WO2016155101A1 - 一种酚氨废水中酚油联合脱除系统及处理工艺 - Google Patents

一种酚氨废水中酚油联合脱除系统及处理工艺 Download PDF

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WO2016155101A1
WO2016155101A1 PCT/CN2015/079705 CN2015079705W WO2016155101A1 WO 2016155101 A1 WO2016155101 A1 WO 2016155101A1 CN 2015079705 W CN2015079705 W CN 2015079705W WO 2016155101 A1 WO2016155101 A1 WO 2016155101A1
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extraction
tank
phenol
extractant
tower
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PCT/CN2015/079705
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English (en)
French (fr)
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宁朋歌
曹宏斌
张懿
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中国科学院过程工程研究所
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  • the invention belongs to the technical field of water treatment, and particularly relates to a combined removal system and treatment process of phenol oil in phenol ammonia wastewater.
  • Phenol ammonia wastewater is industrial wastewater produced by coking, gas purification and chemical product refining. It mainly contains volatile phenols, polycyclic aromatic hydrocarbons and heterocyclic compounds such as oxygen, sulfur and nitrogen. It is a high COD, high phenolic value and high ammonia nitrogen.
  • Industrial organic wastewater that is difficult to handle. It mainly comes from the residual ammonia water, the waste water produced during the gas purification process, the refining process of tar, crude benzene, etc., and the wastewater generated from other occasions.
  • Phenol ammonia wastewater is an industrial wastewater containing a large amount of refractory organic pollutants. Excessive discharges cause serious pollution to the environment.
  • Patent CN10332067A discloses a new method for treating coking residual ammonia water.
  • the invention consists of five processes: ammonia deacidification, gas stripping, extraction, dephenolization, oxidation treatment, and wastewater utilization.
  • Patent CN101597124A discloses a method for treating phenol-containing ammonia gasification wastewater, which comprises single tower pressure stripping to remove acid gas and ammonia, line extraction gas three-stage segregation, diisopropyl ether extraction phenol, solvent recovery Process and get a crude phenol product.
  • the solvent recovery tower and the solvent stripper of the invention recover the extractant to obtain crude phenol, and realize the process of jointly removing the acid gas and ammonia from the single tower of the coal gasification wastewater.
  • the present invention provides a phenolic oil combined removal process in phenol ammonia wastewater. Adding a tar recovery system and an intermediate layer recovery system on the basis of the original process, improving the process, solving the problem that a large amount of intermediate layers are not available in the existing extraction process, improving the recovery rate of the extractant, phenol, etc., and jointly recovering the content of the wastewater Higher by-product tars, thereby reducing wastewater treatment costs, reducing pollutant emissions, and making the COD content of the effluent meet subsequent processing requirements.
  • a phenolic oil combined removal system for phenol ammonia wastewater comprising a degreasing system, an extraction system, a stripping system and a purification system in sequence.
  • the degreasing system comprises a phenol ammonia wastewater storage tank, a coke filter, a ceramic membrane filter and an intermediate tank for deoiling wastewater, the phenol ammonia wastewater is stored in the phenol ammonia wastewater storage tank, and the coke filter and the ceramic membrane filter are used for taking off In addition to solid contaminants and partially solid tar in phenol ammonia wastewater.
  • the extraction system comprises a heat exchanger, an extraction tank, an extraction tower, an intermediate tank of an extractant, an intermediate layer treatment reactor, a dephenolation water intermediate tank and an alkali liquid preparation tank, wherein the heat exchanger discharge port and the extraction tank inlet port Connected, the bottom discharge port of the extraction tank is connected with the top inlet of the extraction tower, and the intermediate layer discharge port of the extraction tank is connected with the inlet of the intermediate layer treatment reactor, and the extraction tower top discharge port and the extraction tank extractant
  • the inlet is connected, the middle layer discharge port of the extraction tower is connected with the intermediate layer processing reactor feed port, the bottom outlet of the extraction tower bottom is connected with the feed port of the dephenolized water intermediate tank, and the extraction tank intermediate tank discharge port and the extraction tower
  • the extractant inlets are connected, and the intermediate layer treatment reactor water phase outlet is connected to the dephenolized water intermediate tank feed port.
  • the stripping system comprises a stripping column, a phenol-rich organic phase intermediate tank and a sodium phenol intermediate tank, wherein the bottom strip outlet of the stripping tower is connected to the intermediate tank inlet of the sodium phenolate, and the water in the middle of the phenol-rich organic phase is The feed port is connected to the phenol sodium intermediate tank feed port.
  • the stripping column is a three-stage stripping column.
  • the purification system comprises an extractant purification tower, an overhead condenser, a tar intermediate tank and a purification extractant intermediate tank, wherein the extractant purification tower top discharge outlet is connected with the overhead condenser feed inlet, and the overhead condenser outlet Connected to the intermediate tank inlet of the purification extractant, the extractant purification tower bottom outlet is connected to the tar intermediate tank.
  • the discharge port of the middle tank of the deoiling waste water in the degreasing system is connected to the inlet of the heat exchanger, and the discharge port at the top of the extraction tank is connected with the top feed port of the stripping tower, and the intermediate layer processes the discharge port of the reactor and the phenol-rich organic
  • the intermediate tank inlet is connected, the lye preparation tank outlet is connected with the stripping bottom inlet and the phenol-rich organic phase intermediate tank inlet, and the stripping tower top outlet and the extractant intermediate tank are connected.
  • the feed port is connected, the top discharge port of the stripping tower is connected with the feed port of the extractant purification tower bottom, and the organic phase outlet of the phenol-rich organic phase intermediate tank is connected with the inlet of the extractant purification tower bottom to purify the extractant.
  • the intermediate tank discharge port is connected to the extractant intermediate tank feed port.
  • the treatment process of the phenol oil combined removal system in the above phenol ammonia wastewater includes a degreasing process, an extraction process, a stripping process and a purification process.
  • the degreasing process is a pretreatment process, which comprises the steps of: phenol ammonia wastewater entering a phenol ammonia wastewater storage tank, sequentially flowing through a coke filter and a ceramic membrane filter into an intermediate tank of deoiling wastewater, coke filter and ceramic membrane filtration
  • phenol ammonia wastewater entering a phenol ammonia wastewater storage tank, sequentially flowing through a coke filter and a ceramic membrane filter into an intermediate tank of deoiling wastewater, coke filter and ceramic membrane filtration
  • the solid pollutants and part of the solid tar in the phenol ammonia wastewater are removed, the removed materials are incinerated, and the treated wastewater enters the intermediate tank of the deoiled wastewater.
  • the extraction process includes the following steps:
  • Extraction of detarred oil The waste water in the intermediate tank of the deoiled wastewater enters the extraction tank after being cooled by the heat exchanger, and the tar and phenol in the waste water are extracted by the extraction method.
  • the extractant used is circulated and replenished by the phenol-rich organic phase extracted by the extraction tower, and the wastewater discharged from the bottom of the extraction tank enters the extraction tower, and the tar-rich and phenol organic phase extracted in the extraction tank enters the stripping tower, and the intermediate layer of the extraction tank is liquid. Enter the intermediate layer to process the reactor.
  • Extraction and dephenolization The wastewater discharged from the bottom of the extraction tank enters the extraction tower, and the extractant used is from the intermediate tank of the extractant and enters the phenols in the countercurrent extraction wastewater of the extraction tower. Extraction tower top phenol-rich organic phase as extraction The reagent is replenished to the extraction tank, and the liquid in the middle layer of the extraction tower enters the intermediate layer to treat the reactor, and the dephenolized wastewater from the bottom of the extraction tower is introduced into the intermediate tank of the dephenolized water for further subsequent treatment.
  • the intermediate layer treatment reactor separates the oil-water two phases, the desorbed oil phase enters the intermediate phase of the phenol-rich organic phase, and the aqueous phase desorbed from the intermediate layer treatment reactor enters the dephenolation water intermediate tank.
  • the stripping process comprises the steps of: extracting the tar-rich oil and the phenol organic phase discharged from the extraction tank into the stripping column, and removing the phenol in the organic phase by stripping, the lye used is from the lye setting tank.
  • the crude phenol product in the bottom of the stripping bottom enters the intermediate tank of sodium phenolate
  • the organic phase of the top of the stripping tower enters the intermediate tank of the extracting agent and the extracting agent purifying tower
  • the alkali liquid in the alkali liquid arranging tank enters the stripping tower and the intermediate tank of the phenol-rich organic phase.
  • the intermediate tank of the phenol-rich organic phase is periodically fed back to the lye by the lye distribution tank, and the phenol-rich sodium aqueous phase separated by the phenol-rich organic phase intermediate tank enters the phenol sodium intermediate tank, and the organic phase separated by the phenol-rich organic phase is separated.
  • the phase enters the extractant purification tower.
  • the purification process comprises the following steps: the organic phase separated by the intermediate phase of the stripping column and the intermediate tank of the phenol-rich organic phase is intermittently introduced into the extractant purification tower regeneration extractant, and the operation is performed once every 2 to 5 days.
  • the extractant discharged from the top of the extractant purification tower passes through the top condenser and enters the middle tank of the purification extractant, and is pumped into the intermediate tank of the extractant to realize the recycling of the extractant.
  • the extracting agent purifies the tar discharged from the bottom of the tower into the tar intermediate tank and then transferred to the tar storage tank for recycling.
  • the wastewater in the intermediate tank of the deoiling wastewater in the extraction process step (1) is cooled to 20 to 50 ° C by a heat exchanger, for example, 20 ° C, 23 ° C, 25 ° C, 27 ° C, 30 ° C, 33 ° C, 35 ° C, 37 °C, 40°C, 43°C, 45°C, 47°C or 50°C.
  • a heat exchanger for example, 20 ° C, 23 ° C, 25 ° C, 27 ° C, 30 ° C, 33 ° C, 35 ° C, 37 °C, 40°C, 43°C, 45°C, 47°C or 50°C.
  • the extracting agent in the extraction tank is an phenol-rich organic phase of the extracting tower, and the phenol-rich organic phase is recycled.
  • the extraction process step (2) The extractant in the intermediate tank of the extractant is a phenol ammonia wastewater extractant disclosed by the patent CN103848468A, and the extractant contains the following components according to the mass fraction:
  • Acidic phosphorus extractant 0.5 ⁇ 10%
  • the extraction process step (2) the oil-water phase volume ratio in the extraction column is 1:1 to 5, for example, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, etc.
  • the extraction process step (2) extraction temperature in the extraction column is 20 ⁇ 30 ° C, such as 20 ° C, 21 ° C, 22 ° C, 23 ° C, 24 ° C, 25 ° C, 26 ° C, 27 ° C, 28 ° C, 29 ° C or 30 ° C and so on.
  • the alkali solution in the lye arrangement tank is an aqueous sodium hydroxide solution.
  • the concentration concentration of the aqueous sodium hydroxide solution in the lye distribution tank of the stripping process is 10 to 30%, for example, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27% or 30%. Wait.
  • the organic phase separated by the topping organic phase and the phenol-rich organic phase intermediate tank intermittently enters the extracting agent purification tower.
  • the extractant purification tower performs an operation of regenerating the extractant for 2 to 5 days, for example, 2 days, 3 days, 4 days, or 5 days.
  • the top temperature of the extractant purification tower in the stripping process is 120-180 ° C, for example, 120 ° C, 125 ° C, 130 ° C, 135 ° C, 140 ° C, 145 ° C, 150 ° C, 155 ° C, 160 ° C, 165 ° C, 170 ° C, 175 ° C or 180 ° C and so on.
  • the top pressure of the extractant purification tower in the stripping process is 0.05 to 0.25 MPa, for example, 0.05 MPa, 0.07 MPa, 0.10 MPa, 0.13 MPa, 0.15 MPa, 0.17 MPa, 0.20 MPa, 0.23 MPa or 0.25 MPa, and the like.
  • the extractant purification tower bottom temperature in the stripping process is 110 to 150 ° C, for example, 110 ° C, 115 ° C, 120 ° C, 125 ° C, 130 ° C, 135 ° C, 140 ° C, 145 ° C or 150 ° C, and the like.
  • the bottom of the extractant purification tower in the stripping process is 0.10 to 0.20 MPa, for example, 0.10 MPa, 0.11 MPa, 0.12 MPa, 0.13 MPa, 0.14 MPa, 0.15 MPa, 0.16 MPa, 0.17 MPa, 0.18 MPa, 0.19 MPa or 0.20 MPa, etc.
  • the present invention has the following beneficial effects:
  • the extractant has excellent performance and has good effect in treating wastewater. After phenol ammonia wastewater treatment, the tar recovery rate of the wastewater was >94%, the phenol removal rate was >99%, and the COD removal rate was >98%. The discharged water meets the requirements of the subsequent ammonia treatment process.
  • FIG. 1 is a schematic view of a phenolic oil combined removal system device in a phenol ammonia wastewater according to the present invention
  • 1-phenol ammonia wastewater storage tank 2-coke filter, 3-ceramic membrane filter, 4-deoiled wastewater intermediate tank, 5-heat exchanger, 6-extraction tank, 7-extraction tower, 8-extraction Intermediate tank, 9-intermediate treatment reactor, 10-dephenolized water intermediate tank, 11-alkali preparation tank, 12-phenol-rich organic phase intermediate tank, 13-phenol sodium intermediate tank, 14-reverse extraction tower, 15 - Extractant purification tower, 16-tower condenser, 17-tar intermediate tank, 18-purified extractant intermediate tank.
  • FIG. 1 is a schematic view of a phenolic oil combined removal system in a phenol ammonia wastewater according to the present invention.
  • the properties of the raw material phenol ammonia wastewater are shown in Table 1.
  • the treated phenol ammonia wastewater was reddish brown, with a pH of 8.9, a water temperature of 92 ° C, and a flow rate of 102 tons per hour, which was treated according to the procedure shown in Figure 1.
  • Table 1 Table of properties of raw material phenol ammonia wastewater (mg/L)
  • the raw material wastewater flows through the coke filter 2 to remove solid contaminants such as coal tar and particles in the phenol ammonia wastewater.
  • the deoiled wastewater is cooled to 25 ° C by the heat exchanger 5, and then enters the extraction tank 6 to remove the tar and part of the phenol.
  • the extractant is replenished by the phenol-rich extractant in the extraction tower 7.
  • the wastewater discharged from the bottom of the extraction tank 6 is dephenolized from the bottom of the column into the extraction column 7, and the extracting agent is the extracting agent 3 prepared in the "CN103848468A Example" of the invention patent.
  • the extractant 3 is prepared by taking 14 g of isoamyldimethylammonate, 4 g of 2-ethylhexylphosphonic acid mono-2-ethylhexyl-ester and 5 g of di(2-ethylhexyl)phosphoric acid, 2 g 3 - heptanone, 0.3 g of propylene glycol butyl ether, 74.7 g of kerosene, uniformly mixed at 40 ° C, and cooled to room temperature to be the extractant 3 of the present invention.
  • the oil-water extraction was 1:1 and the temperature was 20 °C.
  • the top of the column-rich phenol-rich organic phase of the extraction column 7 is supplied to the extraction tank 6.
  • the dephenolized wastewater from the bottom of the extraction column 7 enters the dephenolized water intermediate tank 10, and is further subjected to steaming treatment.
  • the intermediate layer produced by the extraction tank 6 and the extraction column 7 enters the intermediate layer treatment reactor 9 to separate the oil-water two phases, and the desorbed oil phase enters the phenol-rich organic phase intermediate tank 12.
  • the desorbed aqueous phase enters the dephenolized water intermediate tank 10, and the dephenolized water is subjected to subsequent steaming treatment.
  • the tar-rich oil and the phenol organic phase discharged from the extraction tank 6 enter the stripping column 14, and the organic phase is removed by three-stage stripping.
  • the lye used was an aqueous sodium hydroxide solution having a concentration of 16% from the lyolysis tank 11.
  • the reverse column 14 tower low crude phenol product enters the sodium phenolate intermediate tank 13.
  • the top organic phase of the stripping column 14 enters the intermediate tank 8 of the extractant and is recycled.
  • the phenol-rich organic phase intermediate tank 12 is replenished by the alkali solution disposing tank 11 and the phenol-rich sodium aqueous phase is introduced into the phenol sodium intermediate tank 13, and the organic phase enters the extractant purification tower 15 for regeneration.
  • the extractant regeneration in the extractant purification column 15 is performed every 3 days.
  • the temperature of the top of the extractant purification tower 15 is 130 ° C, the pressure is 0.12 MPa; the temperature of the bottom of the extractant purification tower 15 is 110 ° C, and the pressure is 0.10 MPa.
  • the top of the extractant purification tower 15 is discharged through the overhead condenser 16 and then enters the middle tank 18 of the purification extractant, and then pumped into the intermediate tank 8 of the extractant to realize the recycling of the extractant.
  • the bottom of the extractant purification tower 15 removes tar and enters the tar storage tank through the tar intermediate tank 17 for recycling.
  • Table 2 Desulphurization system sewage water quality information table (random sampling)
  • Table 3 Extraction tank outlet water quality information table (random sampling)
  • Table 4 Water quality information table for the wastewater from the stripping tower (random sampling)
  • the waste water in the intermediate tank 4 of the deoiling wastewater is cooled to 20 ° C by the heat exchanger 5, the oil-water ratio in the extraction column 7 is 1:3, the extraction temperature in the extraction column 7 is 25 ° C, and the hydrogen in the lye is arranged in the tank 11.
  • the concentration of the sodium hydroxide aqueous solution is 10%
  • the extractant regeneration in the extractant purification tower 15 is performed every 2 days
  • the top temperature of the extractant purification tower 15 is 120 ° C
  • the top pressure of the extractant purification tower 15 is 0.05 MPa
  • extraction The temperature of the bottom of the purification tower 15 is 135 ° C
  • the pressure of the bottom of the extractant purification tower 15 is 0.15 MPa.
  • the rest of the process is the same as in the first embodiment.
  • the phenolic oil combined removal system of the phenol ammonia wastewater of the present invention the phenol The total phenol removal rate in ammonia wastewater is 95.20%, the tar removal rate is greater than 99%, the recovery utilization rate is greater than 94%, and the COD removal rate is 98.72%.
  • the waste water in the intermediate tank 4 of the deoiling waste water is cooled to 50 ° C by the heat exchanger 5, the oil-water ratio in the extraction tower 7 is 1:5, the extraction temperature in the extraction tower 7 is 30 ° C, and the sodium hydroxide solution in the lye is arranged in the tank 11.
  • the mass concentration is 30%
  • the extractant regeneration in the extractant purification tower 15 is performed every 5 days
  • the top temperature of the extractant purification tower 15 is 180 ° C
  • the top pressure of the extractant purification tower 15 is 0.25 MPa
  • the bottom temperature is 150 ° C
  • the bottom pressure of the extractant purification tower 15 is 0.2 MPa
  • the rest of the process is the same as in the first embodiment.
  • the total phenol removal in the phenol ammonia wastewater The rate is 94.10%, the tar removal rate is greater than 98%, the recovery rate is greater than 95%, and the COD removal rate is 99.20%.
  • the phenolic oil combined removal system and treatment process of the phenol ammonia wastewater disclosed in the present invention the total phenol removal rate of the phenol ammonia wastewater is greater than 94%, the tar removal rate is greater than 98%, and the recovery utilization rate is greater than 94. %, COD removal rate is greater than 98%.
  • the process utilizes the intermediate layer treatment reactor device to completely separate the two phases of the emulsified oil and water, and the extraction agent has high cycle utilization rate.
  • the phenol-rich extractant in the extraction tower is recycled to the extraction tank, and the tar in the phenol ammonia wastewater is carried by the waste extractant, and finally the crude tar product is removed in the extractant purification tower, thereby avoiding the waste of the tar product, and the treated wastewater is satisfied.
  • the factory's subsequent process requirements can also be reused.

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Abstract

提供了一种酚氨废水中酚油联合脱除系统及处理工艺，其包括除油系统、萃取系统、反萃系统和净化系统及其相应的工艺过程。其中萃取过程包括如下步骤：（1）萃取焦油，废弃物焦油得以回收利用；（2）萃取脱酚，废水苯酚去除率达99.7％以上；（3）中间层的回收利用。萃取剂、酚类得以充分回收利用，避免废水二次污染。提供的酚氨废水处理系统及其处理工艺能同步脱除、回收废水中废弃物焦油和苯酚，实现萃取剂最大程度的循环利用。所述系统和工艺对工厂原设备改动小、成本低，运行稳定，处理后出水总酚去除率大于94％，COD去除率大于98％，满足污水后续蒸氨处理要求。

Description

一种酚氨废水中酚油联合脱除系统及处理工艺 技术领域
本发明属于水处理技术领域，特别涉及一种酚氨废水中酚油联合脱除系统及处理工艺。
背景技术
酚氨废水是炼焦、煤气净化及化工产品精制等过程产生的工业废水，主要含有挥发酚、多环芳烃及氧、硫、氮等杂环化合物，是一种高COD、高酚值、高氨氮且很难处理的工业有机废水。其主要来自于剩余氨水、煤气净化过程中产生的废水和焦油、粗苯等的精制过程及其它场合产生的废水。酚氨废水是含有大量难降解有机污染物的工业废水，超标排放对环境造成严重的污染。
由于该水质水量变化大、成分复杂，所以处理酚氨废水的工艺也众多。国内多采用预处理除油，气提法除氨，萃取法去除酚、氰，生物法处理等工序。
专利CN10332067A公布了一种处理焦化剩余氨水的新方法。该发明由五个工序组成：蒸氨脱酸、气提脱酚、萃取脱酚、氧化处理以及废水利用。
专利CN101597124A公开了一种处理含酚氨煤气化废水的方法，该方法包括单塔加压汽提脱除酸性气体和氨、测线抽出气三级分凝、二异丙醚萃取酚、溶剂回收过程，并得到粗酚产品。该发明溶剂回收塔和溶剂汽提塔回收萃取剂，得到粗酚，并实现了煤气化废水单塔联合脱除酸性气体和氨的过程。
但上述各工艺仅仅是脱焦油，未对酚氨废水中含量较大的焦油进行回收利用。而且未解决萃取工艺中一直存在重大问题，即萃取中间层的存在。萃取中间层的产生会浪费大量萃取剂及可回收的酚类等资源，可导致工厂不能正常作业，严重时甚至需要停产整治。
发明内容
为了克服上述现有技术的不足，本发明提供了一种酚氨废水中酚油联合脱除工艺。在原有工艺基础上添加焦油回收系统和中间层回收系统，改进工序，解决现有萃取工艺中产生大量中间层并无法利用的难题，提高萃取剂、苯酚等的回收利用率，联合回收废水中含量较高的副产品焦油类，从而降低废水处理成本，减少污染物排放量，使出水的COD含量达到后续处理要求。
为达此目的，本发明采用以下技术方案：
一种酚氨废水中酚油联合脱除系统，所述系统依次包括除油系统、萃取系统、反萃系统和净化系统。
所述除油系统依次包括酚氨废水储槽、焦炭过滤器、陶瓷膜过滤器和脱油废水中间槽，酚氨废水储存在酚氨废水储槽中，焦炭过滤器和陶瓷膜过滤器用于脱除酚氨废水中的固体污染物和部分固体焦油。
所述萃取系统包括换热器、萃取槽、萃取塔、萃取剂中间槽、中间层处理反应器、脱酚水中间槽和碱液配制槽，其中换热器出料口与萃取槽进料口相连，萃取槽底部出料口与萃取塔塔顶进料口和相连，萃取槽的中间层出料口与中间层处理反应器进料口相连，萃取塔塔顶出料口与萃取槽萃取剂入口相连，萃取塔的中间层出料口与中间层处理反应器进料口相连，萃取塔塔底出料口与脱酚水中间槽进料口相连，萃取剂中间槽出料口与萃取塔萃取剂入口相连，中间层处理反应器水相出口与脱酚水中间槽进料口相连。
所述反萃系统包括反萃塔、富酚有机相中间槽和酚钠中间槽，其中反萃塔塔底出料口与酚钠中间槽进料口相连，富酚有机相中间槽水相出料口与酚钠中间槽进料口相连。
所述反萃塔为三级反萃塔。
所述净化系统包括萃取剂净化塔、塔顶冷凝器、焦油中间槽和净化萃取剂中间槽，其中萃取剂净化塔塔顶出料口与塔顶冷凝器进料口相连，塔顶冷凝器出口与净化萃取剂中间槽进料口相连，萃取剂净化塔塔底出料口与焦油中间槽相连。
所述除油系统中脱油废水中间槽出料口与换热器入口相连，萃取槽顶部出料口与反萃塔塔顶进料口相连，中间层处理反应器出料口与富酚有机相中间槽进料口相连，碱液配制槽出料口与反萃塔塔底进料口和富酚有机相中间槽进料口相连，反萃塔塔顶出料口与萃取剂中间槽进料口相连，反萃塔塔顶出料口与萃取剂净化塔塔底进料口相连，富酚有机相中间槽有机相出料口与萃取剂净化塔塔底进料口相连，净化萃取剂中间槽出料口与萃取剂中间槽进料口相连。
以上所述酚氨废水中酚油联合脱除系统的处理工艺，所述处理工艺包括除油过程、萃取过程、反萃过程和净化过程。
所述除油过程为预处理过程，其包括以下步骤：酚氨废水进入酚氨废水储槽，依次流经焦炭过滤器和陶瓷膜过滤器进入脱油废水中间槽，焦炭过滤器和陶瓷膜过滤器脱除酚氨废水中的固体污染物和部分固体焦油，脱除物进行焚烧处理，处理后的废水进入脱油废水中间槽。
所述萃取过程包括以下步骤：
(1)萃取脱焦油：脱油废水中间槽的废水经换热器降温后进入萃取槽，用萃取法将废水中的焦油和酚萃取出。所用的萃取剂由萃取塔萃取出的富酚有机相循环补给，萃取槽槽底排出的废水进入萃取塔，萃取槽中萃取出的富焦油和酚有机相进入反萃塔，萃取槽中间层液体进入中间层处理反应器。
(2)萃取脱酚：萃取槽槽底排出的废水进入萃取塔，所用萃取剂来自萃取剂中间槽并进入萃取塔逆流萃取废水中的酚类。萃取塔塔顶富酚有机相作为萃 取剂循环补给给萃取槽，萃取塔中间层液体进入中间层处理反应器，萃取塔塔底脱酚废水进入脱酚水中间槽，待进一步的后续处理。
(3)中间层液体的处理：中间层处理反应器分离油水两相，脱出的油相进入富酚有机相中间槽，中间层处理反应器脱出的水相进入脱酚水中间槽。
所述反萃过程包括以下步骤：萃取过程萃取槽排出的富焦油和酚有机相进入反萃塔，经反萃脱除有机相中的酚，其所使用的碱液来自碱液配置槽。反萃塔塔底粗酚产品进入酚钠中间槽，反萃塔塔顶有机相进入萃取剂中间槽和萃取剂净化塔，碱液配置槽中碱液进入反萃塔和富酚有机相中间槽。富酚有机相中间槽定期由碱液配置槽补入碱液同步反萃，富酚有机相中间槽分离出的富酚钠水相进入酚钠中间槽，富酚有机相中间槽分离出的有机相进入萃取剂净化塔。
所述净化过程包括以下步骤：反萃塔塔顶有机相和富酚有机相中间槽分离出的有机相间歇进入萃取剂净化塔再生萃取剂，2～5天进行一次该操作。萃取剂净化塔塔顶排出的萃取剂经塔顶冷凝器后进入净化萃取剂中间槽，再泵入萃取剂中间槽，实现萃取剂循环利用。萃取剂净化塔塔底排出的焦油进入焦油中间槽再转入焦油储罐进行回收利用。
所述萃取过程步骤(1)中脱油废水中间槽的废水经换热器降温至20～50℃，例如20℃、23℃、25℃、27℃、30℃、33℃、35℃、37℃、40℃、43℃、45℃、47℃或50℃等。
所述萃取过程步骤(1)中萃取槽中萃取剂为萃取塔塔顶富酚有机相，使富酚有机相得到循环利用。
所述萃取过程步骤(2)萃取剂中间槽中萃取剂为专利CN103848468A公布的酚氨废水萃取剂，该萃取剂按质量分数含有以下组分：
中性含磷类萃取剂4～25％
酸性含磷类萃取剂0.5～10％
助溶剂0.5～5％
稀释剂60～95％
因萃取剂的配方已为公开的现有技术，此处不再对其具体成分进行赘述。
所述萃取过程步骤(2)萃取塔中油水相体积比1∶1～5，例如1∶1、1∶1.5、1∶2、1∶2.5、1∶3、1∶3.5、1∶4、1∶4.5或1∶5等。
所述萃取过程步骤(2)萃取塔中萃取温度为20～30℃，例如20℃、21℃、22℃、23℃、24℃、25℃、26℃、27℃、28℃、29℃或30℃等。
所述反萃过程碱液配置槽中碱液为氢氧化钠水溶液。
所述反萃过程碱液配置槽中氢氧化钠水溶液的质量浓度为10～30％，例如10％、13％、15％、17％、20％、23％、25％、27％或30％等。
所述反萃过程中反萃塔塔顶有机相和富酚有机相中间槽分离出的有机相间歇进入萃取剂净化塔。
所述反萃过程中萃取剂净化塔2～5天进行一次再生萃取剂的操作，例如2天、3天、4天或5天等。
所述反萃过程中萃取剂净化塔塔顶温度为120～180℃，例如120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃或180℃等。
所述反萃过程中萃取剂净化塔塔顶压力为0.05～0.25MPa，例如0.05MPa、0.07MPa、0.10MPa、0.13MPa、0.15MPa、0.17MPa、0.20MPa、0.23MPa或0.25MPa等。
所述反萃过程中萃取剂净化塔塔底温度为110～150℃，例如110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃或150℃等。
所述反萃过程中萃取剂净化塔塔底压力为0.10～0.20MPa，例如0.10MPa、0.11MPa、0.12MPa、0.13MPa、0.14MPa、0.15MPa、0.16MPa、0.17MPa、0.18MPa、0.19MPa或0.20MPa等。
与现有技术相比，本发明具有以下有益效果：
(1)回收焦油产品，充分利用废水资源。现有酚氨废水处理工艺多采用过滤等技术将焦油与废水中固废物同步滤除，未见有效回收焦油的工艺，且脱除污染物较难处理。本工艺将“萃取塔”中富酚萃取剂循环至“萃取槽”，利用废萃取剂携带分离酚氨废水中的焦油，最终在“萃取剂净化塔”脱除出粗焦油产品。避免了焦油产品的浪费现象，增加了废水处理中产品的产出。
(2)萃取剂回收利用率高。乳化中间层的产生在萃取工艺中是不可避免的，从萃取槽、萃取塔中移除的乳化中间层含有大量有机溶剂。本工艺利用中间层处理反应器装置将乳化油水两相彻底分离，萃取剂回收率达99.5％以上。即有效降低了因溶剂损耗而产生的处理成本，又避免废水二次污染。
(3)萃取剂性能优异，处理废水效果佳。酚氨废水经四过程处理后废水中焦油回收率＞94％，苯酚去除率＞99％，COD去除率＞98％。排出水满足后续蒸氨处理工艺要求。
附图说明
图1是本发明一种酚氨废水中酚油联合脱除系统装置示意图；
其中，1-酚氨废水储槽，2-焦炭过滤器，3-陶瓷膜过滤器，4-脱油废水中间槽，5-换热器，6-萃取槽，7-萃取塔，8-萃取剂中间槽，9-中间层处理反应器，10-脱酚水中间槽，11-碱液配制槽，12-富酚有机相中间槽，13-酚钠中间槽，14-反萃塔，15-萃取剂净化塔，16-塔顶冷凝器，17-焦油中间槽，18-净化萃取剂中间槽。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。
图1是本发明一种酚氨废水中酚油联合脱除系统装置示意图。
实施例1：
原料酚氨废水性质见表1。所处理的酚氨废水水质呈红褐色，pH值为8.9，水温为92℃，流量102吨/小时，按图1所示流程进行处理。
表1：原料酚氨废水性质表(mg/L)
Figure PCTCN2015079705-appb-000001
原料废水流经焦炭过滤器2脱除酚氨废水中的煤焦油、颗粒等固体污染物。脱油废水经换热器5降温至25℃后进入萃取系统中萃取槽6脱除焦油和部分酚，萃取剂由萃取塔7中富酚萃取剂循环补给。萃取槽6槽底排出废水从塔底进入萃取塔7脱酚，萃取剂为发明专利“CN103848468A实施例”中制备的萃取剂3。
其中萃取剂3的制备方法为：取14g异戊基二甲戊酯，4g 2-乙基己基膦酸单-2-乙基己基酯-和5g二(2-乙基己基)磷酸，2g 3-庚酮，0.3g丙二醇丁醚，74.7g煤油，40℃下混合均匀，冷却至室温即为本发明的萃取剂3。
萃取油水相比为1∶1，温度为20℃。萃取塔7塔顶富酚有机相循环补给萃取槽6。萃取塔7塔底脱酚废水进入脱酚水中间槽10，待进一步蒸氨处理。
萃取槽6和萃取塔7产生的中间层进入中间层处理反应器9分离油水两相，脱出的油相进入富酚有机相中间槽12。脱出的水相进入脱酚水中间槽10，脱酚水待后续蒸氨处理。
萃取槽6排出的富焦油和酚有机相进入反萃塔14，经三级反萃脱出有机相 中酚类。使用的碱液为来自碱液配置槽11浓度为16％的氢氧化钠水溶液。反萃塔14塔低粗酚产品进入酚钠中间槽13。反萃塔14塔顶有机相进入萃取剂中间槽8，循环利用。富酚有机相中间槽12由碱液配置槽11补入碱液同步反萃，分离出的富酚钠水相进入酚钠中间槽13，有机相进入萃取剂净化塔15进行再生。
萃取剂净化塔15中的萃取剂再生每3天进行一次。萃取剂净化塔15塔顶温度为130℃，压力为0.12MPa；萃取剂净化塔15塔底温度为110℃，压力为0.10MPa。萃取剂净化塔15塔顶排出萃取剂经塔顶冷凝器16冷却后进入净化萃取剂中间槽18，然后泵入萃取剂中间槽8，实现萃取剂循环利用。萃取剂净化塔15塔底脱除焦油经焦油中间槽17进入焦油储槽，回收利用。
分别对除油系统污水、萃取槽出口污水、反萃塔废水排出口水质进行随机取样分析，其分析结果见表2、表3、表4。
表2：除油系统污水水质信息表(随机取样)
Figure PCTCN2015079705-appb-000002
表3：萃取槽出口水质信息表(随机取样)
Figure PCTCN2015079705-appb-000003
由表2与表3可知，该工艺能有效脱除、回收焦油，去除率大于98％，回收利用率大于94％。
表4：反萃塔废水排出口水质信息表(随机取样)
Figure PCTCN2015079705-appb-000004
由表4可以看出，经过本发明酚氨废水中酚油联合脱除系统后，酚氨废水中总酚去除率达94.16％，焦油去除率大于98％，回收利用率大于94％。COD去除率98.68％。
实施例2：
除萃取过程脱油废水中间槽4的废水经换热器5降温至20℃，萃取塔7中油水相比为1∶3，萃取塔7中萃取温度为25℃，碱液配置槽11中氢氧化钠水溶液质量浓度为10％，萃取剂净化塔15中的萃取剂再生每2天进行一次，萃取剂净化塔15塔顶温度为120℃，萃取剂净化塔15塔顶压力为0.05MPa，萃取剂净化塔15塔底温度为135℃，萃取剂净化塔15塔底压力为0.15MPa外，其余过程均与实施例1中相同，经过本发明酚氨废水中酚油联合脱除系统后，酚氨废水中总酚去除率达95.20％，焦油去除率大于99％，回收利用率大于94％，COD去除率98.72％。
实施例3：
脱油废水中间槽4的废水经换热器5降温至50℃，萃取塔7中油水相比为1∶5，萃取塔7中萃取温度为30℃，碱液配置槽11中氢氧化钠水溶液质量浓度为30％，萃取剂净化塔15中的萃取剂再生每5天进行一次，萃取剂净化塔15塔顶温度为180℃，萃取剂净化塔15塔顶压力为0.25MPa，萃取剂净化塔15塔 底温度为150℃，萃取剂净化塔15塔底压力为0.2MPa，其余过程均与实施例1中相同，经过本发明酚氨废水中酚油联合脱除系统后，酚氨废水中总酚去除率达94.10％，焦油去除率大于98％，回收利用率大于95％，COD去除率99.20％。
综上所述，本发明公布的一种酚氨废水中酚油联合脱除系统及处理工艺，酚氨废水经处理总酚去除率大于94％，焦油去除率大于98％，回收利用率大于94％，COD去除率大于98％。本工艺利用中间层处理反应器装置将乳化油水两相彻底分离，萃取剂循环利用率高。将萃取塔中富酚萃取剂循环至萃取槽，利用废萃取剂携带分离酚氨废水中的焦油，最终在萃取剂净化塔脱除出粗焦油产品，避免了焦油产品的浪费现象，处理后废水满足工厂后续工艺要求，也可回用。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种酚氨废水中酚油联合脱除系统，其特征在于，所述系统依次包括除油系统、萃取系统、反萃系统和净化系统。
  2. 根据权利要求1所述的系统，其特征在于，所述除油系统依次包括酚氨废水储槽、焦炭过滤器、陶瓷膜过滤器和脱油废水中间槽。
  3. 根据权利要求1或2所述的系统，其特征在于，所述萃取系统包括换热器、萃取槽、萃取塔、萃取剂中间槽、中间层处理反应器、脱酚水中间槽和碱液配制槽，其中换热器出料口与萃取槽进料口相连，萃取槽底部出料口与萃取塔塔顶进料口相连，萃取槽的中间层出料口与中间层处理反应器进料口相连，萃取塔塔顶出料口与萃取槽萃取剂入口相连，萃取塔的中间层出料口与中间层处理反应器进料口相连，萃取塔塔底出料口与脱酚水中间槽进料口相连，萃取剂中间槽出料口与萃取塔萃取剂入口相连，中间层处理反应器水相出口与脱酚水中间槽进料口相连。
  4. 根据权利要求1-3任一项所述的系统，其特征在于，所述反萃系统包括反萃塔、富酚有机相中间槽和酚钠中间槽，其中反萃塔塔底出料口与酚钠中间槽进料口相连，富酚有机相中间槽水相出料口与酚钠中间槽进料口相连；
    优选地，所述反萃塔为三级反萃塔。
  5. 根据权利要求1-4任一项所述的系统，其特征在于，所述净化系统包括萃取剂净化塔、塔顶冷凝器、焦油中间槽和净化萃取剂中间槽，其中萃取剂净化塔塔顶出料口与塔顶冷凝器进料口相连，塔顶冷凝器出口与净化萃取剂中间槽进料口相连，萃取剂净化塔塔底出料口与焦油中间槽相连。
  6. 根据权利要求1-5任一项所述的系统，其特征在于，所述除油系统中脱油废水中间槽出料口与换热器入口相连，萃取槽顶部出料口与反萃塔塔顶进料口相连，中间层处理反应器出料口与富酚有机相中间槽进料口相连，碱液配制 槽出料口与反萃塔塔底进料口和富酚有机相中间槽进料口相连，反萃塔塔顶出料口与萃取剂中间槽进料口相连，反萃塔塔顶出料口与萃取剂净化塔塔底进料口相连，富酚有机相中间槽有机相出料口与萃取剂净化塔塔底进料口相连，净化萃取剂中间槽出料口与萃取剂中间槽进料口相连。
  7. 一种如权利要求1-6任一项所述系统的处理工艺，其特征在于，所述处理工艺依次包括除油过程、萃取过程、反萃过程和净化过程。
  8. 根据权利要求7所述的处理工艺，其特征在于，所述除油过程为预处理过程，其包括以下步骤：酚氨废水进入酚氨废水储槽，依次流经焦炭过滤器和陶瓷膜过滤器进入脱油废水中间槽；
    优选地，所述萃取过程包括以下步骤：
    (1)萃取脱焦油：脱油废水中间槽的废水经换热器降温后进入萃取槽脱焦油和酚，萃取槽槽底排出的废水进入萃取塔，萃取槽中富焦油和酚有机相进入反萃塔，萃取槽中间层液体进入中间层处理反应器；
    (2)萃取脱酚：萃取槽槽底排出的废水进入萃取塔，萃取剂由萃取剂中间槽进入萃取塔，萃取塔塔顶富酚有机相进入萃取槽，萃取塔中间层液体进入中间层处理反应器，萃取塔塔底废水进入脱酚水中间槽；
    (3)中间层液体的处理：中间层处理反应器脱出的油相进入富酚有机相中间槽，中间层处理反应器脱出的水相进入脱酚水中间槽；
    优选地，所述反萃过程包括以下步骤：萃取槽中富焦油和酚有机相进入反萃塔，反萃塔塔底产品进入酚钠中间槽，反萃塔塔顶有机相进入萃取剂中间槽和萃取剂净化塔，碱液配置槽中碱液进入反萃塔和富酚有机相中间槽，富酚有机相中间槽分离出的富酚钠水相进入酚钠中间槽，富酚有机相中间槽分离出的有机相进入萃取剂净化塔；
    优选地，所述净化过程包括以下步骤：反萃塔塔顶有机相和富酚有机相中间槽分离出的有机相进入萃取剂净化塔再生萃取剂，萃取剂净化塔塔顶排出的萃取剂经塔顶冷凝器冷凝后进入净化萃取剂中间槽，再泵入萃取剂中间槽，萃取剂净化塔塔底排出的焦油进入焦油中间槽。
  9. 根据权利要求7或8所述的处理工艺，其特征在于，所述萃取过程步骤(1)中脱油废水中间槽的废水经换热器降温至20～50℃；
    优选地，所述萃取过程步骤(1)中萃取槽中萃取剂为萃取塔塔顶富酚有机相；
    优选地，所述萃取过程步骤(2)萃取剂中间槽中萃取剂为专利CN103848468A公布的酚氨废水萃取剂；
    优选地，所述萃取过程步骤(2)萃取塔中油水相体积比为1∶1～5；
    优选地，所述萃取过程步骤(2)萃取塔中萃取温度为20～30℃。
  10. 根据权利要求7-9任一项所述的处理工艺，其特征在于，所述反萃过程碱液配置槽中碱液为氢氧化钠水溶液；
    优选地，所述反萃过程碱液配置槽中氢氧化钠水溶液的质量浓度为10～30％；
    优选地，所述反萃过程中反萃塔塔顶有机相和富酚有机相中间槽分离出的有机相间歇进入萃取剂净化塔；
    优选地，所述反萃过程中萃取剂净化塔2～5天进行一次再生萃取剂的操作；
    优选地，所述反萃过程中萃取剂净化塔塔顶温度为120～180℃；
    优选地，所述反萃过程中萃取剂净化塔塔顶压力为0.05～0.25MPa；
    优选地，所述反萃过程中萃取剂净化塔塔底温度为110～150℃；
    优选地，所述反萃过程中萃取剂净化塔塔底压力为0.10～0.20MPa。
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