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CN104844420B - The continuous treatment technique of neopentyl glycol condensation water cleaning mother liquor and device - Google Patents

The continuous treatment technique of neopentyl glycol condensation water cleaning mother liquor and device Download PDF

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CN104844420B
CN104844420B CN201510028509.1A CN201510028509A CN104844420B CN 104844420 B CN104844420 B CN 104844420B CN 201510028509 A CN201510028509 A CN 201510028509A CN 104844420 B CN104844420 B CN 104844420B
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neopentyl glycol
mother liquor
tower
washing mother
glycol condensation
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CN104844420A (en
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王英龙
张震
朱兆友
张青
马艺心
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Qingdao University of Science and Technology
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment

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Abstract

本发明涉及一种新戊二醇缩合水洗母液的连续化处理装置,其特征在于:所述装置包括过滤器、一级预热器、二级预热器、精馏塔、层析器和旋液分离器,所述过滤器在一级预热器的前端,所述一级预热器通过管路与所述二级预热器连接,所述精馏塔在所述二级预热器的后端,所述精馏塔塔顶设有回流罐和层析器,所述精馏塔塔底设有旋液分离器和再沸器。本发明涉及一种新戊二醇缩合水洗母液的连续化处理工艺流程,能连续稳定脱除新戊二醇缩合水洗母液中的有机杂质并浓缩新戊二醇。The invention relates to a continuous treatment device for neopentyl glycol condensation water washing mother liquor, characterized in that the device includes a filter, a primary preheater, a secondary preheater, a rectification tower, a chromatograph and a cyclone liquid separator, the filter is at the front end of the primary preheater, the primary preheater is connected to the secondary preheater through pipelines, and the rectification column is connected to the secondary preheater The rear end of the rectification tower is provided with a reflux tank and a chromatograph at the top of the rectification tower, and a liquid cyclone separator and a reboiler are provided at the bottom of the rectification tower. The invention relates to a continuous treatment process flow for neopentyl glycol condensation washing mother liquor, which can continuously and stably remove organic impurities in neopentyl glycol condensation washing mother liquor and concentrate neopentyl glycol.

Description

新戊二醇缩合水洗母液的连续化处理工艺与装置Continuous treatment process and equipment for neopentyl glycol condensation water washing mother liquor

技术领域technical field

本发明属于制药行业的分离领域,具体涉及新戊二醇缩合水洗母液的连续化处理工艺与装置。The invention belongs to the separation field of the pharmaceutical industry, and in particular relates to a continuous treatment process and device for neopentyl glycol condensation water washing mother liquor.

背景技术Background technique

新戊二醇简称NPG,白色结晶固体,易溶于水、低碳醇、低碳酮、醚和芳烃化合物。目前,新戊二醇的合成方法主要有加氢法和甲醇法。新戊二醇分子具有特定的新戊基结构,其分子中含有两个伯羰基,中心碳原子上没有α-氢原子,这些特点使新戊二醇具有很高的热稳定性和化学稳定性,因此,它常用于医药、化工、涂料、农药、塑料和石油等生产领域。其中,在医药行业,新戊二醇可作为合成布洛芬的中间体—缩酮的重要原料,它与溶解在石油醚中的氯酮发生缩合反应生成缩酮。未反应的新戊二醇和生成的缩酮产品经过水洗后得到缩酮溶液与含有石油醚的新戊二醇溶液。将含有石油醚等有机杂质的新戊二醇缩合水洗母液浓缩至新戊二醇质量分数为60%后,可循环用于氯酮的缩合反应,降低生产单耗。Neopentyl glycol, referred to as NPG, is a white crystalline solid, easily soluble in water, low-carbon alcohols, low-carbon ketones, ethers and aromatic compounds. At present, the synthesis methods of neopentyl glycol mainly include hydrogenation method and methanol method. Neopentyl glycol molecule has a specific neopentyl structure, which contains two primary carbonyl groups, and there is no α-hydrogen atom on the central carbon atom. These characteristics make neopentyl glycol have high thermal and chemical stability , Therefore, it is often used in the production fields such as medicine, chemical industry, paint, pesticide, plastic and petroleum. Among them, in the pharmaceutical industry, neopentyl glycol can be used as an important raw material for the synthesis of ibuprofen intermediate-ketal, which undergoes condensation reaction with chlorketone dissolved in petroleum ether to form ketal. The unreacted neopentyl glycol and the generated ketal products are washed with water to obtain a ketal solution and a neopentyl glycol solution containing petroleum ether. After concentrating the neopentyl glycol condensation water washing mother liquor containing petroleum ether and other organic impurities to a neopentyl glycol mass fraction of 60%, it can be recycled for the condensation reaction of ketone, reducing the unit consumption of production.

现有水蒸汽平衡蒸馏工艺对新戊二醇缩合水洗母液的处理技术方案为:先将新戊二醇缩合水洗母液输入到20立方米的蒸馏储罐中,然后通入新鲜蒸汽进行加热,随着罐内温度升高,新戊二醇缩合水洗母液中的有机物杂质和水逐渐以气体形式汇集在罐顶。从罐顶引出含有有机杂质与水的气相,再将其冷却形成含有有机杂质的废水,完成一批后重复进行。现有工艺每处理一吨新戊二醇缩合水洗母液,产生废水900升,该废水中的化学需氧量(COD)为2000~3000毫克/升。上述处理过程持续20~22小时后,停止通入新鲜水蒸汽,罐内浓缩后的新戊二醇循环回用于氯酮的缩合反应。The existing water vapor equilibrium distillation process for the treatment of the neopentyl glycol condensation water washing mother liquor is as follows: first, the neopentyl glycol condensation water washing mother liquor is input into a distillation storage tank of 20 cubic meters, and then fresh steam is introduced for heating, and then As the temperature in the tank rises, the organic impurities and water in the neopentyl glycol condensation water washing mother liquor gradually gather on the top of the tank in the form of gas. The gas phase containing organic impurities and water is drawn from the top of the tank, and then cooled to form waste water containing organic impurities, and the process is repeated after a batch is completed. In the existing technology, every ton of neopentyl glycol condensation washing mother liquor is processed, and 900 liters of waste water is produced, and the chemical oxygen demand (COD) in the waste water is 2000-3000 mg/liter. After the above treatment process lasts for 20-22 hours, the introduction of fresh water vapor is stopped, and the concentrated neopentyl glycol in the tank is recycled for the condensation reaction of ketone.

现有水蒸汽平衡蒸馏工艺存在如下问题:第一,处理过程中新戊二醇损失量大,罐顶采出的废水中新戊二醇质量分数为2~3%,处理每吨新戊二醇缩合水洗母液,新戊二醇损失量为20~30千克;第二,操作周期长,每处理一批20吨的新戊二醇缩合水洗母液需要20~22小时,生产效率低;第三,处理后的新戊二醇溶液颜色偏黄,需要经过活性炭脱色才能循环利用,现有工艺采用间歇式处理,罐内溶液长时间处于高温状态下,导致溶液中的有机物部分碳化,颜色偏黄;第四,新戊二醇蒸馏罐中易出现结垢,导致传热效果偏差,新戊二醇缩合水洗母液中含有微量硫酸钙,平衡蒸馏把大量的水蒸出后,罐内硫酸钙逐渐聚集导致蒸馏罐壁内结垢。The existing steam equilibrium distillation process has the following problems: first, the loss of neopentyl glycol is large during the treatment process, and the mass fraction of neopentyl glycol in the wastewater produced from the top of the tank is 2 to 3%, and every ton of neopentyl glycol is processed Alcohol condensation water washing mother liquor, the loss of neopentyl glycol is 20-30 kg; second, the operation period is long, and it takes 20-22 hours to process a batch of 20 tons of neopentyl glycol condensation water washing mother liquor, and the production efficiency is low; third , the color of the treated neopentyl glycol solution is yellowish, and it needs to be decolorized by activated carbon before it can be recycled. The existing process adopts intermittent treatment, and the solution in the tank is kept at high temperature for a long time, resulting in partial carbonization of the organic matter in the solution, and the color is yellowish. 4. Scaling easily occurs in the neopentyl glycol distillation tank, which leads to deviation of heat transfer effect. The neopentyl glycol condensation washing mother liquor contains a small amount of calcium sulfate. After a large amount of water is steamed out by balanced distillation, the calcium sulfate in the tank gradually Accumulation leads to scaling inside the retort walls.

发明内容Contents of the invention

本发明克服了现有技术的不足,开发了一种新戊二醇缩合水洗母液的连续化处理工艺与装置,能有效去除新戊二醇溶液中的有机杂质以浓缩新戊二醇,并提供了实现上述工艺过程的装置。The present invention overcomes the deficiencies in the prior art, and develops a continuous treatment process and device for neopentyl glycol condensation water washing mother liquor, which can effectively remove organic impurities in neopentyl glycol solution to concentrate neopentyl glycol, and provide A device for realizing the above process.

一种新戊二醇缩合水洗母液的连续化处理装置,其特征在于:包括过滤器、一级预热器、二级预热器、精馏塔、层析器和旋液分离器,所述过滤器设有物料进口和物料出口,物料出口通过管道与一级预热器连接,所述一级预热器的物料出口通过管道与二级预热器连接,所述二级预热器物料出口通过管道与精馏塔连接,所述精馏塔设有物料入口、塔顶气相出口、回流入口和塔底物料出口,塔顶气相出口通过管路与一级预热器连接,在所述精馏塔的塔顶设有一个回流罐,一级预热器通过管路与所述回流罐入口连接,所述回流罐设有水相物料出口和有机相物料出口,水相物料出口通过管路与精馏塔回流入口连接,所述精馏塔的塔底设有旋液分离器和二级预热器,所述旋液分离器通过管路与精馏塔和再沸器相连,所述二级预热器通过管路与精馏塔和一级预热器相连。A continuous treatment device for neopentyl glycol condensation water washing mother liquor, characterized in that it includes a filter, a primary preheater, a secondary preheater, a rectifying tower, a chromatograph and a hydrocyclone, the The filter is provided with a material inlet and a material outlet, the material outlet is connected to the primary preheater through a pipeline, the material outlet of the primary preheater is connected to the secondary preheater through a pipeline, and the material of the secondary preheater The outlet is connected to the rectification tower through a pipeline, and the rectification tower is provided with a material inlet, a gas phase outlet at the top of the tower, a reflux inlet and a material outlet at the bottom of the tower, and the gas phase outlet at the top of the tower is connected with a primary preheater through a pipeline. The top of the rectification tower is provided with a reflux tank, the primary preheater is connected to the inlet of the reflux tank through a pipeline, the reflux tank is provided with an outlet for water phase material and an outlet for organic phase material, and the outlet for water phase material is The road is connected with the reflux inlet of the rectification tower, and the bottom of the rectification tower is provided with a liquid cyclone separator and a secondary preheater, and the liquid cyclone separator is connected with the rectification tower and a reboiler through a pipeline. The secondary preheater is connected with the rectification column and the primary preheater through pipelines.

所述的一级预热器为列管式换热器,其材质为石墨;所述的二级预热器为板式换热器。The first-stage preheater is a tube-and-tube heat exchanger made of graphite; the second-stage preheater is a plate heat exchanger.

一种新戊二醇缩合水洗母液的连续化处理工艺流程,其特征在于:所述流程以水和新戊二醇为主要原料,包括以下步骤:A continuous treatment process flow for neopentyl glycol condensation water washing mother liquor, characterized in that: said flow process uses water and neopentyl glycol as main raw materials, comprising the following steps:

第一步:过滤新戊二醇缩合水洗母液中固体颗粒The first step: filter the solid particles in the neopentyl glycol condensation washing mother liquor

所述新戊二醇缩合水洗母液中含有石油醚、二氯甲烷有机杂质和不溶性固体颗粒,用泵从储罐中将新戊二醇缩合水洗母液通过过滤器输送到精馏塔内,拦截其中不溶性固体颗粒,定期清理过滤器中的滤渣,过滤后得到的新戊二醇缩合水洗母液中含有石油醚和二氯甲烷;The neopentyl glycol condensation water washing mother liquor contains petroleum ether, dichloromethane organic impurities and insoluble solid particles, and the neopentyl glycol condensation water washing mother liquor is transported from the storage tank to the rectification tower through a filter by a pump, and intercepted Insoluble solid particles, regularly clean the filter residue in the filter, and the neopentyl glycol condensation washing mother liquor obtained after filtration contains petroleum ether and methylene chloride;

第二步:预热新戊二醇缩合水洗母液The second step: preheating neopentyl glycol condensation water washing mother liquor

以来自精馏塔的塔顶气相和塔底浓缩后的新戊二醇溶液为热源,在所述一级和二级预热器中将新戊二醇缩合水洗母液从常温加热到85~95℃;Using the vapor phase at the top of the rectification tower and the concentrated neopentyl glycol solution at the bottom of the tower as the heat source, the neopentyl glycol condensation water washing mother liquor is heated from normal temperature to 85-95°C in the primary and secondary preheaters. ℃;

第三步:脱除新戊二醇缩合水洗母液中有机杂质The third step: removal of organic impurities in the neopentyl glycol condensation water washing mother liquor

预热后的新戊二醇缩合水洗母液经过泵输送到所述精馏塔内,塔底再沸器通入0.1~0.5MPa(表压)的加热蒸汽,使塔底压力维持在0.01~0.05MPa(表压),塔底部分液体通过再沸器汽化,上升的气体在所述精馏塔内与下降液体进行多级气液传质,石油醚和二氯甲烷有机杂质不断在气相中富集,最终以气体形式从精馏塔气相出口排出;The preheated neopentyl glycol condensation water washing mother liquor is pumped into the rectification tower, and the bottom reboiler is fed with 0.1-0.5 MPa (gauge pressure) heating steam to maintain the tower bottom pressure at 0.01-0.05 MPa (gauge pressure), part of the liquid at the bottom of the tower is vaporized by a reboiler, and the rising gas carries out multi-stage gas-liquid mass transfer with the falling liquid in the rectifying tower, and petroleum ether and methylene chloride organic impurities are constantly enriched in the gas phase. Set, finally discharged from the gas phase outlet of the rectifying tower in the form of gas;

在精馏塔内,塔顶压力维持在0~0.01MPa(表压),含有石油醚、二氯甲烷和水的气体经过冷凝后在回流罐内形成上中下三层,下层二氯甲烷有机相采出,作为溶剂回用于原生产工艺;中间层含少量有机物的水相通过管路回流到精馏塔内,与上升的气相进行热量与质量交换;上层的石油醚随水进入层析器,在层析器内分成两相,有机相石油醚作为溶剂回用于原生产工艺;In the rectification tower, the pressure at the top of the tower is maintained at 0-0.01MPa (gauge pressure). After condensation, the gas containing petroleum ether, dichloromethane and water will form upper, middle and lower layers in the reflux tank. The lower layer of dichloromethane is organic The phase is extracted and used as a solvent for the original production process; the water phase containing a small amount of organic matter in the middle layer is returned to the rectification tower through the pipeline, and exchanges heat and mass with the rising gas phase; the petroleum ether in the upper layer enters the chromatography with water The device is divided into two phases in the chromatograph, and the organic phase petroleum ether is used as a solvent for the original production process;

第四步:采出浓缩后的新戊二醇溶液The fourth step: extract the concentrated neopentyl glycol solution

在精馏塔内,由于新戊二醇沸点高,不断在液相中富集而降至塔底,塔底液体一部分通过再沸器汽化,另一部分为浓缩后的新戊二醇,经过管路流经二级预热器后采出。In the rectification tower, due to the high boiling point of neopentyl glycol, it is continuously enriched in the liquid phase and falls to the bottom of the tower. Part of the liquid at the bottom of the tower is vaporized through the reboiler, and the other part is concentrated neopentyl glycol. The pipeline is extracted after passing through the secondary preheater.

本发明实现的原理为:The principle that the present invention realizes is:

新戊二醇缩合水洗母液中的杂质包括不溶性固体颗粒、微量硫酸钙、石油醚、二氯甲烷等。本发明将新戊二醇缩合水洗母液通过一个过滤器,首先过滤掉溶液中的固体颗粒,再将母液通过一级和二级预热器预热到85~95℃后,从精馏塔中部送入塔内。进入塔内的新戊二醇缩合水洗母液与塔内上升的气相进行热量和质量传递。轻组分有机杂质和部分水不断在气相中富集,上升到塔顶经过冷凝器和层析器后采出有机相和部分水相;重组分新戊二醇不断在液相中富集,下降到塔底后被采出。塔顶采出的水相中新戊二醇含量在10ppm以下,塔底采出的新戊二醇浓缩产品中有机物含量在2ppm以下。由于新戊二醇缩合水洗母液中的微量硫酸钙不挥发,处理过程中会逐渐在塔底聚集,经过旋液分离器分离并采出,从旋液分离器出来的液体被加热汽化,进入塔内与塔内下降的液体进行热量和质量传递。Impurities in the neopentyl glycol condensation washing mother liquor include insoluble solid particles, trace amounts of calcium sulfate, petroleum ether, dichloromethane, and the like. In the present invention, the neopentyl glycol condensation water-washing mother liquor is passed through a filter, the solid particles in the solution are firstly filtered out, and then the mother liquor is preheated to 85-95°C through the first-stage and second-stage preheaters. into the tower. The neopentyl glycol condensation water washing mother liquor entering the tower conducts heat and mass transfer with the rising gas phase in the tower. The light component organic impurities and part of water are continuously enriched in the gas phase, rise to the top of the tower and pass through the condenser and chromatography to extract the organic phase and part of the water phase; the heavy component neopentyl glycol is continuously enriched in the liquid phase, It is extracted after falling to the bottom of the tower. The content of neopentyl glycol in the water phase extracted from the top of the tower is below 10ppm, and the content of organic matter in the concentrated product of neopentyl glycol extracted from the bottom of the tower is below 2ppm. Since the trace amount of calcium sulfate in the neopentyl glycol condensation water washing mother liquor is not volatile, it will gradually accumulate at the bottom of the tower during the treatment process, and be separated and extracted by the hydrocyclone. The liquid coming out of the hydrocyclone is heated and vaporized, and enters the tower The heat and mass transfer between the inside and the descending liquid in the tower.

本发明具有如下有益效果:The present invention has following beneficial effect:

(1)本发明减少了新戊二醇缩合水洗母液处理过程中新戊二醇的损失量。现有水蒸汽蒸馏工艺在浓缩新戊二醇缩合水洗母液时,随着有机物杂质被蒸出,平衡蒸馏罐顶部冷凝的液体中新戊二醇的质量分数为2~3%,造成了原料的浪费。本发明所采用的工艺和装置在处理新戊二醇缩合水洗母液过程中,塔顶蒸出的水中新戊二醇含量在10ppm以下,处理每批母液多回收新戊二醇35~55千克。(1) The present invention reduces the loss of neopentyl glycol during the treatment process of neopentyl glycol condensation water washing mother liquor. When the existing water steam distillation process concentrates neopentyl glycol condensation water washing mother liquor, along with the organic matter impurities are distilled off, the mass fraction of neopentyl glycol in the liquid condensed on the top of the equilibrium distillation tank is 2 to 3%, resulting in the loss of raw materials. waste. The technology and device adopted in the present invention process neopentyl glycol condensation washing mother liquor, the neopentyl glycol content in the water evaporated from the tower top is below 10ppm, and 35-55 kg more neopentyl glycol is recovered for each batch of mother liquor.

(2)本发明增加了新戊二醇缩合水洗母液的处理效率。现有水蒸汽蒸馏工艺在浓缩新戊二醇溶液时,每批物料约为20吨,需要处理20小时。本发明采用连续化处理工艺,处理20吨新戊二醇溶液仅需要6小时。(2) The present invention increases the treatment efficiency of the neopentyl glycol condensation water washing mother liquor. When the existing steam distillation process concentrates the neopentyl glycol solution, each batch of material is about 20 tons and needs to be processed for 20 hours. The invention adopts a continuous treatment process, and it only takes 6 hours to process 20 tons of neopentyl glycol solution.

(3)本发明减少了水蒸汽与循环水用量,降低了生产成本。本发明采用了热量集成法,新戊二醇缩合水洗母液经过精馏塔塔顶气相和塔底液相两级预热,预热后溶液温度达到85~95℃,一方面减少了新鲜蒸汽用量,另一方面减少了塔顶冷凝器的循环水用量。处理每吨新戊二醇缩合水洗母液节约新鲜水蒸汽110~130千克,节约循环水6000~7000千克。(3) The present invention reduces the consumption of steam and circulating water, and reduces the production cost. The invention adopts the heat integration method, and the neopentyl glycol condensation washing mother liquor is preheated in two stages of the gas phase at the top of the rectification tower and the liquid phase at the bottom of the tower. , On the other hand, it reduces the circulating water consumption of the overhead condenser. Treating each ton of neopentyl glycol condensation washing mother liquor saves 110-130 kg of fresh water vapor and 6,000-7,000 kg of circulating water.

(4)本发明改进了浓缩后的新戊二醇外观特征。现有水蒸汽蒸馏工艺采用间歇式操作,处理一批新戊二醇缩合水洗母液用时为20~22小时,由于罐内溶液长时间处于高温状态下,导致部分溶液碳化,颜色偏黄。本发明采用连续化处理工艺,处理合格后的新戊二醇溶液及时从塔底被采出,保证了新戊二醇产品的纯度和色度。(4) The present invention improves the appearance characteristics of the concentrated neopentyl glycol. The existing steam distillation process adopts intermittent operation, and it takes 20 to 22 hours to process a batch of neopentyl glycol condensation washing mother liquor. Because the solution in the tank is kept at high temperature for a long time, part of the solution is carbonized and the color is yellowish. The invention adopts a continuous treatment process, and the qualified neopentyl glycol solution is extracted from the bottom of the tower in time to ensure the purity and chroma of the neopentyl glycol product.

(5)本发明具有处理新戊二醇缩合水洗母液中微量硫酸钙的能力。现有水蒸汽蒸馏工艺利用蒸馏罐间歇处理新戊二醇缩合水洗母液,随着母液中的水不断被蒸出,罐内溶液中的硫酸钙逐渐聚集,导致蒸馏罐壁内结垢。本发明利用旋液分离器及时将塔底聚集的硫酸钙移出,增加了新戊二醇缩合水洗母液连续化处理装置对硫酸钙的处理能力,防止硫酸钙在精馏塔壁内结垢。(5) The present invention has the ability to handle trace amounts of calcium sulfate in the neopentyl glycol condensation washing mother liquor. The existing steam distillation process uses a distillation tank to intermittently process the neopentyl glycol condensation water washing mother liquor. As the water in the mother liquor is continuously evaporated, calcium sulfate in the solution in the tank gradually accumulates, resulting in scaling in the distillation tank wall. The present invention utilizes the hydrocyclone to remove the calcium sulfate accumulated at the bottom of the tower in time, increases the calcium sulfate treatment capacity of the neopentyl glycol condensation water washing mother liquor continuous treatment device, and prevents the calcium sulfate from scaling in the rectifying tower wall.

附图说明Description of drawings

附图为本发明的结构示意图。Accompanying drawing is the structural representation of the present invention.

图中,1.过滤器;2.一级预热器;3.二级预热器;4.精馏塔;5.回流罐;6.再沸器;7.层析器;8.旋液分离器。In the figure, 1. filter; 2. primary preheater; 3. secondary preheater; 4. rectification column; 5. reflux tank; 6. reboiler; liquid separator.

具体实施方式detailed description

以下结合附图进一步说明,并非限制本发明所涉及的范围。The following will be further described in conjunction with the accompanying drawings, not to limit the scope of the present invention.

如附图所示,本发明首先将新戊二醇缩合水洗母液通过过滤器1,过滤掉其中不溶性固体颗粒。过滤后的溶液通过一级预热器2和二级预热器3预热到一定温度后进入精馏塔4内。精馏塔由再沸器6加热,塔内上升的气体经过冷却后进入回流罐5。二氯甲烷从回流罐5底部采出,石油醚和水从回流罐上部采出进入层析器7,水从层析器7底部采出,石油醚从层析器7上部采出。新戊二醇缩合水洗母液中含有微量的硫酸钙,在加热过程中会逐渐被浓缩,经过旋液分离器8后从底部排出,液体进入再沸器进行加热汽化。As shown in the drawings, the present invention first passes the neopentyl glycol condensation washing mother liquor through the filter 1 to filter out insoluble solid particles therein. The filtered solution is preheated to a certain temperature by the primary preheater 2 and the secondary preheater 3 and then enters the rectification column 4 . The rectification column is heated by a reboiler 6, and the rising gas in the column enters the reflux tank 5 after being cooled. Dichloromethane is extracted from the bottom of the reflux tank 5, petroleum ether and water are extracted from the upper part of the reflux tank and enter the chromatography 7, water is extracted from the bottom of the chromatography 7, and petroleum ether is extracted from the upper part of the chromatography 7. The neopentyl glycol condensation water washing mother liquor contains a small amount of calcium sulfate, which will be gradually concentrated during the heating process, and will be discharged from the bottom after passing through the hydrocyclone 8, and the liquid will enter the reboiler for heating and vaporization.

以下是本发明的具体实施实例:The following are specific implementation examples of the present invention:

实施实例1:新戊二醇缩合水洗母液进料量为4000千克/小时,经过一级预热器后温度从20℃升高到70℃,经过二级预热器后温度升高到90℃,精馏塔塔底物料温度从109℃降到75℃,蒸汽用量为450千克/小时。20吨新戊二醇溶液处理时间约5小时,塔顶采出二氯甲烷的体积为800升,石油醚的体积为500升。塔顶采出的水经过分水器后,其中新戊二醇含量为8ppm且COD为236毫克/升,塔底采出的新戊二醇质量分数为70%,其中二氯甲烷和石油醚未检测出。Implementation example 1: The feed rate of neopentyl glycol condensation water washing mother liquor is 4000 kg/h, the temperature rises from 20°C to 70°C after passing through the primary preheater, and the temperature rises to 90°C after passing through the secondary preheater , The temperature of the bottom material of the rectification tower dropped from 109°C to 75°C, and the steam consumption was 450 kg/hour. The treatment time of 20 tons of neopentyl glycol solution is about 5 hours, the volume of dichloromethane produced at the top of the tower is 800 liters, and the volume of petroleum ether is 500 liters. After the water produced at the top of the tower passes through the water separator, the neopentyl glycol content is 8ppm and the COD is 236 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 70%, wherein dichloromethane and petroleum ether Not detected.

实施实例2:新戊二醇缩合水洗母液进料量为4000千克/小时,经过一级预热器后温度从20℃升高到75℃,经过二级预热器后温度升高到95℃,精馏塔塔底物料温度从108℃降到70℃,蒸汽用量为400千克/小时。20吨新戊二醇溶液处理时间约5小时,塔顶采出二氯甲烷的体积为830升,石油醚的体积为550升。塔顶采出的水经过分水器后,其中新戊二醇含量为9ppm且COD为156毫克/升,塔底采出的新戊二醇质量分数为68%,其中二氯甲烷和石油醚浓度为1ppm。Implementation example 2: The feed rate of neopentyl glycol condensation water washing mother liquor is 4000 kg/h, the temperature rises from 20°C to 75°C after passing through the first-stage preheater, and the temperature rises to 95°C after passing through the second-stage preheater , The temperature of the bottom material of the rectification tower dropped from 108°C to 70°C, and the steam consumption was 400 kg/hour. The treatment time of 20 tons of neopentyl glycol solution is about 5 hours, the volume of dichloromethane extracted from the tower top is 830 liters, and the volume of petroleum ether is 550 liters. After the water produced at the top of the tower passes through the water separator, the content of neopentyl glycol is 9ppm and the COD is 156 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 68%, of which dichloromethane and petroleum ether The concentration is 1ppm.

实施实例3:新戊二醇缩合水洗母液进料量为5000千克/小时,经过一级预热器后温度从20℃升高到65℃,经过二级预热器后温度升高到92℃,精馏塔塔底物料温度从108℃降到72℃,蒸汽用量为550千克/小时。20吨新戊二醇溶液处理时间约4小时,塔顶采出二氯甲烷的体积为850升,石油醚的体积为520升。塔顶采出的水经过分水器后,其中新戊二醇含量为5ppm且COD为221毫克/升,塔底采出的新戊二醇浓质量分数为67%,其中二氯甲烷和石油醚浓度为1ppm。Implementation example 3: The feed rate of neopentyl glycol condensation water washing mother liquor is 5000 kg/hour, the temperature rises from 20°C to 65°C after passing through the primary preheater, and the temperature rises to 92°C after passing through the secondary preheater , The temperature of the bottom material of the rectification tower dropped from 108°C to 72°C, and the steam consumption was 550 kg/hour. The treatment time of 20 tons of neopentyl glycol solution is about 4 hours, the volume of dichloromethane extracted from the tower top is 850 liters, and the volume of petroleum ether is 520 liters. After the water produced at the top of the tower passes through the water separator, the neopentyl glycol content is 5ppm and the COD is 221 mg/liter, and the concentrated mass fraction of neopentyl glycol produced at the bottom of the tower is 67%, of which dichloromethane and petroleum The ether concentration was 1 ppm.

实施实例4:新戊二醇缩合水洗母液进料量为5000千克/小时,经过一级预热器后温度从20℃升高到63℃,经过二级预热器后温度升高到95℃,精馏塔塔底物料温度从110℃降到68℃,蒸汽用量为580千克/小时。20吨新戊二醇溶液处理时间约4小时,塔顶采出二氯甲烷的体积为900升,石油醚的体积为550升。塔顶采出的水经过分水器后,其中新戊二醇含量为2ppm且COD为250毫克/升,塔底采出的新戊二醇质量分数为72%,其中二氯甲烷和石油醚未检测出。Implementation example 4: The feed rate of neopentyl glycol condensation water washing mother liquor is 5000 kg/h, the temperature rises from 20°C to 63°C after passing through the primary preheater, and the temperature rises to 95°C after passing through the secondary preheater , The temperature of the bottom material of the rectification tower dropped from 110°C to 68°C, and the steam consumption was 580 kg/hour. The treatment time of 20 tons of neopentyl glycol solution is about 4 hours, the volume of dichloromethane extracted from the tower top is 900 liters, and the volume of petroleum ether is 550 liters. After the water produced at the top of the tower passes through the water separator, the content of neopentyl glycol is 2ppm and the COD is 250 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 72%, of which dichloromethane and petroleum ether Not detected.

实施实例5:新戊二醇缩合水洗母液进料量为3000千克/小时,经过一级预热器后温度从20℃升高到78℃,经过二级预热器后温度升高到95℃,精馏塔塔底物料温度从112℃降到73℃,蒸汽用量为350千克/小时。18吨新戊二醇溶液处理时间约6小时,塔顶采出二氯甲烷的体积为700升,石油醚的体积为450升。塔顶采出的水经过分水器后,其中新戊二醇含量为8ppm且COD为153毫克/升,塔底采出的新戊二醇质量分数为73%,其中二氯甲烷和石油醚未检测出。Implementation example 5: The feed rate of neopentyl glycol condensation water washing mother liquor is 3000 kg/h, the temperature rises from 20°C to 78°C after passing through the primary preheater, and the temperature rises to 95°C after passing through the secondary preheater , The temperature of the bottom material of the rectification tower dropped from 112°C to 73°C, and the steam consumption was 350 kg/hour. The treatment time of 18 tons of neopentyl glycol solution is about 6 hours, the volume of dichloromethane extracted from the tower top is 700 liters, and the volume of petroleum ether is 450 liters. After the water produced at the top of the tower passes through the water separator, the content of neopentyl glycol is 8ppm and the COD is 153 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 73%, wherein dichloromethane and petroleum ether Not detected.

实施实例6:新戊二醇缩合水洗母液进料量为3000千克/小时,经过一级预热器后温度从20℃升高到74℃,经过二级预热器后温度升高到93℃,精馏塔塔底物料温度从109℃降到67℃,蒸汽用量为380千克/小时。18吨新戊二醇溶液处理时间约6小时,塔顶采出二氯甲烷的体积为720升,石油醚的体积为440升。塔顶采出的水经过分水器后,其中新戊二醇含量为5ppm且COD为142毫克/升,塔底采出的新戊二醇质量分数为70%,其中二氯甲烷和石油醚浓度为1ppm。Implementation Example 6: The feed rate of neopentyl glycol condensation water washing mother liquor is 3000 kg/h, the temperature rises from 20°C to 74°C after passing through the primary preheater, and the temperature rises to 93°C after passing through the secondary preheater , The temperature of the bottom material of the rectification tower dropped from 109°C to 67°C, and the steam consumption was 380 kg/hour. The treatment time of 18 tons of neopentyl glycol solution is about 6 hours, the volume of dichloromethane extracted from the tower top is 720 liters, and the volume of petroleum ether is 440 liters. After the water produced at the top of the tower passes through the water separator, the neopentyl glycol content is 5ppm and the COD is 142 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 70%, wherein dichloromethane and petroleum ether The concentration is 1ppm.

实施实例7:新戊二醇缩合水洗母液进料量为4500千克/小时,经过一级预热器后温度从20℃升高到69℃,经过二级预热器后温度升高到91℃,精馏塔塔底物料温度从110℃降到70℃,蒸汽用量为500千克/小时。18吨新戊二醇溶液处理时间约4小时,塔顶采出二氯甲烷的体积为710升,石油醚的体积为450升。塔顶采出的水经过分水器后,其中新戊二醇含量为5ppm且COD为285毫克/升,塔底采出的新戊二醇质量分数为71%,其中二氯甲烷和石油醚未检测出。Implementation Example 7: The feed rate of neopentyl glycol condensation water washing mother liquor is 4500 kg/h, the temperature rises from 20°C to 69°C after passing through the primary preheater, and rises to 91°C after passing through the secondary preheater , The temperature of the material at the bottom of the rectification tower dropped from 110°C to 70°C, and the steam consumption was 500 kg/hour. The treatment time of 18 tons of neopentyl glycol solution is about 4 hours, the volume of dichloromethane extracted from the tower top is 710 liters, and the volume of petroleum ether is 450 liters. After the water produced at the top of the tower passes through the water separator, the content of neopentyl glycol is 5ppm and the COD is 285 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 71%, wherein dichloromethane and petroleum ether Not detected.

实施实例8:新戊二醇缩合水洗母液进料量为4500千克/小时,经过一级预热器后温度从20℃升高到70℃,经过二级预热器后温度升高到88℃,精馏塔塔底物料温度从107℃降到69℃,蒸汽用量为520千克/小时。18吨新戊二醇溶液处理时间约4小时,塔顶采出二氯甲烷的体积为730升,石油醚的体积为400升。塔顶采出的水经过分水器后,其中新戊二醇含量为3ppm且COD为213毫克/升,塔底采出的新戊二醇质量分数为66%,其中二氯甲烷和石油醚浓度为2ppm。Implementation Example 8: The feed rate of neopentyl glycol condensation water washing mother liquor is 4500 kg/h, the temperature rises from 20°C to 70°C after passing through the primary preheater, and the temperature rises to 88°C after passing through the secondary preheater , The temperature of the bottom material of the rectification tower dropped from 107°C to 69°C, and the steam consumption was 520 kg/hour. The treatment time of 18 tons of neopentyl glycol solution is about 4 hours, the volume of dichloromethane extracted from the tower top is 730 liters, and the volume of petroleum ether is 400 liters. After the water produced at the top of the tower passes through the water separator, the content of neopentyl glycol is 3ppm and the COD is 213 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 66%, of which dichloromethane and petroleum ether The concentration is 2ppm.

实施实例9:新戊二醇缩合水洗母液进料量为6000千克/小时,经过一级预热器后温度从20℃升高到72℃,经过二级预热器后温度升高到95℃,精馏塔塔底物料温度从111℃降到72℃,蒸汽用量为850千克/小时。22吨新戊二醇溶液处理时间约4小时,塔顶采出二氯甲烷的体积为880升,石油醚的体积为530升。塔顶采出的水经过分水器后,其中新戊二醇含量为4ppm且COD为157毫克/升,塔底采出的新戊二醇质量分数为72%,其中二氯甲烷和石油醚未检测出。Implementation example 9: The feed rate of neopentyl glycol condensation water washing mother liquor is 6000 kg/h, the temperature rises from 20°C to 72°C after passing through the primary preheater, and the temperature rises to 95°C after passing through the secondary preheater , The temperature of the bottom material of the rectification tower dropped from 111°C to 72°C, and the steam consumption was 850 kg/hour. The treatment time of 22 tons of neopentyl glycol solution is about 4 hours, the volume of dichloromethane extracted from the tower top is 880 liters, and the volume of petroleum ether is 530 liters. After the water produced at the top of the tower passes through the water separator, the content of neopentyl glycol is 4ppm and the COD is 157 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 72%, wherein dichloromethane and petroleum ether Not detected.

实施实例10:新戊二醇缩合水洗母液进料量为6000千克/小时,经过一级预热器后温度从20℃升高到70℃,经过二级预热器后温度升高到86℃,精馏塔塔底物料温度从115℃降到76℃,蒸汽用量为800千克/小时。22吨新戊二醇溶液处理时间约4小时,塔顶采出二氯甲烷的体积为800升,石油醚的体积为580升。塔顶采出的水经过分水器后,其中新戊二醇含量为6ppm且COD为108毫克/升,塔底采出的新戊二醇质量分数为76%,其中二氯甲烷和石油醚未检测出。Implementation example 10: The feed rate of neopentyl glycol condensation water washing mother liquor is 6000 kg/hour, the temperature rises from 20°C to 70°C after passing through the primary preheater, and the temperature rises to 86°C after passing through the secondary preheater , The temperature of the bottom material of the rectification tower dropped from 115°C to 76°C, and the steam consumption was 800 kg/hour. The treatment time of 22 tons of neopentyl glycol solution is about 4 hours, the volume of dichloromethane produced at the top of the tower is 800 liters, and the volume of petroleum ether is 580 liters. After the water produced at the top of the tower passes through the water separator, the content of neopentyl glycol is 6ppm and the COD is 108 mg/liter, and the mass fraction of neopentyl glycol produced at the bottom of the tower is 76%, of which dichloromethane and petroleum ether Not detected.

Claims (7)

1.一种新戊二醇缩合水洗母液的连续化处理工艺流程,其特征在于:所述流程以水和新戊二醇为主要原料,包括以下步骤:1. a continuous treatment process flow for neopentyl glycol condensation washing mother liquor, is characterized in that: described flow process is main raw material with water and neopentyl glycol, comprises the following steps: 第一步:过滤新戊二醇缩合水洗母液中固体颗粒The first step: filter the solid particles in the neopentyl glycol condensation washing mother liquor 所述新戊二醇缩合水洗母液中含有石油醚、二氯甲烷有机杂质和不溶性固体颗粒,用泵从储罐中将新戊二醇缩合水洗母液通过过滤器输送到精馏塔内,拦截其中不溶性固体颗粒,定期清理过滤器中的滤渣,过滤后得到的新戊二醇缩合水洗母液中含有石油醚和二氯甲烷;The neopentyl glycol condensation water washing mother liquor contains petroleum ether, dichloromethane organic impurities and insoluble solid particles, and the neopentyl glycol condensation water washing mother liquor is transported from the storage tank to the rectification tower through a filter by a pump, and intercepted Insoluble solid particles, regularly clean the filter residue in the filter, and the neopentyl glycol condensation washing mother liquor obtained after filtration contains petroleum ether and methylene chloride; 第二步:预热新戊二醇缩合水洗母液The second step: preheating neopentyl glycol condensation water washing mother liquor 以来自精馏塔的塔顶气相和塔底浓缩后的新戊二醇溶液为热源,在所述一级和二级预热器中将新戊二醇缩合水洗母液从常温加热到85~95℃;Using the vapor phase at the top of the rectification tower and the concentrated neopentyl glycol solution at the bottom of the tower as the heat source, the neopentyl glycol condensation water washing mother liquor is heated from normal temperature to 85-95°C in the primary and secondary preheaters. ℃; 第三步:脱除新戊二醇缩合水洗母液中有机杂质The third step: removal of organic impurities in the neopentyl glycol condensation water washing mother liquor 预热后的新戊二醇缩合水洗母液经过泵输送到所述精馏塔内,塔底再沸器通入0.1~0.5MPa表压的加热蒸汽,使塔底压力维持在0.01~0.05MPa表压,塔底部分液体通过再沸器汽化,上升的气体在所述精馏塔内与下降液体进行多级气液传质,石油醚和二氯甲烷有机杂质不断在气相中富集,最终以气体形式从精馏塔气相出口排出;The preheated neopentyl glycol condensation water washing mother liquor is pumped to the rectification tower, and the bottom reboiler is fed with heating steam with a gauge pressure of 0.1-0.5MPa to maintain the pressure at the bottom of the tower at 0.01-0.05MPa gauge. pressure, part of the liquid at the bottom of the tower is vaporized through the reboiler, and the rising gas and the descending liquid carry out multi-stage gas-liquid mass transfer in the rectifying tower, and petroleum ether and dichloromethane organic impurities are continuously enriched in the gas phase, and finally The gas form is discharged from the gas phase outlet of the rectification tower; 在精馏塔内,塔顶压力维持在0~0.01MPa表压,含有石油醚、二氯甲烷和水的气体经过冷凝后在回流罐内形成上中下三层,下层二氯甲烷有机相采出,作为溶剂回用于原生产工艺;中间层含少量有机物的水相通过管路回流到精馏塔内,与上升的气相进行热量与质量交换;上层的石油醚随水进入层析器,在层析器内分成两相,有机相石油醚作为溶剂回用于原生产工艺;In the rectification tower, the pressure at the top of the tower is maintained at 0-0.01MPa gauge pressure, the gas containing petroleum ether, dichloromethane and water is condensed to form upper, middle and lower layers in the reflux tank, and the organic phase of the lower layer of dichloromethane is recovered. It is used as a solvent and reused in the original production process; the water phase containing a small amount of organic matter in the middle layer flows back into the rectification tower through the pipeline, and exchanges heat and mass with the rising gas phase; the petroleum ether in the upper layer enters the chromatograph with water, It is divided into two phases in the chromatograph, and the organic phase petroleum ether is used as a solvent for the original production process; 第四步:采出浓缩后的新戊二醇溶液The fourth step: extract the concentrated neopentyl glycol solution 在精馏塔内,由于新戊二醇沸点高,不断在液相中富集而降至塔底,塔底液体一部分通过再沸器汽化,另一部分为浓缩后的新戊二醇,经过管路流经二级预热器后采出。In the rectification tower, due to the high boiling point of neopentyl glycol, it is continuously enriched in the liquid phase and falls to the bottom of the tower. Part of the liquid at the bottom of the tower is vaporized through the reboiler, and the other part is concentrated neopentyl glycol. The pipeline is extracted after passing through the secondary preheater. 2.根据权利要求1所述的新戊二醇缩合水洗母液的连续化处理工艺流程,其特征在于:所处理的新戊二醇缩合水洗母液中,石油醚的质量分数为0.02~8%,二氯甲烷的质量分数为0.02~2%,新戊二醇的质量分数为10~50%。2. the continuous treatment technological process of neopentyl glycol condensation washing mother liquor according to claim 1, is characterized in that: in the neopentyl glycol condensation washing mother liquor handled, the massfraction of sherwood oil is 0.02~8%, The mass fraction of dichloromethane is 0.02-2%, and the mass fraction of neopentyl glycol is 10-50%. 3.根据权利要求1所述的新戊二醇缩合水洗母液的连续化处理工艺流程,其特征在于:可以连续化处理新戊二醇缩合水洗母液。3. The continuous processing technological process of neopentyl glycol condensation washing mother liquor according to claim 1, characterized in that: the neopentyl glycol condensation washing mother liquor can be processed continuously. 4.根据权利要求3所述的新戊二醇缩合水洗母液的连续化处理工艺流程,其特征在于:采用连续化处理工艺流程,处理每吨新戊二醇溶液所需时间为2~3小时。4. the continuous treatment process flow of neopentyl glycol condensation water washing mother liquor according to claim 3, is characterized in that: adopt continuous treatment process flow, the time required for processing every ton of neopentyl glycol solution is 2~3 hours . 5.根据权利要求1所述的新戊二醇缩合水洗母液的连续化处理工艺流程,其特征在于:蒸出的水中新戊二醇质量分数在10ppm以下,新戊二醇的回收率在99.9%以上。5. the continuous treatment technological process of neopentyl glycol condensation washing mother liquor according to claim 1, is characterized in that: the mass fraction of neopentyl glycol in the water that steams out is below 10ppm, and the rate of recovery of neopentyl glycol is 99.9% %above. 6.根据权利要求1所述的新戊二醇缩合水洗母液的连续化处理工艺流程,其特征在于:采用热量集成工艺,处理每吨新戊二醇缩合水洗母液,精馏塔所需要的蒸汽为100~500kg。6. the continuous treatment technological process of neopentyl glycol condensation washing mother liquor according to claim 1, is characterized in that: adopt heat integration process, process every ton of neopentyl glycol condensation washing mother liquor, the steam needed by rectification tower 100-500kg. 7.根据权利要求1所述的新戊二醇缩合水洗母液的连续化处理工艺流程,其特征在于:可以处理新戊二醇缩合水洗母液中硫酸钙的固体。7. the continuous treatment technological process of neopentyl glycol condensation washing mother liquor according to claim 1, is characterized in that: can handle the solid of calcium sulfate in neopentyl glycol condensation washing mother liquor.
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