CN102874986B - Treatment method for wastewater containing organic matters during production of N-phenyl maleimide - Google Patents
Treatment method for wastewater containing organic matters during production of N-phenyl maleimide Download PDFInfo
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- CN102874986B CN102874986B CN201210403184.7A CN201210403184A CN102874986B CN 102874986 B CN102874986 B CN 102874986B CN 201210403184 A CN201210403184 A CN 201210403184A CN 102874986 B CN102874986 B CN 102874986B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 41
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000005416 organic matter Substances 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 229940023913 cation exchange resins Drugs 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005504 petroleum refining Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 239000008235 industrial water Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- JCJIZBQZPSZIBI-UHFFFAOYSA-N 2-[2,6-di(propan-2-yl)phenyl]benzo[de]isoquinoline-1,3-dione Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C1=O)C(=O)C2=C3C1=CC=CC3=CC=C2 JCJIZBQZPSZIBI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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Abstract
本发明公开了一种N-苯基马来酰亚胺生产过程中含有机物废水的处理方法，首先将该含有机物的废水在20-40℃、0.1-0.15MPa条件下以10ml/分钟的速率通过装有酸性树脂的处理柱，再以相同的压力条件及速率通过装有碱性树脂的处理柱，最后将得到除去有机物的废水排入厌氧池中进行常规化处理。检测结果表明：废水中有机物的化学耗氧量CODcr为95mg/L，生化耗氧量BOD5值为25mg/L，达到石油炼制工业水污染物排放标准。本发明处理方法可应用于不同取代基团的N-苯基马来酰亚胺同类产品的废水处理，适于工业生产过程中废水的连续化处理。The invention discloses a method for treating waste water containing organic matter in the production process of N-phenylmaleimide. Firstly, the waste water containing organic matter is treated at a rate of 10ml/min under the conditions of 20-40°C and 0.1-0.15MPa. Pass through the treatment column equipped with acid resin, then pass through the treatment column equipped with basic resin under the same pressure conditions and speed, and finally discharge the waste water obtained from the removal of organic matter into the anaerobic tank for conventional treatment. The test results show that the chemical oxygen demand COD cr of organic matter in wastewater is 95mg/L, and the biochemical oxygen demand BOD 5 is 25mg/L, reaching the discharge standard of petroleum refining industrial water pollutants. The treatment method of the invention can be applied to the wastewater treatment of similar products of N-phenylmaleimide with different substituent groups, and is suitable for the continuous treatment of wastewater in the industrial production process.
Description
技术领域 technical field
本发明涉及一种N-苯基马来酰亚胺生产过程中含有机物废水的处理方法。The invention relates to a method for treating waste water containing organic matter in the production process of N-phenylmaleimide.
背景技术 Background technique
N-苯基马来酰亚胺(简称NPMI)是一种耐热有机单体，具有五元环状平面结构，将其嵌入高分子链中可以增加链的内旋阻力，从而提高材料的耐热性，是目前世界上致力开发的精细化工产物之一。目前，N-苯基马来酰亚胺的主要用途是作为ABS耐热改性剂，可以有效地改善ABS树脂的耐热性、加工性、相容性和耐冲击性。但是，N-苯基马来酰亚胺的生产过程中必然会产生含N-苯基马来酰亚胺、马来酸等有机物的废水，其中N-苯基马来酰亚胺在废水中的含量达到2-5wt％，马来酸在废水中的含量达到3-8wt％，pH＝4-5，这类废水如果不加处理直接排放到厌氧池中有机物的含量极高，会对环境造成严重的污染，影响到人体的健康，人类生存的危机。N-phenylmaleimide (NPMI for short) is a heat-resistant organic monomer with a five-membered ring planar structure. Embedding it in a polymer chain can increase the internal rotation resistance of the chain, thereby improving the resistance of the material. Heat is one of the fine chemical products that are currently being developed in the world. At present, the main use of N-phenylmaleimide is as an ABS heat-resistant modifier, which can effectively improve the heat resistance, processability, compatibility and impact resistance of ABS resin. However, in the production process of N-phenylmaleimide, waste water containing organic matter such as N-phenylmaleimide and maleic acid will inevitably be produced, wherein N-phenylmaleimide is contained in waste water The content of maleic acid reaches 2-5wt%, the content of maleic acid in wastewater reaches 3-8wt%, pH=4-5, if this kind of wastewater is discharged directly into the anaerobic tank without treatment, the content of organic matter is very high, it will be harmful to The environment has caused serious pollution, which affects human health and is a crisis of human survival.
为保护环境，控制污染的排放，国家规定了废水容许排放浓度的标准，要求在工业废水排放前进行无害化处理，即对生产过程中产生的含有机物的工业废水应有针对性的将其有机物去除后再排入厌氧池，以有效控制废水排放的指标，现有技术中未见N-苯基马来酰亚胺生产过程中含有机物废水处理方法的相关报道。In order to protect the environment and control the discharge of pollution, the state has stipulated the standard for the allowable discharge concentration of wastewater, requiring harmless treatment before the discharge of industrial wastewater, that is, the industrial wastewater containing organic matter generated during the production process should be targeted. After the organic matter is removed, it is discharged into the anaerobic pond to effectively control the indicators of waste water discharge. In the prior art, there is no relevant report on the treatment method of waste water containing organic matter in the production process of N-phenylmaleimide.
发明内容 Contents of the invention
本发明所要解决的问题在于提供一种N-苯基马来酰亚胺生产过程中含有机物废水的处理方法，以满足N-苯基马来酰亚胺及含不同取代基团的同类产品废水处理方法缺失的不足。The problem to be solved by the present invention is to provide a treatment method for wastewater containing organic matter in the production process of N-phenylmaleimide, so as to meet the requirements of N-phenylmaleimide and similar product wastewater containing different substituent groups. Handling methodological deficiencies.
本发明的技术构思是这样的：Technical concept of the present invention is such:
首先将N-苯基马来酰亚胺生产过程中含有机物的废水依次通过装有酸性树脂的处理柱进行处理，通过碱性树脂的处理柱处理，最后将得到去除有机物的废水排入厌氧池中进行常规化处理。Firstly, the waste water containing organic matter in the production process of N-phenylmaleimide is treated sequentially through the treatment column equipped with acid resin, then through the treatment column of basic resin, and finally the waste water obtained from the removal of organic matter is discharged into the anaerobic Normalized treatment in the pool.
所述的N-苯基马来酰亚胺生产过程中含有机物废水的处理方法，包括如下步骤：The processing method that contains organic matter waste water in the described N-phenylmaleimide production process, comprises the steps:
首先，将N-苯基马来酰亚胺生产过程中含有机物的废水在20-40℃、0.1-0.15MPa条件下以10ml/分钟的速率通过装有酸性树脂的处理柱，再以相同的压力条件及速率通过装有碱性树脂的处理柱，最后，将得到除去有机物的废水排入厌氧池中进行常规化处理。First of all, the wastewater containing organic matter in the N-phenylmaleimide production process is passed through the treatment column equipped with acid resin at a rate of 10ml/min under the conditions of 20-40°C and 0.1-0.15MPa, and then the same The pressure conditions and the rate pass through the treatment column equipped with basic resin, and finally, the waste water obtained from the removal of organic matter is discharged into the anaerobic tank for conventional treatment.
其中，上述处理方法中，所述的含有机物的废水中，N-苯基马来酰亚胺的含量为2-5wt％，马来酸的含量为3-8wt％，pH＝4-5。Wherein, in the above treatment method, in the waste water containing organic matter, the content of N-phenylmaleimide is 2-5wt%, the content of maleic acid is 3-8wt%, and the pH=4-5.
所述的酸性树脂为强酸性732阳离子交换树脂，所述的碱性树脂为大孔弱碱性树脂。The acidic resin is strongly acidic 732 cation exchange resin, and the basic resin is macroporous weakly basic resin.
所述的含有机物的废水与酸性树脂、碱性树脂的质量比为1∶2-5∶2-5，g/g/g。The mass ratio of the waste water containing organic matter to the acidic resin and basic resin is 1:2-5:2-5, g/g/g.
本发明的N-苯基马来酰亚胺生产过程中含有机物的废水经处理后排入厌氧池中进行常规处理，检测结果表明：有机物的化学耗氧量CODcr为95mg/L，生化耗氧量BOD5值为25mg/L，pH＝6，达到石油炼制工业水污染物排放标准。In the N-phenylmaleimide production process of the present invention, the waste water containing organic matter is discharged into the anaerobic tank after being treated and carried out routine treatment, and test result shows: the chemical oxygen consumption COD cr of organic matter is 95mg/L, biochemical Oxygen consumption BOD 5 value is 25mg/L, pH=6, reaching the discharge standard of water pollutants in petroleum refining industry.
本发明所使用的强酸性732阳离子交换树脂，碱性树脂为大孔弱碱性树脂，均可以从市场上采购得到。The strongly acidic 732 cation exchange resin used in the present invention and the basic resin are macroporous weakly basic resins, both of which can be purchased from the market.
本发明与现有技术相比较的有益效果：The beneficial effect that the present invention compares with prior art:
本发明的处理方法作为工业废水排放前进行无害化处理，操作简单，成本低廉，能显著降低N-苯基马来酰亚胺含有机物废水中的COD、BOD值，除去有机物的废水排入厌氧池中进行常规处理(本领域技术人员公知，皆可想到的方法)，即可达到石油炼制工业水污染物排放标准，而且可应用于不同取代基团的N-苯基马来酰亚胺同类产品的废水处理，适于工业生产过程中废水的连续化处理。The treatment method of the present invention is used as a harmless treatment before the discharge of industrial waste water. The operation is simple and the cost is low. It can significantly reduce the COD and BOD values in the N-phenylmaleimide wastewater containing organic matter. In the anaerobic tank, conventional treatment (well known to those skilled in the art, all conceivable methods) can reach the petroleum refining industry water pollutant discharge standard, and can be applied to the N-phenylmaleic acid of different substituting groups The waste water treatment of similar products of imine is suitable for the continuous treatment of waste water in the process of industrial production.
具体实施方式 Detailed ways
下面结合实施例对本发明作进一步说明，但实施例并不限制本发明的保护范围。The present invention will be further described below in conjunction with embodiment, but embodiment does not limit protection scope of the present invention.
实施例1Example 1
将1000g N-苯基马来酰亚胺生产过程中含有机物的废水(其中N-苯基马来酰亚胺含量为2wt％，马来酸含量为3wt％，pH＝4)在20℃、0.15MPa的条件下以10ml/分钟的速率通过装有2000g 732阳离子交换树脂的处理柱，再以相同的压力条件及速率通过装有2000g大孔弱碱性树脂的处理柱，将得到除去有机物的废水排入厌氧池中进行常规化处理。废水检测结果表明：处理前废水CODCr值大于50000mg/L(理论值)，处理后废水中有机物的化学耗氧量CODcr为95mg/L，生化耗氧量BOD5为25mg/L。The waste water (wherein N-phenylmaleimide content is 2wt%, and maleic acid content is 3wt%, pH=4) containing organic matter in 1000g N-phenylmaleimide production process is at 20 ℃, Pass through the treatment column that 2000g 732 cation exchange resins are housed with the speed of 10ml/min under the condition of 0.15MPa, then pass through the treatment post that 2000g macroporous weakly basic resin is housed with the same pressure condition and speed, will obtain to remove organic matter Wastewater is discharged into the anaerobic pond for routine treatment. The test results of wastewater show that the COD Cr value of wastewater before treatment is greater than 50000 mg/L (theoretical value), the chemical oxygen demand COD cr of organic matter in wastewater after treatment is 95 mg/L, and the biochemical oxygen demand BOD 5 is 25 mg/L.
实施例2Example 2
将1000g 5％N-苯基马来酰亚胺生产过程中含有机物的废水(其中N-苯基马来酰亚胺含量为5wt％，马来酸含量为8wt％，pH＝5)在40℃、0.15MPa的条件下以10ml/分钟的速率通过装有5000g 732阳离子树脂的处理柱，再以相同的压力条件及速率通过装有5000g大孔弱碱性树脂的处理柱，将得到除去有机物的废水排入厌氧池中进行常规化处理。废水检测结果表明：处理前废水CODCr值大于140000mg/L(理论值)，处理后废水中有机物的化学耗氧量CODCr为95mg/L，生化耗氧量BOD5为25mg/L。The waste water (wherein N-phenylmaleimide content is 5wt%, and maleic acid content is 8wt%, pH=5) containing organic matter in 1000g 5% N-phenylmaleimide production process is at 40 Under the conditions of ℃ and 0.15MPa, pass through the treatment column equipped with 5000g 732 cationic resin at a rate of 10ml/min, and then pass through the treatment column equipped with 5000g macroporous weakly basic resin under the same pressure conditions and speed, and the organic matter will be removed. The waste water is discharged into the anaerobic pond for routine treatment. The test results of wastewater show that the COD Cr value of wastewater before treatment is greater than 140,000 mg/L (theoretical value), the chemical oxygen demand COD Cr of organic matter in wastewater after treatment is 95 mg/L, and the biochemical oxygen demand BOD 5 is 25 mg/L.
表1 N-苯基马来酰亚胺有机物废水处理前后有机物含量的测定Table 1 Determination of organic content in N-phenylmaleimide organic wastewater before and after treatment
需要说明的是，以上实施例仅用以说明本发明的技术方案而非限制。尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的范围，其均应涵盖在本发明的权利要求范围中。It should be noted that the above embodiments are only used to illustrate the technical solution of the present invention and not to limit. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solution of the invention can be modified or equivalently replaced without departing from the scope of the technical solution of the present invention, which should be covered in this within the scope of the claimed invention.
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