CN113754163B - Method for treating wastewater of methyl methacrylate device - Google Patents
Method for treating wastewater of methyl methacrylate device Download PDFInfo
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- CN113754163B CN113754163B CN202010485978.7A CN202010485978A CN113754163B CN 113754163 B CN113754163 B CN 113754163B CN 202010485978 A CN202010485978 A CN 202010485978A CN 113754163 B CN113754163 B CN 113754163B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 53
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 230000007935 neutral effect Effects 0.000 claims abstract description 14
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 62
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 62
- 238000000605 extraction Methods 0.000 claims description 43
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- 238000010992 reflux Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 3
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000012071 phase Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000012856 packing Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for treating wastewater of a methyl methacrylate device. The method comprises the following steps: extracting methyl methacrylate from the wastewater by adopting a plurality of extractants to obtain a first raffinate phase; adjusting the pH value of the first raffinate phase to be neutral to obtain a second raffinate phase; and rectifying the second raffinate phase to obtain treated wastewater. The method solves the problem that methyl methacrylate is polymerized when heated in the process of removing organic matters in the wastewater in the prior art, and ensures that the COD value of the treated wastewater is lower than 15000mg/L and the PH value is close to neutral, thereby meeting the biochemical treatment requirement.
Description
Technical Field
The invention relates to the field of chemical wastewater treatment, in particular to a method for treating wastewater of a methyl methacrylate device.
Background
The equipment such as a tail gas blower, a refining layering device, a steam jet pump and the like in the device generates waste water in the normal operation process, the waste water has high COD value and strong acidity, and the waste water mainly contains organic matters such as methanol, acetone, methyl methacrylate and the like through chemical analysis, and the COD value is mainly contributed by the organic matters, so that the COD value of the waste water can be reduced only by removing the organic matters in the waste water. Methyl methacrylate contained in the wastewater starts to polymerize under the condition of normal pressure heating at the temperature of 60 ℃, and the common methyl methacrylate polymerization inhibitor cannot have a good polymerization inhibition effect in the wastewater heating process because the wastewater has complex composition and strong acidity. If methyl methacrylate in the wastewater is polymerized, the wastewater is turbid and has polymers, and biochemical treatment cannot be performed.
Taking a methyl methacrylate device of a certain factory in China as an example, the matched biochemical treatment device requires that the biochemical treatment of wastewater can meet three conditions:
(1) The wastewater is clear and has no suspended matters;
(2) COD value is lower than 20000mg/L;
(3) Neutral pH or weakly acidic.
The COD of the wastewater of the device reaches 238000mg/L, the pH value of the wastewater is 2.38, the wastewater is strong in acidity, and the wastewater cannot be directly subjected to biochemical treatment. At present, the part of waste water is mainly treated by using natural gas as fuel in a combustion way, waste gas is generated in the waste water combustion process, and the waste water treatment cost is high and the environment is not protected.
Disclosure of Invention
The invention mainly aims to provide a method for treating wastewater of a methyl methacrylate device, which aims to solve the problem that the wastewater after treatment is difficult to meet biochemical treatment requirements in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for wastewater treatment of a methyl methacrylate plant, the method comprising: extracting methyl methacrylate from the wastewater by adopting a plurality of extractants to obtain a first raffinate phase; adjusting the pH value of the first raffinate phase to be neutral to obtain a second raffinate phase; and rectifying the second raffinate phase to obtain treated wastewater.
Further, the plurality of extractants includes n-hexane, cyclohexane, and octanol.
Further, the mass ratio of n-hexane, cyclohexane and octanol is 95-97: 3.0 to 2.0:2.0 to 1.0.
Further, the ratio of the total mass of the plurality of extractants to the mass of the wastewater is 1:9-1:11.
Further, the extraction temperature is 293K to 300K.
Further, extraction is carried out under the condition of stirring, the stirring speed is 30 r/min-50 r/min, and the stirring time is controlled to be 10 min-20 min.
Further, standing for 25-35 min after stirring to obtain a first raffinate phase.
Further, the pH of the raffinate phase is adjusted to 6.0-8.0 with a base.
Further, the second raffinate phase is rectified at a pressure of less than 0.1 MPa.
Further, rectifying the second raffinate phase by adopting a rectifying tower, controlling the temperature of the tower bottom of the rectifying tower between 99 and 101 ℃, controlling the temperature of the tower top between 55 and 56 ℃ and controlling the reflux ratio between 3:1 and 5:1.
By adopting the technical scheme of the invention, the polymer methyl methacrylate in the wastewater is extracted and removed by adopting the extractant combination formed by a plurality of extractants, so that the condition that the raffinate phase is polymerized in the subsequent rectification process is avoided, and then the pH value is regulated, and the treated wastewater meets the biochemical treatment requirement by a one-step normal pressure rectification method. The method solves the problem that methyl methacrylate is polymerized when heated in the process of removing organic matters in the wastewater in the prior art, and ensures that the COD value of the treated wastewater is lower than 15000mg/L and the PH value is close to neutral, thereby meeting the biochemical treatment requirement.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
The methyl methacrylate device wastewater in the invention refers to wastewater with high COD value generated by a methyl methacrylate device (comprising equipment such as a device tail gas blower, a refining layering device, a steam jet pump and the like) produced by an acetone cyanohydrin method (ACH method) in the normal operation process.
As mentioned in the background art, the existing methyl methacrylate plant waste water contains high concentration of methyl methacrylate, which is easy to cause polymerization in the existing method, so that the treated waste water is difficult to meet the requirement of biochemical treatment. To improve this situation, in one exemplary embodiment of the present application, a method for wastewater treatment of a methyl methacrylate plant is provided, the method comprising: extracting methyl methacrylate from the wastewater by adopting a plurality of extractants to obtain a first raffinate phase; adjusting the pH value of the first raffinate phase to be neutral to obtain a second raffinate phase; and rectifying the second raffinate phase to obtain treated wastewater.
The method adopts the extractant combination formed by a plurality of extractants to extract and remove the polymer methyl methacrylate in the wastewater, so that the raffinate phase is not polymerized in the subsequent rectification process, and then the pH value is regulated, and the treated wastewater meets the biochemical treatment requirement by a one-step normal pressure rectification method. The method solves the problem that methyl methacrylate is polymerized when heated in the process of removing organic matters in the wastewater in the prior art, and ensures that the COD value of the treated wastewater is lower than 15000mg/L and the PH value is close to neutral, thereby meeting the biochemical treatment requirement.
According to the wastewater treatment method, the organic methyl methacrylate which is easy to polymerize in the wastewater is separated in an extraction mode, so that the problem that biochemical treatment cannot be performed due to the polymerization of the organic matters in the wastewater is solved, the methyl methacrylate is recovered, and the product yield is improved. The extractant for extracting methyl methacrylate can be selected according to the following principle: 1) The extraction capacity is large, namely the unit concentration of the extractant has larger extraction capacity on the extracted substances; 2) The selectivity is high, namely, the separation coefficient of the separated related substances is larger; 3) The chemical stability is good, namely, the hydrolysis is not easy, the decomposition is not easy when heated, and the acid, alkali, salt, oxidant or reducing agent can be resisted; 4) The water-solubility is small, the oil solubility is large, the water-solubility and the water-solubility are easy to delaminate, a third phase is not generated, and the emulsification phenomenon is not generated; 5) The extraction conditions are easily changed, and the extracted substances can be easily transferred from the organic phase to the water phase.
In a preferred embodiment of the present application, the plurality of extractants described above includes n-hexane, cyclohexane, and octanol.
When the proper extracting agents are selected for combination, the proportion of the specific combination can be optimized and adjusted according to the extraction effect. In a preferred embodiment of the present application, the mass ratio of n-hexane, cyclohexane and octanol is controlled to be 95-97: 3.0 to 2.0:2.0 to 1.0. At this ratio, the extraction efficiency for methyl methacrylate is higher.
In another preferred embodiment, the ratio of the total mass of the plurality of extractants to the mass of the wastewater is from 1:9 to 1:11. The total mass of the extractant and the mass of the wastewater are controlled to be about 1:10, and the extraction efficiency of methyl methacrylate in the wastewater is higher.
The extraction is carried out at normal temperature. In a preferred embodiment, the extraction temperature is 293K to 300K. The extraction is performed in the preferred temperature range, and the extraction efficiency is higher.
Under the above extraction conditions, in order to further increase the extraction rate of methyl methacrylate in the wastewater, in a preferred embodiment, the extraction is performed under stirring at a speed of 30r/min to 50r/min for a time of 10min to 20min. The stirring promotes the contact time and contact area of the extractant and the extracted object, thereby improving the extraction rate.
After stirring, standing for a certain time to effectively separate the aqueous phase from the organic phase, preferably standing for 25-35 min after stirring to separate the organic phase, thereby obtaining a first raffinate phase.
The pH value is firstly adjusted to be neutral after the first raffinate phase is obtained, and then the rectification of methanol and propanol in the wastewater is carried out, so that on one hand, the biochemical treatment requires the wastewater to be close to the neutral, and on the other hand, the pH value is firstly adjusted to be neutral, and the acidic raffinate phase can also be prevented from corroding and damaging the environment relative to rectification equipment. The specific manner of adjusting the pH is not limited, and preferably, the pH of the raffinate phase is adjusted to 6.0 to 8.0 with a base.
And rectifying the second raffinate phase regulated to be neutral under normal pressure. Preferably, the second raffinate phase is rectified at a pressure of less than 0.1 MPa.
In order to further improve the rectification efficiency of the methanol and the acetone, in a preferred embodiment, a rectification tower is adopted to rectify the second raffinate phase, the temperature of the tower bottom of the rectification tower is controlled between 99 and 101 ℃, the temperature of the tower top is controlled between 55 and 56 ℃, and the reflux ratio is controlled between 3:1 and 5:1.
The beneficial effects of the present application will be further described below in conjunction with specific embodiments.
Example 1
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-hexane, cyclohexane, octanol. The mass ratio of each component is as follows: n-hexane: cyclohexane: octanol = 96:2.5:1.5. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the following steps: the extraction mass of the extractant and the wastewater is 1:10, the extraction temperature is 298K, the stirring speed is 40r/min, the stirring time is 15min, the standing time is 30min, and then the methyl methacrylate is extracted and separated to obtain a raffinate phase.
Adding alkali (sodium hydroxide) into the raffinate phase to adjust the pH value to 7.0.
The rectification process comprises the following steps: the total height of the packing of the rectifying tower is 40cm (20 tower plates), the height of the rectifying section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 100 ℃, the temperature of the tower top is 56 ℃, the reflux ratio is 4:1, and the operating pressure is normal pressure.
The waste water in the tower kettle after 10 times of rectification is continuously sampled, the appearance of the waste water is observed, and the COD value and the PH value of the waste water are analyzed, and the results are shown in Table 1.
The data in Table 1 show that the treated wastewater is continuously sampled for 10 times, the COD average value is 3500, the PH average value is 6.94, the wastewater is clear and transparent in appearance, and the biochemical treatment requirement of the device is met.
Example 2
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-hexane, cyclohexane, octanol. The mass ratio of each component is as follows: n-hexane: cyclohexane: octanol=95: 3:2. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the steps of extracting the extractant and the wastewater at an extraction mass of 1:10, extracting at 298K, stirring at a speed of 40r/min for 15min and standing for 30min.
Adding alkali (sodium hydroxide) into the raffinate to adjust the pH value to 7.0.
The rectification process is that the total height of the packing of the rectification tower is 40cm (20 tower plates), the height of the rectification section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 100 ℃, the temperature of the tower top is 56 ℃, the reflux ratio is 4:1, and the operation pressure is normal pressure.
The waste water in the tower kettle after 10 times of rectification is continuously sampled, the appearance of the waste water is observed, and the COD value and the PH value of the waste water are analyzed, and the results are shown in Table 2.
The data in Table 2 shows that the treated wastewater is sampled 10 times continuously, the COD average value is 4550, the PH average value is 6.89, the wastewater has a slightly turbid appearance and a small amount of suspended matters, and the biochemical treatment requirement of the device is basically met.
Example 3
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-hexane, cyclohexane, octanol. The mass ratio of each component is as follows: n-hexane: cyclohexane: octanol = 97:2:1. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the steps of extracting the extractant and the wastewater at an extraction mass of 1:10, extracting at 298K, stirring at a speed of 40r/min for 15min and standing for 30min.
Adding alkali (sodium hydroxide) into the raffinate to adjust the pH value to 7.0.
The rectification process is that the total height of the packing of the rectification tower is 40cm (20 tower plates), the height of the rectification section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 100 ℃, the temperature of the tower top is 56 ℃, the reflux ratio is 4:1, and the operation pressure is normal pressure.
The waste water in the tower kettle after 10 times of rectification is continuously sampled, the appearance of the waste water is observed, and the COD value and the PH value of the waste water are analyzed, and the result is shown in Table 3.
TABLE 3 COD, PH and appearance of wastewater
The data in Table 3 shows that the treated wastewater is sampled 10 times continuously, the COD average value is 5300, the PH average value is 6.91, and the biochemical treatment requirement is met, but the wastewater has a slightly suspended matter in appearance, and the biochemical treatment effect of the wastewater is affected by the suspended matter.
Example 4
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-hexane, cyclohexane, octanol. The mass ratio of each component is as follows: n-hexane: cyclohexane: octanol=95: 3:2. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the steps of extracting the extractant and the wastewater at an extraction mass of 1:9, extracting at 300K, stirring at a speed of 30r/min for 20min and standing for 35min.
Adding alkali (sodium hydroxide) into the raffinate to adjust the pH value to 7.0.
The rectification process is that the total height of the packing of the rectification tower is 40cm (20 tower plates), the height of the rectification section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 101 ℃, the temperature of the tower top is 56 ℃, the reflux ratio is 5:1, and the operation pressure is normal pressure.
Continuously sampling the wastewater in the tower kettle after 10 times of rectification, observing the appearance of the wastewater, and analyzing the COD value and the PH value of the wastewater, wherein the results are shown in Table 4:
example 5
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-hexane, cyclohexane, octanol. The mass ratio of each component is as follows: n-hexane: cyclohexane: octanol=95: 3:2. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the steps of extracting the extractant and the wastewater at an extraction mass of 1:9, extracting at 293K, stirring at a speed of 30r/min for 20min and standing for 25min.
Adding alkali (sodium hydroxide) into the raffinate to adjust the pH value to 8.0.
The rectification process is that the total height of the packing of the rectification tower is 40cm (20 tower plates), the height of the rectification section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 99 ℃, the temperature of the tower top is 55 ℃, the reflux ratio is 3:1, and the operation pressure is normal pressure.
The waste water in the tower kettle after 10 times of rectification is continuously sampled, the appearance of the waste water is observed, and the COD value and the PH value of the waste water are analyzed, and the results are shown in Table 5.
Example 6
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-hexane, cyclohexane, octanol. The mass ratio of each component is as follows: n-hexane: cyclohexane: octanol=94: 3:3. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the steps of extracting the extractant and the wastewater at an extraction mass of 1:9, extracting at 293K, stirring at a speed of 30r/min for 20min and standing for 25min.
Adding alkali (sodium hydroxide) into the raffinate to adjust the pH value to 8.0.
The rectification process is that the total height of the packing of the rectification tower is 40cm (20 tower plates), the height of the rectification section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 99 ℃, the temperature of the tower top is 55 ℃, the reflux ratio is 3:1, and the operation pressure is normal pressure.
The waste water in the tower kettle after 10 times of rectification is continuously sampled, the appearance of the waste water is observed, and the COD value and the PH value of the waste water are analyzed, and the results are shown in Table 6.
Example 7
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-octane, cyclohexane, octanol. The mass ratio of each component is as follows: n-octane: cyclohexane: octanol=95: 3:2. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the steps of extracting the extractant and the wastewater at an extraction mass of 1:9, extracting at 293K, stirring at a speed of 30r/min for 20min and standing for 25min.
Adding alkali (sodium hydroxide) into the raffinate to adjust the pH value to 8.0.
The rectification process is that the total height of the packing of the rectification tower is 40cm (20 tower plates), the height of the rectification section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 99 ℃, the temperature of the tower top is 55 ℃, the reflux ratio is 3:1, and the operation pressure is normal pressure.
The waste water in the tower kettle after 10 times of rectification is continuously sampled, the appearance of the waste water is observed, and the COD value and the PH value of the waste water are analyzed, and the results are shown in Table 7.
Example 8
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-hexane, cyclohexane, hexanol. The mass ratio of each component is as follows: n-hexane: cyclohexane: hexanol=95: 3:2. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the steps of extracting the extractant and the wastewater at an extraction mass of 1:9, extracting at 293K, stirring at a speed of 30r/min for 20min and standing for 25min.
Adding alkali (sodium hydroxide) into the raffinate to adjust the pH value to 8.0.
The rectification process is that the total height of the packing of the rectification tower is 40cm (20 tower plates), the height of the rectification section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 99 ℃, the temperature of the tower top is 55 ℃, the reflux ratio is 3:1, and the operation pressure is normal pressure.
The waste water in the tower kettle after 10 times of rectification is continuously sampled, the appearance of the waste water is observed, and the COD value and the PH value of the waste water are analyzed, and the results are shown in Table 8.
Example 9
Taking the waste water of the methyl methacrylate device of a certain factory in China.
The preparation of the extractant: the components of the composition comprise: n-hexane, cyclohexane, octanol. The mass ratio of each component is as follows: n-hexane: cyclohexane: octanol=95: 3:2. and mixing n-hexane, cyclohexane and octanol according to a proportion, and uniformly stirring to obtain the extractant.
The extraction process comprises the steps of extracting the extractant and the wastewater at an extraction mass of 1:9, extracting at 293K, stirring at a speed of 30r/min for 20min and standing for 25min.
Adding alkali (sodium hydroxide) into the raffinate to adjust the pH value to 8.0.
The rectification process is that the total height of the packing of the rectification tower is 40cm (20 tower plates), the height of the rectification section is 12cm (6 tower plates), the height of the stripping section is 28cm (14 tower plates), the temperature of the tower kettle is 95 ℃, the temperature of the tower top is 58 ℃, the reflux ratio is 3:1, and the operation pressure is normal pressure.
The waste water in the tower kettle after 10 times of rectification is continuously sampled, the appearance of the waste water is observed, and the COD value and the PH value of the waste water are analyzed, and the results are shown in Table 9.
Comparative example 1
The pH adjustment step and the extraction step in example 5 were sequentially exchanged, i.e., the pH was adjusted to neutral before extraction, and the results are shown in table 10.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the extraction agent combination formed by a plurality of extraction agents is adopted to extract and remove the polymer methyl methacrylate in the wastewater, so that the raffinate phase is not polymerized in the subsequent rectification process, and then the pH value is regulated, and the treated wastewater meets the biochemical treatment requirement by a one-step normal pressure rectification method. The method solves the problem that methyl methacrylate is polymerized when heated in the process of removing organic matters in the wastewater in the prior art, and ensures that the COD value of the treated wastewater is lower than 15000mg/L and the PH value is close to neutral, thereby meeting the biochemical treatment requirement.
Compared with the existing treatment method, the treatment method for the methyl methacrylate device wastewater has the following advantages:
(1) The extractant is easy to obtain and has better economy, and the extractant has good extraction effect on methyl methacrylate.
(2) The extractant is easy to recycle.
(3) The extracted wastewater does not contain methyl methacrylate, and no polymer is generated in the rectification process.
(4) The COD average value of the treated tower kettle wastewater is 3500mg/L, which is far lower than the requirement of 20000mg/L;
(5) The treatment process is environment-friendly and no waste gas is generated.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for treating wastewater from a methyl methacrylate plant, the method comprising:
extracting methyl methacrylate from the wastewater by adopting a plurality of extractants to obtain a first raffinate phase;
adjusting the pH value of the first raffinate phase to be neutral to obtain a second raffinate phase;
rectifying the second raffinate phase to obtain treated wastewater;
the plurality of extractants includes n-hexane, cyclohexane, and octanol;
the mass ratio of the n-hexane to the cyclohexane to the octanol is 95-97: 3.0 to 2.0:2.0 to 1.0;
adjusting the pH value of the raffinate phase to 6.0-8.0 by adopting alkali;
the waste water of the methyl methacrylate device refers to waste water with high COD value generated in the normal operation process of the methyl methacrylate device produced by an acetone cyanohydrin method;
the device for producing methyl methacrylate comprises a tail gas blower, a refining layering device and a steam jet pump.
2. The method of claim 1, wherein a ratio of a total mass of the plurality of extractants to a mass of the wastewater is 1:9 to 1:11.
3. The method of claim 1, wherein the extraction temperature is 293K to 300K.
4. The method according to claim 1, wherein the extraction is performed under stirring conditions, the stirring speed is 30r/min to 50r/min, and the stirring time is controlled to be 10min to 20min.
5. The method of claim 4, wherein the first raffinate phase is obtained by standing for 25min to 35min after the stirring.
6. The process of claim 1, wherein the second raffinate phase is rectified at a pressure of less than 0.1 MPa.
7. The method according to claim 1, wherein the second raffinate phase is rectified by a rectifying tower, the temperature of the tower bottom of the rectifying tower is controlled between 99 ℃ and 101 ℃, the temperature of the tower top is controlled between 55 ℃ and 56 ℃, and the reflux ratio is controlled between 3:1 and 5:1.
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| JP2007045803A (en) * | 2005-08-12 | 2007-02-22 | Asahi Kasei Chemicals Corp | Method for obtaining purified methyl methacrylate |
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