let it stand for precipitation, and then filter;

[0066] S4: Take 85 g of the filtered clear liquid, blow it off with nitrogen, and control the mass concentration of DO; add 2 g of activated sludge, and use mechanical stirring to keep the sludge in a uniform fluidization state in the clear liquid for anaerobic treatment and aerobic treatment;

[0067] The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuran-based acrylamide.

[0068] The pH value of S1 is 2.

[0069] The mass concentration of the H2O2 solution is 25%.

[0070] The pH value of S2 is 8.

[0071] The mass concentration of DO is 0.15 mg / L.

[0072] The anaerobic treatment time is 140 min.

[0073] The aerobic treatment time is 9 h.

[0074] The preparation method of the coagulant is as follows:

[0075] Add 9 g of ferrocenyl hexanethiol, 60 g of benzofuran-based acrylamide, and 350 g of toluene into a stirring kettle. After mixing, add 0.2 g of photoinitiator, and carry out a click chemical reaction under ultraviolet light irradiation with a maximum absorption wavelength of 365 nm. The reaction time is 50 minutes. After the reaction is completed, remove toluene by distillation to obtain the coagulant.

[0076] The photoinitiator is photoinitiator TPO.

[0077] The preparation method of the benzofuran-based acrylamide is as follows:

[0078] Add 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 into a stirring kettle, react at 65 °C for 70 minutes, and distill off DMF to obtain benzofuran-based acrylamide.

[0079] Example 3

[0080] A method for efficiently treating methyl ethyl ketone oxime production wastewater, the operation steps of which are:

[0081] S1: Take 95 g of methyl ethyl ketoxime wastewater and 43 g of iron-carbon material, react for 100 min, and control the pH value during the reaction.

[0082] S2: After the reaction is completed, add 0.4 g of H2O2 solution and continue to react for 9 min, and control the pH value during the reaction.

[0083] S3: Add 0.008 g of coagulant, react for 2 min, let it stand for precipitation, and then filter.

[0084] S4: Take 95 g of the filtered supernatant, blow it off with nitrogen, and control the DO mass concentration; add 4 g of activated sludge, and use mechanical stirring to keep the sludge in a uniform fluidized state in the supernatant for anaerobic treatment and aerobic treatment.

[0085] The coagulant is prepared by reacting ferrocenyl hexanethiol and benzofuran-based acrylamide.

[0086] The pH value of S1 is 3.

[0087] The mass concentration of the H2O2 solution is 25%.

[0088] The pH value of S2 is 9.

[0089] The DO mass concentration is 0.15 mg / L.

[0090] The anaerobic treatment time is 160 min.

[0091] The aerobic treatment time is 11 h.

[0092] The preparation method of the coagulant is as follows:

[0093] Add 13 g of ferrocenyl hexanethiol, 70 g of benzofuran-based acrylamide, and 450 g of toluene into a stirring kettle. After mixing, add 0.4 g of photoinitiator and carry out a click chemical reaction under ultraviolet light irradiation with a maximum absorption wavelength of 365 nm. The reaction time is 80 minutes. After the reaction is completed, remove toluene by distillation to obtain the coagulant.

[0094] The photoinitiator is photoinitiator 819.

[0095] The preparation method of the benzofuran-based acrylamide is as follows:

[0096] Add 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 into a stirring kettle, react at 65 °C for 90 minutes, and distill off DMF to obtain benzofuran-based acrylamide.

[0097] Example 4

[0098] A method for efficiently treating the wastewater produced in the production of methyl ethyl ketoxime, and its operation steps are as follows:

[0099] S1: Take 100 g of methyl ethyl ketoxime wastewater and 45 g of iron-carbon material, react for 120 min, and control the pH value during the reaction;

[0100] S2: After the reaction is completed, add 0.5 g of H2O2 solution, continue to react for 10 min, and control the pH value during the reaction;

[0101] S3: Add 0.01 g of coagulant, react for 3 min, stand for sedimentation, and filter;

[0102] S4: Take 100 g of the filtered clear liquid, blow it off with nitrogen, and control the mass concentration of DO; add 5 g of activated sludge, and use mechanical stirring to keep the sludge in a uniform fluidized state in the clear liquid, and carry out anaerobic treatment and aerobic treatment;

[0103] The coagulant is prepared by reacting ferrocenyl hexanethiol and benzofuran-based acrylamide.

[0104] The pH value of S1 is 3.

[0105] The mass concentration of the H2O2 solution is 30%.

[0106] The pH value of S2 is 9.

[0107] The mass concentration of DO is 0.2 mg / L.

[0108] The anaerobic treatment time is 180 min.

[0109] The aerobic treatment time is 12 h.

[0110] The preparation method of the coagulant is as follows:

[0111] Add 15 g of ferrocenyl hexanethiol, 80 g of benzofuran-based acrylamide, and 500 g of toluene into a stirring kettle. After mixing, add 0.5 g of photoinitiator, and carry out a click chemical reaction under ultraviolet light irradiation with a maximum absorption wavelength of 365 nm. The reaction time is 100 minutes. After the reaction is completed, remove toluene by distillation to obtain the coagulant.

[0112] The photoinitiator is benzophenone photoinitiator.

[0113] The preparation method of the benzofuran-based acrylamide is as follows:

[0114] Add 30 g of 2,3-dihydro-1-benzofuran-5-yl isocyanate, 120 g of hydroxymethylacrylamide, 6 g of organotin, and 400 g of DMF to a stirring kettle, react at 70 °C for 100 minutes, and distill off DMF to obtain benzofuranyl acrylamide.

[0115] Comparative Example 1

[0116] Instead of adding a coagulant, add polyacrylamide, and the others are the same as in Example 1.

[0117] Comparative Example 2

[0118] Do not add benzofuranyl acrylamide, and the others are the same as in Example 1.

[0119] Comparative Example 3

[0120] Do not add ferrocenyl hexanethiol, and the others are the same as in Example 1.

[0121] Table 1

[0122] 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

[0123] Through the data analysis of the above examples and comparative examples, the coagulant prepared by the present invention can effectively remove various impurities such as COD, ammonia nitrogen, and TP in methyl ethyl ketoxime wastewater.

[0124] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to the equivalent embodiments by using the disclosed technical content within the scope of the technical solution of the present invention. However, any brief modification, equivalent change, and modification made to the above embodiments based on the technical essence of the present invention still fall 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 of which 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 complete, add 0.1-0.5 parts of H2O2 solution and continue the reaction for 5-10 minutes, controlling the pH value during the reaction; S3: Add 0.001-0.01 parts of coagulant, react for 1-3 minutes, let it 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 acrylamide; The preparation method of the coagulant is: In a stirred tank, 7-15 parts of ferrocenyl hexanethiol, 50-80 parts of benzofuranyl acrylamide, and 300-500 parts of toluene are added by weight, 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 for 30-100 minutes. After the reaction is completed, the toluene is removed by distillation to obtain a coagulant; The preparation method of the benzofuranyl-containing acrylamide is as follows: In a stirred tank, 20-30 parts by weight 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. The mixture is reacted at 60-70° C. for 60-100 minutes, and the DMF is removed by distillation to obtain acrylamide containing benzofuranyl.

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, wherein: The pH value of the S2 is 8-9.

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

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

8. The method for efficiently treating butanone oxime production wastewater according to claim 1, wherein: The photoinitiator is one of photoinitiator 1173, photoinitiator TPO, photoinitiator 819, photoinitiator benzophenone, and photoinitiator ITX.