順酐是順丁烯二酸酐的簡(jiǎn)稱，又稱馬來(lái)酸酐或者失水蘋果酸酐，是一種重要的有機(jī)化工原料或精細(xì)化學(xué)品，主要用于不飽和聚酯樹(shù)脂、醇酸樹(shù)脂、1,4-丁二醇(BDO)、四氫苯酐等化工產(chǎn)品，開(kāi)發(fā)應(yīng)用前景十分廣闊。目前國(guó)內(nèi)外在正丁烷為原料的順酐工藝中，多采用有機(jī)溶劑為吸收劑，有機(jī)溶劑一般為六氫化鄰苯二甲酸二異丁酯(DIBE)和鄰苯二甲酸二丁酯(DBP)。
Maleic anhydride is the abbreviation of maleic anhydride, also known as maleic anhydride or dehydrated malic anhydride. It is an important organic chemical raw material or fine chemical. It is mainly used to produce unsaturated polyester resin, alkyd resin, 1,4-butanediol (BDO), tetrahydrophthalic anhydride and other chemical products. Its development and application prospects are very broad. At present, in the production process of maleic anhydride with n-butane as raw material at home and abroad, most organic solvents are used as absorbents, and the organic solvents are generally diisobutyl hexahydrophthalate (DIBE) and dibutyl phthalate (DBP).
有機(jī)溶劑吸收順酐后通過(guò)氣提工段提純順酐，吸收劑經(jīng)分離機(jī)處理之后循環(huán)使用。以正丁烷為原料順酐產(chǎn)生的廢水來(lái)源于三部分，即解析真空泵排出的廢水、精制真空泵排出的廢水和離心機(jī)輕相排出的廢水，其中混合有機(jī)酸及醋成分包括丙烯酸、馬來(lái)酸、富馬酸、鄰苯二甲酸、六氫化鄰苯二甲酸二異丁酯(DIBE)或者鄰苯二甲酸二丁醋(DBP) 、丙烯酸二聚體，廢水pH=0.5-1.5，總有機(jī)物含量在1.0%-1.4% ，幾乎不含氮、磷和無(wú)機(jī)鹽類，屬于高濃度化工廢水。有機(jī)酸及DIBE等溶劑是增加水體COD的源頭，還含有一定量的氨(胺)基化合物、雜環(huán)化合物、酚類、苯類，屬生物不易降解高濃度有機(jī)廢水成分，對(duì)微生物生長(zhǎng)具有抑制作用。此類廢水中間產(chǎn)物均對(duì)微生物有較強(qiáng)的抑制作用，我們常稱為生物毒性，并具有很強(qiáng)的腐蝕性。
After the organic solvent absorbs the maleic anhydride, the maleic anhydride is purified through the gas extraction section, and the absorbent is recycled after being processed by the separator. The waste water generated from the production of maleic anhydride using n-butane as raw material comes from three parts, namely, the waste water from the analytical vacuum pump, the waste water from the refining vacuum pump, and the waste water from the light phase of the centrifuge. The mixed organic acid and vinegar components include acrylic acid, maleic acid, fumaric acid, phthalic acid, diisobutyl hexahydrophthalate (DIBE), or dibutyl phthalate (DBP), and acrylic acid dimer. The pH of the waste water is 0.5-1.5, The total organic content is 1.0% - 1.4%, almost free of nitrogen, phosphorus and inorganic salts, belonging to high concentration chemical wastewater. Solvents such as organic acids and DIBE are the sources of increasing COD in water bodies, and also contain a certain amount of ammonia (amine) compounds, heterocyclic compounds, phenols, and benzene, which are the components of organic wastewater with high concentration that are not easily degraded by organisms, and have an inhibitory effect on microbial growth. The intermediate products of this kind of wastewater have strong inhibitory effect on microorganisms, which are often called biological toxicity and have strong corrosivity.
目前的順酐廢水處理工藝一般是：順酐工藝廢水-集水井-隔油調(diào)節(jié)池-EBR反應(yīng)器(鐵碳微電解)-破乳反應(yīng)池-氣浮系統(tǒng)-緩沖水池-混凝沉淀池-配水池-IC反應(yīng)器-一階氧化-中間沉淀池-二階氧化池-二級(jí)沉淀池-臭氧氧化池-生物濾池-清水池，由于其中含有較多的難降解有機(jī)物，經(jīng)過(guò)現(xiàn)有技術(shù)進(jìn)行生物降解后仍很難達(dá)到排放標(biāo)準(zhǔn)，并且造成廢水處理費(fèi)用高。
At present, the treatment process of maleic anhydride wastewater is generally: maleic anhydride process wastewater - water collecting well - oil separation regulating tank - EBR reactor (iron and carbon micro-electrolysis) - demulsification reaction tank - air flotation system - buffer tank - coagulation sedimentation tank - distribution tank - IC reactor - first stage oxidation - intermediate sedimentation tank - second stage oxidation tank - second stage sedimentation tank - ozone oxidation tank - biological filter - clean water tank, because it contains more refractory organics, It is still difficult to meet the discharge standard after biodegradation by the existing technology, and the waste water treatment cost is high.
現(xiàn)有技術(shù)中處理順酐廢水時(shí)，把順酐廢水中的馬來(lái)酸異構(gòu)為富馬酸，然后降溫結(jié)晶得到富馬酸，同時(shí)降低廢水中有機(jī)物含量，但是此方法僅適用于水吸收法順酐工藝，而不適用普遍使用的有機(jī)溶劑吸收法。
When treating maleic anhydride wastewater in the existing technology, the maleic acid in the maleic anhydride wastewater is isomerized into fumaric acid, and then the fumaric acid is obtained by cooling and crystallizing, while reducing the content of organic matter in the wastewater. However, this method is only applicable to the water absorption method of maleic anhydride process, not the commonly used organic solvent absorption method.
另外，有人提出一種順酐廢水處理的新工藝，即使用堿性萃取劑回收其中的馬來(lái)酸和富馬酸，降低廢水中的有機(jī)物，然后再去生化處理廢水，但是廢水中六氫化鄰苯二甲酸二異丁酯(DIBE)或者鄰苯二甲酸二丁醋(DBP)的可生化降解性比富馬酸、馬來(lái)酸等要低很多，其主要是針對(duì)廢水中的有機(jī)酸性物質(zhì)的回收處理，但該方法對(duì)于廢水中的難降解有機(jī)物如DIBE或者DBP沒(méi)有考慮，廢水難降解有機(jī)物含量依然較高，亦難以進(jìn)行生化處理，主要依靠其他水稀釋處理達(dá)標(biāo)排放?？梢?jiàn)，順酐廢水處理工藝需要進(jìn)行改進(jìn)。
In addition, a new process for the treatment of maleic anhydride wastewater was proposed, that is, to use alkaline extractants to recover the maleic acid and fumaric acid in the wastewater, reduce the organic matter in the wastewater, and then go to biochemical treatment of the wastewater. However, the biodegradability of DIBE or DBP in the wastewater is much lower than that of fumaric acid and maleic acid, It is mainly aimed at the recovery and treatment of organic acid substances in wastewater, but this method does not consider the refractory organics in wastewater, such as DIBE or DBP. The content of refractory organics in wastewater is still high, and it is also difficult to carry out biochemical treatment. It mainly depends on other water dilution treatment to meet the discharge standard. It can be seen that the treatment process of maleic anhydride wastewater needs to be improved.
