Treatment method of menadione nicotinamide bisulfite production wastewater

Abstract

The invention discloses a treatment method of menadione nicotinamide bisulfite production wastewater, which comprises the following steps: the menadione nicotinamide bisulfite production wastewater is subjected to static layering, the upper layer is a butanol organic phase, and the lower layer is a water phase; distilling the butanol organic phase to obtain wastewater; introducing the wastewater into an ozone pool for exposure; the upper layer is a menadione nicotinamide bisulfite phase, and the lower layer is a wastewater phase; after standing and layering the menadione nicotinamide bisulfite phase, extracting the upper-layer light liquid again, and returning the lower-layer heavy liquid to be used for blending the menadione nicotinamide bisulfite; performing low-temperature evaporation and concentration on the exposed wastewater and the wastewater phase to obtain mixed wastewater; and pouring the mixed wastewater into a microbial tank for treatment. The treatment process is clean, environmentally friendly, stable, low in operation cost, high in pollutant removal rate and free of secondary pollution. The COD in the treated wastewater reaches the national second-level or even first-level standard of sewage organic matter discharge.

Description

Technical Field

[0001] The invention belongs to the technical field of wastewater treatment, and more specifically, relates to a method for treating wastewater produced by the production of nicotinamide menadione bisulfite. Background Art

[0002] At present, the vitamin K3 products on the market mainly include menadione sodium bisulfite (MSB), menadione sodium bisulfite complex (MSBC), menadione dimethylpyrimidine sulfite (MPB), and menadione nicotinamide sulfite (MNB). Vitamin K3 has medical effects. It is the earliest used vitamin and the most biologically active one in the vitamin K family. It is also an important intermediate for anti-hemorrhagic drugs and is clinically used for the prevention and treatment of bleeding, spasm relief, and analgesia. It can also be used as a feed additive, plant growth regulator, promoter, and herbicide; it can also be used in coatings for ships, warships, etc. It has a wide range of uses and a broad market prospect.

[0003] MNB (nicotinamide menadione bisulfite) is produced by the reaction of 2-methyl-1,4-naphthoquinone with sodium bisulfite and nicotinamide. During the synthesis of MNB, a large amount of solvents such as butanol and water are required, resulting in the final wastewater containing a large amount of salt and organic matter.

[0004] At present, the commonly used treatment method is "evaporation concentration + multi-stage distillation", and then incineration is used for treatment. For example, the method for zero discharge of high-salt wastewater disclosed in Chinese patent CN102616873A adopts efficient evaporation to achieve zero discharge of high-salt wastewater. The method for treating high-salt and high-organic content wastewater taught by Chinese patent CN102351269A adopts extraction phase separation, the aqueous phase is evaporated, and the organic phase is incinerated. However, for wastewater with high salinity and high organic content, evaporation and concentration not only consumes a lot of energy, but also has great difficulty in evaporation and low operational stability. At the same time, incineration treatment will release odorous gases, which is easy to cause secondary pollution and increase the treatment cost.

[0005] Therefore, in view of the above-mentioned prior art status, it is hoped to find a method for treating MNB production wastewater with low pollution, environmental friendliness and low energy consumption. Summary of the invention

[0006] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0007] In order to achieve these purposes and other advantages according to the present invention, a method for treating wastewater produced by nicotinamide menadione bisulfite is provided, comprising the following steps:

[0008] Step 1, the wastewater produced by nicotinamide menadione bisulfite is statically layered, wherein the upper layer is a butanol organic phase and the lower layer is an aqueous phase;

[0009] Step 2: distilling the butanol organic phase to recover the solvent and obtain waste water;

[0010] Step 3: Expose the wastewater from solvent recovery into an ozone tank;

[0011] Step 4, extracting and stratifying the aqueous phase, wherein the upper layer is a nicotinamide menadione hydrogen sulfite phase, and the lower layer is a wastewater phase; after the nicotinamide menadione hydrogen sulfite phase is allowed to stand for stratification, the upper light liquid of the stratified upper layer is extracted again, the extracted lower aqueous liquid is added to the wastewater phase, the extracted upper organic phase is allowed to stand and circulate for extraction according to the treatment method of the nicotinamide menadione hydrogen sulfite phase, and the lower heavy liquid of the stratified lower layer is returned for use in the nicotinamide menadione hydrogen sulfite ingredient preparation;

[0012] Step 5, performing low-temperature evaporation and concentration on the wastewater after exposure in step 3 and the wastewater obtained in step 4 to obtain mixed wastewater;

[0013] Step 6: Pour the mixed wastewater concentrated by low-temperature evaporation into the microbial pool for treatment.

[0014] Preferably, in the step 1, the butanol organic phase comprises butanol, menadione, sodium menadione bisulfite, and nicotinamide menadione bisulfite.

[0015] Preferably, in the step 1, the aqueous phase comprises sodium sulfate and nicotinamide menadione bisulfite.

[0016] Preferably, in the step 2, the distillation temperature is 120-180° C., and the distillation time is 1-8 hours.

[0017] Preferably, in step three, the exposure time of the wastewater in the ozone tank is 8 to 16 hours.

[0018] Preferably, in step five, the low-temperature evaporation concentration temperature is 50-80°C.

[0019] Preferably, in step five, the evaporated and concentrated mixed wastewater enters the microbial pool for treatment for 12 to 36 hours.

[0020] Preferably, in step 4, the extractant used for aqueous phase extraction is ether, and liquid-liquid extraction is performed.

[0021] Preferably, the volume of the ether is 1 to 2 times the volume of the aqueous phase.

[0022] Preferably, in the step 4, the specific method of extracting and stratifying the aqueous phase includes: adding dilute sulfuric acid to the aqueous phase to adjust the pH value of the aqueous phase to 1-2; adding ether, sampling to preliminarily determine that the pH value of the aqueous phase is 3.5-4.5, stopping stirring and standing to separate, to obtain an upper nicotinamide menadione hydrogen sulfite phase and a lower wastewater phase; adding alkali to the upper nicotinamide menadione hydrogen sulfite phase to adjust the pH to 6-7, standing to separate, continuing to add dilute sulfuric acid to the upper light liquid to adjust the pH to 1-2, adding ether, sampling to preliminarily determine that the pH value is 3.5-4.5, stopping stirring and standing to separate, the extracted lower aqueous liquid is added to the wastewater phase, the extracted upper organic phase is stood and cyclically extracted for multiple times according to the treatment method of the nicotinamide menadione hydrogen sulfite phase, and the stood lower heavy liquid is returned to be used for nicotinamide menadione hydrogen sulfite ingredient.

[0023] In order to further reduce the COD of the mixed wastewater treated in the microbial pool in step six, a carbon-aluminum adsorbent is added to the microbial pool, and the mass volume ratio of the carbon-aluminum adsorbent to the mixed wastewater in step six is ​​1-50g:500-1000mL; the preparation method of the carbon-aluminum adsorbent includes:

[0024] S1. Dry the wheat straw and crush it into powder, sieve it with 200-300 mesh, and carbonize the sieved powder at a carbonization temperature of 400-600°C for 4-8 hours. Take out the carbonized powder after cooling to room temperature, and then put it into 1.5 mol / L hydrochloric acid for 12-24 hours to remove ash. The mass volume ratio of biochar powder to hydrochloric acid is 0.5-0.8 g:10 mL. After filtering, wash it with distilled water until it is neutral, and dry it at a temperature of 80-90°C to obtain biochar.

[0025] S2. Magnesium acetate, magnesium hydroxide, aluminum hydroxide and calcium sulfate are weighed in a mass ratio of 1:1:5:1, and mixed to obtain a mixed powder. The mixed powder is mixed with biochar in a mass ratio of 1:4-6 and ground. After grinding for 6-12 hours, the mixed powder is sieved with 80-150 mesh, and then vacuum calcined at 600-900° C. for 6-12 hours, and cooled to room temperature to obtain a carbon-aluminum mixed powder.

[0026] S3. Evenly mix the carbon-aluminum mixed powder with ethanol and polyaluminum chloride in a mass ratio of 20-50:2-15:5-10, and then evaporate and remove the ethanol at 110-160° C. to obtain a carbon-aluminum adsorbent.

[0027] The invention at least includes the following beneficial effects: the present invention adopts the treatment process of "grading → organic phase treatment + water phase treatment" which is clean and environmentally friendly, with stable process, low operating cost, high pollutant removal rate and no secondary pollution. At the same time, the COD in the treated wastewater reaches the national sewage organic matter discharge level 2 or even level 1 standard (GB / 8978-1996--"Comprehensive Sewage Discharge Standard" has specific requirements for the "maximum allowable discharge concentration of the second class of pollutants", the first-level discharge standard for pharmaceutical wastewater is COD≤100mg / L, the second-level discharge standard is COD≤300mg / L, and the third-level discharge standard is COD≤1000mg / L), directly returning to production for use will not have a significant impact on product quality, can greatly reduce the use of fresh salting-out agent and process water, save production costs, and improve resource recycling rate. In addition, the wastewater treated by the present invention achieves zero discharge of wastewater by recycling.

[0028] At the same time, the present invention also adds a carbon-aluminum adsorbent to the microbial pool in step six, and the carbon-aluminum adsorbent further reduces the COD concentration in the wastewater after the circulation treatment by adsorbing organic matter (mainly containing menadione, sodium menadione bisulfite, and nicotinamide menadione bisulfite) in the wastewater phase obtained by separating the butanol organic phase and extracting the aqueous phase, so as to meet the emission standards. Among them, the carbon-aluminum adsorbent uses biochar obtained by carbonization treatment and magnesium acetate, magnesium hydroxide, aluminum hydroxide and calcium sulfate with extremely high adsorption capacity for organic pollutants as main raw materials, ethanol and polyaluminum chloride as binders and complexing sedimentation agents, and mixes the powdered raw materials into an adsorbent as a whole, and then removes ethanol to obtain a porous and large-surface carbon-aluminum adsorbent.

[0029] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. DETAILED DESCRIPTION

[0030] The present invention is described in further detail below so that those skilled in the art can implement it according to the description.

[0031] It should be understood that the terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more other elements or combinations thereof.

[0032] Example 1

[0033] This embodiment provides a method for treating nicotinamide menadione bisulfite production wastewater, comprising the following steps:

[0034] Step 1: 10000 ml of nicotinamide menadione bisulfite production wastewater is statically layered, the upper layer is a butanol organic phase with a volume of 3000 ml and COD = 100000 mg / L, and the lower layer is an aqueous phase with a volume of 7000 mL;

[0035] Step 2: distill the butanol organic phase to recover the solvent, distill at 130° C. for 4 hours to obtain waste water;

[0036] Step 3: Expose the wastewater from solvent recovery into an ozone tank for 16 hours;

[0037] Step 4: adding dilute sulfuric acid to the aqueous phase to adjust the pH value of the aqueous phase to 2; adding ether, sampling to determine that the pH value of the aqueous phase is 4, stopping stirring and allowing to stand for stratification to obtain an upper nicotinamide menadione hydrogen sulfite phase and a lower wastewater phase; adding alkali to the upper nicotinamide menadione hydrogen sulfite phase to adjust the pH to 6, allowing to stand for stratification, continuing to add dilute sulfuric acid to the upper light liquid to adjust the pH to 2, adding ether, sampling to preliminarily determine that the pH value is 4, stopping stirring and allowing to stand for stratification, the extracted lower aqueous liquid is added to the wastewater phase, and the extracted upper organic phase is allowed to stand and circulate for 5 times according to the treatment method of the nicotinamide menadione hydrogen sulfite phase. The upper organic phase (mainly containing nicotinamide menadione hydrogen sulfite) extracted for the last time and the lower heavy liquid (nicotinamide menadione hydrogen sulfite is slightly soluble in water and has a density greater than that of water, so after standing for stratification, the lower heavy liquid mainly contains nicotinamide menadione hydrogen sulfite) are returned together for use as an ingredient for nicotinamide menadione hydrogen sulfite;

[0038] Step 5: The wastewater after exposure in step 3 and the wastewater obtained in step 4 are evaporated and concentrated at 70° C. for 6 hours to obtain mixed wastewater;

[0039] Step 6: Pour the low-temperature evaporated and concentrated mixed wastewater into the microbial pool for treatment for 24 hours. Finally, the COD of the wastewater discharged from the microbial pool is tested, and the measured COD is 300 mg / L, which meets the secondary discharge standard for pharmaceutical wastewater.

[0040] At the same time, when the nicotinamide menadione bisulfite ingredient is returned for use in the production of vitamin K3 in step 4, new nicotinamide menadione bisulfite production wastewater will also be generated. The new nicotinamide menadione bisulfite production wastewater is recycled according to the method of step 1 to step 6. After the nicotinamide menadione bisulfite production wastewater is recycled 20 times, it is found that the quality of the MNB product is not adversely affected by the use of the recycled wastewater.

[0041] Example 2

[0042] This embodiment provides a method for treating wastewater produced by nicotinamide menadione bisulfite. The difference from Example 1 is that in this embodiment, a carbon-aluminum adsorbent is added to the microbial pool in step six, and the mass volume ratio of the carbon-aluminum adsorbent to the mixed wastewater in step six is ​​1 g: 100 mL; the preparation method of the carbon-aluminum adsorbent includes:

[0043] S1. Dry the wheat straw and crush it into powder, sieve it through 300 mesh, and carbonize the sieved powder at a carbonization temperature of 500°C for 4 hours; take out 50g of the carbonized powder cooled to room temperature after carbonization, and then put it into 1L of 1.5mol / L hydrochloric acid for 12 hours to remove ash, filter it, wash it with distilled water until it is neutral, and dry it at 90°C to obtain biochar;

[0044] S2, weighing 100g of magnesium acetate, 100g of magnesium hydroxide, 500g of aluminum hydroxide and 100g of calcium sulfate, mixing to obtain a mixed powder, mixing the mixed powder with 4000g of biochar and grinding, grinding for 6h, sieving with 100 mesh, then calcining under vacuum at 700°C for 6h, and cooling to room temperature to obtain a carbon-aluminum mixed powder;

[0045] S3. Evenly mix 400 g of carbon-aluminum mixed powder, 150 g of ethanol and 50 g of polyaluminum chloride, and then evaporate to remove the ethanol at 120° C. to obtain a carbon-aluminum adsorbent.

[0046] The methods and process parameters of the remaining steps of this embodiment are the same as those of Example 1. The COD of the wastewater discharged from the microbial pool in Step 6 of this embodiment is measured to be 84.7 mg / L, which meets the first-level discharge standard for pharmaceutical wastewater.

[0047] Example 3

[0048] This embodiment provides a method for treating wastewater produced by nicotinamide menadione bisulfite. The difference from Embodiment 1 is that in this embodiment, a carbon-aluminum adsorbent is added to the microbial pool in step six, and the mass volume ratio of the carbon-aluminum adsorbent to the mixed wastewater in step six is ​​1 g: 100 mL; the preparation method of the carbon-aluminum adsorbent includes:

[0049] S1. Dry the wheat straw and crush it into powder, sieve it through 200 mesh, and carbonize the sieved powder at a carbonization temperature of 600°C for 8 hours; take out 80g of the carbonized powder that has been cooled to room temperature after carbonization, and then put it into 1L of 1.5mol / L hydrochloric acid for 24 hours to remove ash, filter it, wash it with distilled water until it is neutral, and dry it at 90°C to obtain biochar;

[0050] S2, weighing 100g of magnesium acetate, 100g of magnesium hydroxide, 500g of aluminum hydroxide and 100g of calcium sulfate, mixing to obtain a mixed powder, mixing the mixed powder with 4800g of biochar and grinding, using zirconium oxide as grinding, grinding for 6h, sieving through 150 mesh, then vacuum calcining at 900°C for 2h, and cooling to room temperature to obtain a carbon-aluminum mixed powder;

[0051] S3. Evenly mix 500 g of carbon-aluminum mixed powder, 150 g of ethanol and 80 g of polyaluminum chloride, and then evaporate to remove the ethanol at 120° C. to obtain a carbon-aluminum adsorbent.

[0052] The methods and process parameters of the remaining steps of this embodiment are the same as those of Example 1. The COD of the wastewater discharged from the microbial pool in Step 6 of this embodiment is measured to be 68.2 mg / L, which meets the first-level discharge standard for pharmaceutical wastewater.

[0053] Comparative Example 1

[0054] This comparative example provides a method for treating wastewater from the production of nicotinamide menadione bisulfite, which is different from Example 3 in that polyaluminium chloride of the same mass as the carbon-aluminium adsorbent of Example 3 is added to the microbial pool in step 6, and the methods and process parameters of the remaining steps of this comparative example are the same as those of Example 3. The COD of the wastewater discharged from the microbial pool in step 6 of this comparative example is measured to be 207.1 mg / L, which is significantly lower than that in Example 1, but higher than that in Example 2 and Example 3, and does not meet the primary discharge standard for pharmaceutical wastewater.

[0055] Comparative Example 2

[0056] This comparative example provides a method for treating wastewater produced by nicotinamide menadione bisulfite, which is different from Example 3 in that biochar and polyaluminium chloride having the same total mass as the carbon-aluminium adsorbent in Example 3 are added to the microbial pool in step 5, and the preparation method of biochar is the same as that in Example 3, and biochar, polyaluminium chloride and ethanol are first mixed according to the method in Example 3 and then ethanol is removed, and the methods and process parameters of the remaining steps of this comparative example are the same as those in Example 3. The COD of the wastewater discharged from the microbial pool in step 6 of this comparative example is measured to be 160.0 mg / L, which is lower than that in Example 1, but higher than that in Example 2 and Example 3, and does not meet the primary discharge standard for pharmaceutical wastewater.

[0057] Comparative Example 3

[0058] This comparative example provides a method for treating wastewater from the production of nicotinamide menadione bisulfite, which is different from Example 3 in that magnesium acetate, magnesium hydroxide, aluminum hydroxide, calcium sulfate and polyaluminum chloride having the same total mass as the carbon-aluminum adsorbent in Example 3 are added to the microbial pool in step 6 of this comparative example, and magnesium acetate, magnesium hydroxide, aluminum hydroxide, calcium sulfate and polyaluminum chloride are mixed using the mixing method of Example 3, that is, first mixed with ethanol and then the ethanol is removed; the methods and process parameters of the remaining steps of this comparative example are the same as those of Example 3. The COD of the wastewater discharged from the microbial pool in step 6 of this comparative example was measured to be 127.4 mg / L, which is significantly lower than that in Example 1, but higher than that in Example 2 and Example 3, and does not meet the primary discharge standard for pharmaceutical wastewater.

[0059] The number of devices and processing scales described here are used to simplify the description of the present invention. Applications, modifications and variations of the present invention will be obvious to those skilled in the art.

[0060] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the examples shown and described herein.

Claims

1. A method for treating wastewater from the production of nicotinamide menadione bisulfite, characterized in that: The following steps are involved: Step 1, the wastewater from the production of nicotinamide menadione bisulfite is statically layered, wherein the upper layer is a butanol organic phase and the lower layer is an aqueous phase; Step 2: distilling the butanol organic phase to recover the solvent and obtain waste water; Step 3: Expose the wastewater from solvent recovery into an ozone tank; Step 4, extracting and stratifying the aqueous phase, wherein the upper layer is a nicotinamide menadione hydrogen sulfite phase, and the lower layer is a wastewater phase; after the nicotinamide menadione hydrogen sulfite phase is allowed to stand for stratification, the upper light liquid of the stratified upper layer is extracted again, the extracted lower aqueous liquid is added to the wastewater phase, the extracted upper organic phase is allowed to stand and circulate for extraction according to the treatment method of the nicotinamide menadione hydrogen sulfite phase, and the lower heavy liquid of the stratified lower layer is returned for use in the nicotinamide menadione hydrogen sulfite ingredient preparation; Step 5, performing low-temperature evaporation and concentration on the wastewater after exposure in step 3 and the wastewater obtained in step 4 to obtain mixed wastewater; Step 6: Pour the mixed wastewater concentrated by low-temperature evaporation into the microbial pool for treatment.

2. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 1, characterized in that: In the step 1, the butanol organic phase includes butanol, menadione, sodium menadione bisulfite, and nicotinamide menadione bisulfite.

3. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 1, characterized in that: In the step 1, the aqueous phase includes sodium sulfate and nicotinamide menadione bisulfite.

4. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 1, characterized in that: In the step 2, the distillation temperature is 120-180° C., and the distillation time is 1-8 hours.

5. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 1, characterized in that: In the step 3, the exposure time of the wastewater in the ozone tank is 8 to 16 hours.

6. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 1, characterized in that: In the step 5, the low temperature evaporation concentration temperature is 50-80°C.

7. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 1, characterized in that: In the step 5, the evaporated and concentrated mixed wastewater enters the microbial pool for treatment for 12 to 36 hours.

8. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 1, characterized in that: In the step 4, the extraction solvent used for aqueous phase extraction is ether, and liquid-liquid extraction is performed.

9. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 8, characterized in that: The volume of ether is 1 to 2 times the volume of the water phase.

10. The method for treating wastewater from the production of nicotinamide menadione bisulfite according to claim 1, characterized in that: In the step 4, the specific method of extracting and stratifying the aqueous phase includes: adding dilute sulfuric acid to the aqueous phase to adjust the pH value of the aqueous phase to 1-2; adding ether, sampling to preliminarily determine that the pH value of the aqueous phase is 3.5-4.5, stopping stirring and standing to separate, to obtain an upper nicotinamide menadione hydrogen sulfite phase and a lower wastewater phase; adding alkali to the upper nicotinamide menadione hydrogen sulfite phase to adjust the pH to 6-7, standing to separate, continuing to add dilute sulfuric acid to the upper light liquid to adjust the pH to 1-2, adding ether, sampling to preliminarily determine that the pH value is 3.5-4.5, stopping stirring and standing to separate, the extracted lower aqueous liquid is added to the wastewater phase, the extracted upper organic phase is repeatedly stood and cyclically extracted according to the treatment method of the nicotinamide menadione hydrogen sulfite phase, and the lower heavy liquid that is stood is returned to be used for nicotinamide menadione hydrogen sulfite ingredients.