WO2010066181A1 - 高效回收利用pta装置精制母液的简易方法和系统 - Google Patents

高效回收利用pta装置精制母液的简易方法和系统 Download PDF

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Publication number
WO2010066181A1
WO2010066181A1 PCT/CN2009/075352 CN2009075352W WO2010066181A1 WO 2010066181 A1 WO2010066181 A1 WO 2010066181A1 CN 2009075352 W CN2009075352 W CN 2009075352W WO 2010066181 A1 WO2010066181 A1 WO 2010066181A1
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Prior art keywords
ion exchange
mother liquor
ultrafiltration
liquid
heat
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PCT/CN2009/075352
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English (en)
French (fr)
Inventor
罗文德
周华堂
姚瑞奎
张莼
陈孟和
李利军
袁骏
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China National Petroleum Corp
China Textile Industrial Engineering Institute
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China National Petroleum Corp
China Textile Industrial Engineering Institute
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Priority to RU2011127991/04A priority Critical patent/RU2471767C1/ru
Publication of WO2010066181A1 publication Critical patent/WO2010066181A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a simple method for efficiently recycling a mother liquor by using a PTA device and a recycling system using the same method, and belongs to the technical field of chemical industry and environmental protection.
  • the refining unit of the PTA (fine terephthalic acid) device uses water as a solvent to dissolve the crude terephthalic acid (CTA) by heating and then enters the refining reactor. In the presence of the catalyst, hydrogen (H 2 ) is used.
  • the main impurity in the slurry is reduced to carboxybenzaldehyde (4-CBA) to water-soluble p-nonylbenzoic acid (p-TA), and then processed by crystallization, filtration or centrifugation, drying, etc.
  • the product is refined with p-benzoic acid (PTA).
  • aqueous solution (refined mother liquor) is contained, which contains TA, p-TA, HAC and a small amount of catalyst (ca t ), 4-CBA and other metal ions, the conventional PTA device
  • the refined mother liquor is directly discharged into the sewage treatment plant, and the useful components and water are not recovered. As a result, the material consumption and energy consumption of the device are high, and the sewage treatment is difficult.
  • No. 3 invention patent application discloses a comprehensive treatment and utilization method of PTA purified wastewater, which can be combined with the original PTA production device and PTA recovery.
  • the system includes the following steps: (A) After cooling the PTA refined wastewater to a temperature lower than 60 degrees, the first membrane separation device is introduced for separation, and the retained concentrated liquid is introduced.
  • step B introduce the filtrate from step (A) into the secondary membrane separation unit for separation, and the trapped concentrate enters (D) step, filter The liquid is directly reused, or enters (C) step treatment;
  • the filtrate obtained in step B is introduced into the water recovery ion exchange system, and further removes trace ions to meet the water quality requirements of deionized water, and is reused as process water for production.
  • step (D) The concentrated liquid obtained in the step (B) is pretreated and introduced into a catalyst recovery ion exchange system to adsorb cobalt manganese ions, and after adsorption saturation, a high concentration cobalt manganese solution is obtained, and the cobalt manganese catalyst is recovered.
  • the first membrane separation device adopts a stainless steel membrane or a ceramic membrane or a submerged membrane group, and the filtration pore diameter of the membrane is selected from the range of 10 to 1 000; and the secondary membrane separation device uses a polymer membrane, The magnesium sulfate rejection rate is above 90%; the polymer membrane is a reverse osmosis membrane or a nanofiltration membrane; the water recovery ion exchange system comprises a cation exchange column and an anion exchange column, and the flow rate of the ion exchange column is controlled at 1 - 8BV;
  • the catalyst recovery ion exchange system uses a chelating resin or a strong acid resin or a cationic resin to adsorb cobalt manganese, and the resin is saturated and then eluted and regenerated with an acid.
  • This patent application greatly improves the recovery rate of TA, p-TA, cobalt, manganese and water in the refined mother liquor, and the water purification degree after treatment is relatively high, and the recycling range is wide, but it is used more
  • the membrane separation technology, especially the second membrane treatment uses high-energy treatment such as reverse osmosis, so the power consumption is large, the equipment is complicated, the investment is large, and the running cost is high, which affects the actual situation, especially in the power shortage area. Promote the application.
  • the present invention provides a simple method for efficiently recycling a mother liquor by using a PTA device, and also provides a specific implementation process for efficiently recycling a mother liquor using the PTA device by using the method. It satisfies the high-efficiency recycling of the useful components in the refined mother liquor, greatly simplifies the treatment process, reduces the complexity of the system, and especially eliminates the high energy-consuming steps such as reverse osmosis in the prior art, and reduces the investment cost and operation. Cost, not only environmental protection and energy saving, but also High economic efficiency.
  • An easy way to efficiently recycle the mother liquor from the PTA unit including the following steps:
  • step (1) the liquid is used as the heat absorption medium of step (1) to exchange heat with the refined mother liquor.
  • step (1) most of the liquid is sent to the dryer spray tower, according to the spray demand and refining of the spray tower of the dryer. The material balance of the unit, the excess part is discharged, and the liquid sprayed by the spray tower of the dryer is returned to the refining system.
  • the refined mother liquid is cooled in two steps.
  • the first step is to use the step (4) to transfer the liquid as the heat absorption medium for heat exchange, to lower the temperature of the refined mother liquid, and the second step is to cool.
  • the refined mother liquor is further cooled by wind or cooling water so that the temperature of the refined mother liquor satisfies the subsequent ultrafiltration requirements.
  • the temperature of the refined mother liquor can be lowered to 72 ⁇ 77 °C, or about 74 °C, after the second heat exchange (cooling), the temperature of the refined mother liquor It is 40 ⁇ 45 °C.
  • the sintered metal coated T i0 2 membrane filter material is preferably used, and the filtration precision is 50-100 nm, and the filtration method is concentrated by cross-flow, and the discharged concentrate has a solid content of 15-20%.
  • the ion exchange is carried out in two steps, and the first step uses ion exchange resin capable of selectively adsorbing Co and Mn ions, and then the broad spectrum absorption of the liquid helium after the first step is separated.
  • the metal ion ion exchange resin adsorbs the remaining various metal ions, including Fe, Ni, Na ions, and the first step of ion exchange, using HBr as an eluent to elute and regenerate the ion exchange resin, and the resulting Co and Mn are desorbed.
  • the liquid can be sent to the oxidation unit for use as a catalyst, and the second step is ion exchanged with HC 1 as a wash.
  • the ion exchange resin is eluted and regenerated by deliquoring, and the resulting desorbed liquid containing Fe, Ni, Na ions can be sent to a sewage treatment system for purification treatment.
  • the post-dissociation liquid of the step (3) is sent to the heat exchange system of the first step in the step (1) as a heat absorption medium, and the temperature of the post-dissociation liquid after the endothermic heat is generally It should be around 72 °C (for example, 70 ⁇ 75 °C).
  • a simple system for efficiently recycling a mother liquor by using a PTA apparatus comprising a heat exchange system, an ultrafiltration system, an ion exchange system, and a dryer spray tower, the heat exchange system including a first heat exchanger and a cooling device, the ion The exchange system includes a first ion exchange unit and a second ion exchange unit, the heat release medium outlet of the first heat exchanger is connected to the heat release medium inlet of the cooling device, and the heat release medium outlet of the cooling device is connected to the ultrafiltration An inlet of the system, an ultrafiltration filtrate outlet of the ultrafiltration system is connected to an inlet of the first ion exchange unit, an outlet of the first ion exchange unit is connected to an inlet of the second ion exchange unit, and the second ion exchange unit The outlet is connected to the heat absorption medium inlet of the first heat exchanger, and the heat absorption medium outlet of the first heat exchanger is connected to the spray pipe of the dryer spray tower.
  • the heat-releasing medium inlet of the first heat exchanger is connected to the refined mother liquid pipeline, and the heat-absorbing medium inlet and the heat-absorbing medium outlet of the cooling device can be connected to a cooling air duct or a cooling water pipeline, and the ultrafiltration system is ultrafiltered.
  • the concentrate outlet is connected to the oxidation reactor feed line of the oxidation unit, the desorption liquid outlet of the first ion exchange unit is connected to the oxidation reactor feed line of the oxidation unit, and the desorption liquid outlet of the second ion exchange unit
  • a sewage treatment system is connected, and the spray liquid discharge port of the dryer spray tower can be connected to the recirculating solvent pipeline of the refining system.
  • the ultrafiltration system preferably has a cross-flow concentration structure and is provided with a plurality of circulation pumps for cross-flow concentration.
  • the filter material is preferably a sintered metal coated Ti0 2 film structure filter material, and the filtration precision is 50 - 100 nm.
  • the ultrafiltration system may be provided with an ultrafiltration concentrate tank, and the ultrafiltration concentrate tank is provided with a stirrer.
  • the ultrafiltration system may also be provided with an ultrafiltration filtrate tank.
  • a heater may be provided on the connecting pipe between the ultrafiltration filtrate outlet of the ultrafiltration system and the inlet of the first ion exchange unit, and the heater is preferably a low pressure steam heater.
  • the ion exchange system is preferably a continuous ion exchange system
  • the first ion exchange unit is an ion exchange unit capable of selectively adsorbing Co, Mn ions
  • the second ion exchange unit is capable of broadly adsorbing Fe, Ni, Na, etc.
  • a metal ion ion exchange unit, the first ion exchange unit may be provided with a desorption liquid tank.
  • the first ion exchange unit and the second ion exchange unit are respectively provided with an input port for rinsing and regenerating liquid such as an HBr input port for ion exchange resin regeneration and an HC 1 input port.
  • the beneficial effects of the invention are: integration with the PTA production system, realizing the reuse of most of the water and other useful materials in the refined mother liquor, greatly reducing the pollutant discharge, saving the production cost of the PTA, especially
  • the rational process of recycling the process of refining the mother liquor is simplified without reducing the quality of PTA, and the excessive purification of the refined mother liquor is avoided, thereby greatly reducing
  • the energy consumption in the refined mother liquor treatment reduces the processing cost of the refined mother liquor and improves the investment benefit of the refined mother liquor reuse.
  • the investment recovery period is about 2 years, which is significantly lower than the prior art.
  • Figure 1 is a schematic diagram of the process of the present invention
  • FIG. 2 is a schematic view showing the system structure and process flow of the present invention.
  • the main impurities of the refined mother liquor include: TA 0. 5 ⁇ 1%, p-TA ⁇ 0.2% and a small amount of HAC, 4CBA, Co ions, Mn ions and other metal ions.
  • these impurities TA, p-TA, Co ion, Mn ion, etc. are all useful materials in the production of PTA. Therefore, according to the specific requirements of the production process and the material balance in the production process, the refined mother liquor can be treated moderately.
  • the materials that can be recycled, heavy metals and water are used in the step-by-step process for the relevant process units without the need to purify these useful materials and reuse the water.
  • the present invention changes the prior art method for excessive purification of the refined mother liquor.
  • the refined mother liquor is only subjected to a moderate treatment, and is sent when the treated refined mother liquor meets the requirements of the production process.
  • the production system is reused. Because different production processes have different requirements for the reuse of the refined mother liquor, a reasonable and appropriate treatment step is selected in the process of the refined mother liquor, so that the different production can be stepped in the process of the refined mother liquor.
  • the requirements of the process are continuously introduced into the production system, especially because the high-efficiency reverse osmosis treatment of the refined mother liquor is no longer carried out, which greatly reduces the energy consumption and treatment cost of the refined mother liquor treatment, and also greatly reduces the refined mother liquor. Processing investment.
  • the solid content of the ultrafiltration concentrate fed to the oxidation unit is preferably 15 - 20%. Too low a solid content will have an adverse effect on PTA, while too high a solid content will increase significantly.
  • the main impurity content in the ultrafiltration filtrate should generally be controlled at TA: 0. 01 - 0. 02 %, p-TA: 0. 07 - 0. 08 %, HAC: 0. 02 - 0. 03 %, 4CBA : 0. 0001 - 0. 0002 %, Co ion: 0. 0015 - 0.
  • the main impurity content in the liquid after the separation should generally be controlled at TA: 0. 01 - 0. 02 %, p-TA: 0. 07 - 0. 08 %, HAC: 0. 02 - 0. 03 %, 4CBA: 0. 0001 - 0. 0002 %, Co ion: 0 0002 - 0. 0003 %, Mn ion: 0. 0002 - 0. 0003 %, Fe, Ni, Na Other metal ions: 0. 00005 - 0.
  • the proportion of the spray tower and the outer row (usually sent to the sewage treatment plant for sewage treatment) sent to the dryer should be determined.
  • the amount of liquid after the departure of the general discharge can account for the departure.
  • the total amount of post-liquid is about 15 - 25 %.
  • the main treatment process of this patent is to recover TA and p-TA fine particles by ultrafiltration technology, and to recover Co ions, Mn ions and other metal ions by ion exchange technology, which will contain certain TA and p-TA components after treatment.
  • the water is reused in a suitable production process, rather than using a further purification method to completely remove these impurities.
  • the filter material in the ultrafiltration system is coated with Ti0 2 film with sintered metal, the precision is up to 50 ⁇ 100 nanometers (nm), and the filtration method is cross-flow concentration. The recovery rate of this filtration concentration method is higher, the solid content of the concentrate 15-20%, can be directly used in production systems, and operation is relatively easy.
  • the catalyst cobalt (Co) and manganese (Mn) in the filtrate are selectively adsorbed by ion exchange resin, then desorbed with HBr aqueous solution, and the desorbed liquid (Ca t ) is returned to the production system for use.
  • the filtrate after removal of Co and Mn metal is adsorbed by an ion resin to remove other metal ions (Fe, Ni, Na, etc.), and then the ultrafiltration filter after secondary ion exchange according to the demand of the production system.
  • the amount of ⁇ 80% of the liquid is directly returned to the refining system for use, and the other ⁇ 20% amount determines the amount of the discharge according to the product quality and the system water balance, and the discharge liquid enters the sewage treatment plant.
  • the filtered wastewater (refined mother liquor) separated by the PTA unit refining unit is cooled to a design temperature by heat exchange and cooling, and then enters a stainless steel membrane ultrafiltration separation device, and is concentrated and filtered by a circulating pump.
  • the stainless steel membrane separation device intercepts the TA and p-TA suspended solids which are crystallized in the wastewater, and the concentrated liquid formed by the retained suspended solids is collected in the ultrafiltration concentrate storage tank and pumped to the oxidation unit of the PTA unit for recycling.
  • the stainless steel membrane separator filters out the supernatant and enters the filtrate tank, which is then pumped into the heater to slightly increase its temperature before entering the continuous ion exchange catalyst recovery system.
  • the ion exchange resin first selectively adsorbs and concentrates the cobalt manganese ions, and after adsorption saturation, is analyzed by dilute HBr aqueous solution to obtain a cobalt manganese catalyst solution, and the analytical solution enters the catalyst tank, and is pumped to the oxidation system for reuse.
  • the ion exchange resin effluent is again passed through the secondary ion exchange resin, adsorbed to other metal ions, and then desorbed with dilute hydrochloric acid, and the desorbed liquid is discharged into the sewage treatment.
  • the liquid stream from which the metal ions are removed enters the liquid tank after the separation, and is sent out by the transfer pump.
  • the heat is exchanged with the refined mother liquid of about 100 ° to increase the temperature to ⁇ 72 ° C, ⁇ 80 % of the liquid.
  • the flow enters the dryer rinsing tower spray and returns to the refining system. According to the operation of the device and the water balance, ⁇ 20% of the liquid is discharged into the sewage treatment.
  • the temperature of the refined mother liquor after flashing is reduced to about 100 °C.
  • the concentration of p-TA in the mother liquor is 2000 ⁇ 2500 PPM, and the TA content is about 0.5 to 1. 0% Wt.
  • Liquid heat exchange the temperature is reduced to ⁇ 72 °C, and then cooled by circulating cooling water through the cooler, the mother liquid is cooled to 40 ⁇ 45 °C, at this time, about 65% of the P-TA in the mother liquor is precipitated, and the TA is basically precipitated. 6 ⁇ 1. 0%Wt ⁇ (95% or more), the mother liquid solid content is about 0. 6 ⁇ 1. 0% Wt.
  • the mother liquor is pumped into the stainless steel membrane ultrafiltration system through the mother liquor tank, and is circulated and filtered by a circulation pump to concentrate and concentrate to a solid content of 16 to 18% of Wt.
  • the concentrate is withdrawn and discharged to the belt.
  • the concentrate tank is then pumped to the oxidation unit for recycling.
  • the ultrafiltration system filtrate enters the filtrate tank and is pumped to the heater for heating with low pressure steam, which is heated to about 45 °C into the first ion exchange unit of the continuous ion exchange catalyst recovery system, through the ion exchange resin.
  • the cobalt manganese metal ions are selectively adsorbed first, and the saturated resin is desorbed with an aqueous solution of HBr, and the analytical solution is pumped back to the oxidation system through the catalyst tank for recycling.
  • the stream enters the secondary ion resin exchange column (second ion exchange unit), adsorbs to other metal ions, and is desorbed with dilute hydrochloric acid, and the metal ion-containing desorption liquid is discharged to the sewage treatment.
  • the liquid is pumped out, sent to the heat exchanger for heat exchange with the refined mother liquor after the flashing of 100'C, and the temperature is raised to 70-75 ° C, and 80% is sent to the dryer rinsing tower. Return to the refining system, and the remaining 20% is discharged to the sewage treatment.
  • the ultrafiltration and ion exchange systems all have backwashing facilities. They are regularly cleaned with acid, alkali and demineralized water, and the washing liquid is discharged to the sewage treatment.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Description

说 明 书
高效回收利用 PTA装置精制母液的简易方法和系统 技术领域
本发明涉及一种高效回收利用 PTA 装置精制母液的简易方法和釆用这种 方法的回收系统， 属化工和环保技术领域。
背景技术
PTA(精对苯二曱酸）装置的精制单元是以水为溶剂 ,将粗对苯二曱酸（ CTA ) 经打浆加热溶解后进入精制反应器， 在催化剂存在下， 用氢气（H2 )使浆料中 主要杂质对羧基苯曱醛（4-CBA )还原成可溶于水的对曱基苯曱酸（p-TA ), 再 通过结晶、过滤或离心分离、干燥等工艺过程，制得产品精对苯二曱酸（PTA )。 在 TA过滤或离心分离过程中， 分离出大量的水溶液（精制母液）， 此溶液中含 有 TA、 p-TA , HAC和少量催化剂 （ca t )、 4-CBA以及其它金属离子， 传统的 PTA 装置中的精制母液是直接排入污水处理场， 不对其中的有用成分和水进行回 收， 由此造成装置的物耗、 能耗高， 并给污水处理带来困难。
随着社会发展， 人们环保意识增强， 同时企业为降低成本、 提高产品竟争 力， 迫切需要降低物耗、 减少能耗。 近年来， PTA装置大都增设精制母液回收 设施， 釆用各种滤机将母液中 TA、 p-TA回收利用， 使产品物耗降低、 减轻污 水处理压力。 这些回收设施虽然都有一定实效， 但对有用成分的回收不完全， 装置仍有含较多 TA、 p-TA及其它杂质的大量污水外排， 对环境造成污染。
为提高精制母液中有用成分和水的回收利用率， 中国 20071 0044416. 3号 发明专利申请案公开了一种 PTA精制废水的综合处理利用方法， 这种方法可以 结合原有 PTA生产装置及 PTA回收系统进行， 包括以下步骤： （A )将 PTA精制废 水冷却降温低于 60度后， 引入一级膜分离装置进行分离， 截留的浓缩液引入 到原有 PTA回收系统回收 gTA , 滤出液进入 B步骤处理； （B )将步骤（A ) 所得 滤出液引入二级膜分离装置进行分离， 截留的浓缩液进入（D ) 步骤处理， 滤 出液直接回用， 或进入 ( C ) 步骤处理； （C )将步骤 B所得滤出液引入水回收 离子交换系统， 进一步去除微量离子后达到去离子水水质要求，作为工艺水回 用到生产； （D )将步骤（B )所得浓缩液经预处理后引入催化剂回收离子交换 系统， 对钴锰离子进行吸附， 吸附饱和后经过解析得到高浓度的钴锰溶液， 回 收其中的钴锰催化剂。所述的一级膜分离装置釆用不锈钢膜或陶瓷膜或浸没式 膜组， 膜的过滤孔径选用范围为 1 0 - 1 000讓； 所述的二级膜分离装置釆用高 分子膜， 其对硫酸镁截留率在 90 % 以上； 所述的高分子膜为反渗透膜或纳滤 膜； 所述的水回收离子交换系统包括阳离子交换柱和阴离子交换柱， 离子交换 柱的流速控制在 1 - 8BV; 所述的催化剂回收离子交换系统选用螯合树脂或强 酸性树脂或阳离子树脂对钴锰进行吸附， 树脂吸附饱和后用酸进行洗脱和再 生。 该专利申请在很大程度上提高了精制母液中 TA、 p-TA、 钴、 锰和水的回收 利用率， 并且处理后的水净化程度比较高， 回用范围广， 但由于釆用了多级膜 分离技术，特别是第二膜处理釆用反渗透等高耗能的处理方式， 因此电力消耗 大， 设备复杂， 投资大， 运行成本高， 影响了其在实际中特别是电力短缺地区 的推广应用。
发明内容
为克服现有技术的上述缺陷，本发明提供了一种高效回收利用 PTA装置精 制母液的简易方法，还提供一种釆用这种方法的高效回收利用 PTA装置精制母 液的具体实施流程工艺， 在满足高效回收利用精制母液中的有用成分的同时， 大幅度简化了处理工艺， 降低了系统的复杂程度， 特别是取消了现有技术下的 反渗透等高耗能步骤， 降低了投资成本和运行费用， 不仅环保节能， 而且还提 高了经济效益。
本发明实现上述目的的技术方案是：
一种高效回收利用 PTA装置精制母液的简易方法， 包括下列步骤：
(1)釆用热交换方法对精制母液进行降温；
(2)釆用超滤方法处理降温后的精制母液， 超滤浓缩液回用于氧化单元；
(3)对超滤滤出液进行离子交换处理，先选择吸附滤出液中的 Co、Mn离子， 将 Co、 Mn脱吸液回用 #丈催化剂， 再吸附其它金属离子；
(4)离交后液作为步骤 ( 1 )的吸热介质同精制母液进行热交换， 换热后这 些液体大部分送干燥机喷淋塔，根据干燥机喷淋塔的喷淋需求量和精制单元的 物料平衡， 多余部分排放， 干燥机喷淋塔喷淋后的液体回用于精制系统。
所述步骤（1 ) 中， 分两步对精制母液进行降温， 第一步是利用步骤（4 ) 离交后液作为吸热介质进行热交换， 降低精制母液的温度， 第二步是通过冷却 风或冷却水对精制母液进行进一步的冷却，使精制母液的温度满足后续的超滤 要求。 通常， 经过步骤（1 )第一步的热交换后， 精制母液的温度可降为 72 ~ 77 °C , 或者说 74 °C左右， 经过第二步热交换（冷却）后， 精制母液的温度为 40 ~ 45 °C。
所述步骤（2 ) 中， 优选烧结金属涂附 T i02膜滤材， 过滤精度为 50 ~ 100 纳米， 过滤方式釆用错流浓缩， 排出的浓缩液含固量为 15-20%。
所述步骤（3 ) 中， 分两步进行离子交换， 第一步釆用能够对 Co、 Mn离子 选择吸附的离子交换树脂进行离子交换，然后对第一步离交后液釆用广谱吸收 金属离子的离子交换树脂吸附剩余的各种金属离子， 包括 Fe、 Ni、 Na等离子， 第一步离子交换釆用 HBr 作为洗脱液对离子交换树脂进行洗脱再生， 产生的 Co、 Mn脱吸液可送入氧化单元用做催化剂， 第二步离子交换釆用 HC 1作为洗 脱液对离子交换树脂进行洗脱再生， 产生的含有 Fe、 Ni、 Na等离子的脱吸液 通常可以送入污水处理系统进行净化处理。
所述步骤（4 ) 中， 将所述步骤（3 ) 的离交后液送入步骤（1 ) 中第一步 的热交换系统作为吸热介质，吸热后的离交后液的温度一般应为 72 °C左右（例 如 70 ~ 75 °C )。
经过步骤（4 )升温的离交后液， 应根据后续回用系统的物料平衡， 将少 量多余部分排出， 大部分送入干燥机喷淋塔作为喷淋液， 然后将喷淋后的离交 后液送入精制系统加以利用。
一种高效回收利用 PTA装置精制母液的简易系统， 包括换热系统、超滤系 统、离子交换系统和干燥机喷淋塔，所述换热系统包括第一换热器和冷却装置， 所述离子交换系统包括第一离子交换单元和第二离子交换单元，所述第一换热 器的放热介质出口连接冷却装置的放热介质进口，所述冷却装置的放热介质出 口连接所述超滤系统的进口，所述超滤系统的超滤滤出液出口连接第一离子交 换单元的进口， 所述第一离子交换单元的出口连接第二离子交换单元的进口， 所述第二离子交换单元的出口连接所述第一换热器的吸热介质进口，所述第一 换热器的吸热介质出口连接干燥机喷淋塔的喷淋管道。
所述第一换热器的放热介质进口连接精制母液管道，所述冷却装置的吸热 介质进口和吸热介质出口可接入冷却风管道或冷却水管道，所述超滤系统的超 滤浓缩液出口连接氧化单元的氧化反应器进料管道，所述第一离子交换单元的 脱吸液出口耳连接氧化单元的氧化反应器进料管道，所述第二离子交换单元的 脱吸液出口连接污水处理系统，所述干燥机喷淋塔的喷淋液排放口可连接精制 系统循环溶剂管道。
所述超滤系统优选错流浓缩结构， 并设有多个用于错流浓缩的循环泵， 所 用滤材优选烧结金属涂附 Ti02膜结构滤材， 其过滤精度为 50 - 100纳米。
所述超滤系统可以设有超滤浓缩液罐， 所述超滤浓缩液罐内带有搅拌器。 所述超滤系统还可以设有超滤滤出液罐。
所述超滤系统的超滤滤出液出口和所述第一离子交换单元进口之间的连 接管道上可以设有加热器 , 所述加热器优选低压蒸汽加热器。
所述离子交换系统优选连续离子交换系统，所述第一离子交换单元是可以 选择吸附 Co、 Mn离子的离子交换单元， 所述第二离子交换单元是可以广谱吸 附 Fe、 Ni、 Na等各种金属离子的离子交换单元， 所述第一离子交换单元可以 设有脱吸液罐。
所述第一离子交换单元和第二离子交换单元分别设有用于离子交换树脂 再生的 HBr输入管口和 HC 1输入管口等漂洗和再生用液体的输入管口。
本发明的有益效果是： 与 PTA生产系统配套整合， 实现了精制母液中大部 分水和其它有用物料的回用， 大幅度减少了污染物的排放量， 节省了 PTA的生 产成本，特别是本发明根据 PTA生产过程中的各种物料平衡关系，通过合理的 回用方式，在不降低 PTA品质的前提下简化了精制母液的处理工艺，避免了对 精制母液的过度净化， 由此大幅度减少了精制母液处理中的能耗， 降低了精制 母液的处理成本， 提高了精制母液回用的投资效益， 经初步估算， 投资回收期 约为 2年， 明显低于现有技术。
附图说明
图 1是本发明的工艺原理图；
图 2是本发明的系统结构和工艺流程示意图。
具体实施方式
参见图 1和图 2 ,本发明的具体实施可依据上述技术方案，不再——赘述。 仅就本发明的特点和主要内容结合工艺过程说明如下：
基本思路：
在目前的 PTA生产技术下，精制母液主要杂质包括： TA 0. 5 ~ 1%、 p-TA ~ 0. 2% 以及少量的 HAC、 4CBA、 Co离子、 Mn离子和其它金属离子。 在这些杂质 中， TA、 p-TA, Co离子、 Mn离子等都是在 PTA生产中有用的物质， 因此， 根 据生产工艺的具体要求和生产过程的物料平衡，精制母液经过适度处理， 可将 能回收的物料、 重金属及水， 阶梯式回用于相关工艺单元， 而不需要将这些有 用物料都净化掉再进行水的回用。
因此， 本发明改变了现有技术对精制母液过度净化的做法，根据 PTA生产 各工艺过程的实际需要，将精制母液只进行适度的处理，在处理后的精制母液 符合生产工艺要求时就送入生产系统进行回用，由于不同生产工艺环节对回用 精制母液的要求不同，因此在精制母液的处理过程中选择了合理适度的处理步 骤，使得在精制母液的处理过程中能够阶梯式满足不同生产过程的要求， 不断 被引入生产系统，特别是由于不再对精制母液进行耗能很高的反渗透处理，极 大地减少了精制母液处理的能耗和处理成本，同时也大幅度降低了精制母液处 理的投资。
根据申请人的实验， 送入氧化单元的超滤浓缩液的含固量优选为 15 - 20 % , 过低的含固量将对 PTA产生不利影响， 而过高的含固量将明显地增大超滤 费用；经过离子交换后直接回用于精制系统的离交后液的比例可以是离交后液 总量的 80 %左右。超滤滤出液中的主要杂质含量一般应控制在 TA: 0. 01 - 0. 02 %、 p-TA: 0. 07 - 0. 08 %、 HAC: 0. 02 - 0. 03 %、 4CBA: 0. 0001 - 0. 0002 %、 Co 离子： 0. 0015 - 0. 002 %、 Mn离子： 0. 0015 - 0. 002 %、 Fe、 Ni、 Na其 它金属离子： 0. 0005 - 0. 001 %; 离交后液中的主要杂质含量一般应控制在 TA: 0. 01 - 0. 02 %、 p-TA: 0. 07 - 0. 08 %、 HAC: 0. 02 - 0. 03 %、 4CBA: 0. 0001 - 0. 0002 %、 Co离子： 0. 0002 - 0. 0003 %、 Mn离子： 0. 0002 - 0. 0003 %、 Fe、 Ni、 Na 其它金属离子： 0. 00005 - 0. 0001 %; 经过第一换热器后的离交 后液应按照精制系统的水平衡和物料平衡确定分别送入干燥机喷淋塔和外排 (一般是送入污水处理厂进行污水处理）的比例， 一般外排的离交后液量可占 离交后液总量的 15 - 25 %左右。 在上述参数下， 釆用本发明的处理和回用方 式， 不会对 PTA生产和产品品质产生不利影。
根据实际情况，还可以在本发明各处理设备之间的连接管道或处理设备的 出口上设置旁路管道， 以便将被处理液体引出后加以利用， 这些利用可以釆用 任意适宜的现有技术或其它可能的技术。
主要技术：
本专利的主要处理工艺是釆用超滤技术回收 TA、 p-TA细微颗粒， 釆用离子 交换技术回收 Co离子、 Mn离子并且消除其它金属离子， 将处理后含有一定 TA、 p-TA成分的水回用于适宜的生产工艺，而不是釆用进一步的净化方式彻底去除 这些杂质。 超滤系统中的滤材为烧结金属涂附 Ti02膜， 精度可达 50 ~ 100纳米 ( nm ), 过滤方式为错流浓缩， 这种过滤浓缩方式的回收率较高， 浓缩液含固 量 15-20%, 可直接回用于生产系统， 操作也相对容易。 对超滤后滤液， 再釆 用离子交换树脂将滤液中催化剂钴（Co )、 锰（Mn )选择吸附， 然后用 HBr水溶 液脱吸， 脱吸液（Ca t )返回生产系统使用。 脱除 Co、 Mn金属后的滤出液， 再 经一次离子树脂吸附， 去除其它金属离子（Fe、 Ni、 Na等）， 然后根据生产系 统的需求量，将二次离子交换后的超滤滤出液的 ~ 80 %量直接返回精制系统使 用， 另外〜 20 %量根据产品质量及系统水平衡决定外排量大小，排出液进入污 水处理场。 主要工艺流程：
PTA装置精制单元分离的过滤废水（精制母液）， 经过换热及冷却降温至设 计温度后， 进入不锈钢膜超滤分离装置， 通过循环泵加压浓缩过滤。 不锈钢膜 分离装置截留废水中结晶析出的 TA和 p-TA悬浮固体，截留悬浮固体形成的浓 缩液收集在超滤浓缩液储罐，再以泵送到 PTA装置氧化单元回收利用。 不锈钢 膜分离装置滤出清液进入到滤出液罐， 然后通过泵送入加热器，使其温度微升 后进入连续离子交换催化剂回收系统。离子交换树脂先对钴锰离子进行选择吸 附富集， 吸附饱和后用稀 HBr水溶液进行解析， 获得钴锰催化剂溶液， 解析液 进入催化剂罐，再以泵送到氧化系统回用。 离子交换树脂出水再次经二次离子 交换树脂， 对其它金属离子吸附， 然后用稀盐酸脱吸， 解吸液排入污水处理。 脱除金属离子的液流先进入离交后液体罐，再以输送泵送出， 经换热器和 1 00 左右的精制母液换热使其温度上升至 ~ 72 °C , ~ 80 %的液流进入干燥机淋洗 塔喷淋， 返回精制系统使用， 根据装置运转及水平衡情况， ~ 20 %的液流排入 污水处理。
对于超滤膜系统定期进行冲洗和化学清洗， 冲洗和清洗废水排放； 对离子 交换系统定期进行漂洗以及酸、 碱再生， 再生废水排放。
实施示例：
精制母液经闪蒸后温度降至 1 00 °C左右， 此时母液中 p-TA浓度在 2000 ~ 2500PPM, TA含量大约为 0. 5 ~ 1. 0%Wt ,经换热器与离交后液体热交换， 使其温 度降至〜 72 °C，再经冷却器用循环冷却水冷却， 使母液降温至 40 ~ 45 °C , 此时 母液中 P-TA大约有 65%析出， TA基本完成析出 （95%以上）， 母液含固量大约 在 0. 6 ~ 1. 0%Wt。 冷却后母液经母液罐以泵送入不锈钢膜超滤系统， 并以循环 泵使其循环过滤浓缩， 浓缩至含固量 1 6 ~ 18%Wt时， 浓缩液抽出， 排至带搅拌 的浓缩液罐， 而后以泵送至氧化单元回收利用。超滤系统滤出液则进入滤出液 罐， 再以泵送到加热器用低压蒸汽加热， 使其升温至 45°C左右进入连续离子 交换催化剂回收系统的第一离子交换单元，通过离子交换树脂先选择性地吸附 钴锰金属离子， 吸附饱和的树脂用 HBr水溶液解吸，解析液经催化剂罐以泵送 回氧化系统循环使用。 脱除 Co、 Mn离子后物流进入二次离子树脂交换柱（第 二离子交换单元）， 对其它金属离子吸附， 并以稀盐酸脱吸， 含金属离子脱吸 液排往污水处理。 离交后液体以泵送出， 送入换热器与闪蒸后 100'C的精制母 液进行热交换， 使其升温至 70~ 75°C, ~ 80%量送入干燥机淋洗塔， 返回精 制系统， 其余 20%量排往污水处理。
超滤、 离子交换系统均有反冲洗设施， 定期用酸、 碱、 除盐水清洗防堵， 洗液也排到污水处理。

Claims

权 利 要 求 书
1. 一种高效回收利用 PTA装置精制母液的简易方法， 其特征是包括下列 步骤：
(1)釆用热交换方法对精制母液进行降温；
(2)釆用超滤方法处理降温后的精制母液， 超滤浓缩液回用于氧化单元；
(3)对超滤滤出液进行离子交换处理，先选择吸附滤出液中的 Co、Mn离子， 将 Co、 Mn脱吸液回用 #丈催化剂， 再吸附其它金属离子；
(4)离交后液作为步骤 ( 1 )的吸热介质同精制母液进行热交换， 换热后液 体大部分送至干燥机喷淋塔喷淋多余部分排放，干燥机喷淋塔喷淋后的液体回 用于精制系统。
2. 如权利要求 1所述的高效回收利用 PTA装置精制母液的简易方法， 其 特征是所述步骤（ 1 )中， 分两步对精制母液进行降温， 第一步是利用步骤 ( 4 ) 离交后液作为吸热介质进行热交换， 降低精制母液温度， 第二步是通过冷却风 或冷却水对精制母液进行进一步的冷却，使精制母液的温度满足后续的超滤要 求。
3. 如权利要求 1所述的高效回收利用 PTA装置精制母液的简易方法， 其 特征是经过步骤（1 ) 第一步的热交换后， 离交后液的温度升高为 70 ~ 75 °C , 精制母液的温度降为 72 ~ 77 °C ,经过第二步热交换后，精制母液的温度为 40 ~ 45 °C。
4. 如权利要求 1、 2或 3所述的高效回收利用 PTA装置精制母液的简易方 法， 其特征是所述步骤（2 ) 中， 选用烧结金属涂附 T i 02膜滤材， 过滤精度为 50 ~ 1 00纳米， 过滤方式釆用错流浓缩， 排出的浓缩液含固量为 15-20%。
5. 如权利要求 4所述的高效回收利用 PTA装置精制母液的简易方法， 其 特征是所述步骤（3 ) 中， 分两步进行离子交换， 第一步釆用能够对 Co、 Mn 离子选择吸附的离子交换树脂进行离子交换，然后对第一步离交后液釆用广谱 吸收金属离子的离子交换树脂吸附剩余的各种金属离子，第一步离子交换釆用
HBr作为洗脱液对离子交换树脂进行洗脱再生， 第二步离子交换釆用 HC1作为 洗脱液对离子交换树脂进行洗脱再生。
6. 一种高效回收利用 PTA装置精制母液的简易系统， 其特征在于包括换 热系统、 超滤系统、 离子交换系统和干燥机喷淋塔， 所述换热系统包括第一换 热器和冷却装置，所述离子交换系统包括第一离子交换单元和第二离子交换单 元， 所述第一换热器的放热介质出口连接冷却装置的放热介质进口， 所述冷却 装置的放热介质出口连接所述超滤系统的进口，所述超滤系统的超滤滤出液出 口连接第一离子交换单元的进口，所述第一离子交换单元的出口连接第二离子 交换单元的进口，所述第二离子交换单元的出口连接所述第一换热器的吸热介 质进口， 所述第一换热器的吸热介质出口连接干燥机喷淋塔的喷淋管道。
7. 如权利要求 6所述的高效回收利用 PTA装置精制母液的简易系统， 其 特征在于所述第一换热器的放热介质进口连接精制母液管道，所述冷却装置的 吸热介质进口和吸热介质出口接入冷却风管道或冷却水管道，所述超滤系统的 超滤浓缩液出口连接氧化单元的氧化反应器进料管道，所述第一离子交换单元 的脱吸液出口连接氧化单元的氧化反应器进料管道，所述第二离子交换单元的 脱吸液出口连接污水处理系统，所述第二离子交换单元出口和所述第一换热器 吸热介质出口管道接入精制系统的干燥机淋洗塔喷淋管道，所述第二离子交换 单元出口和所述第一换热器吸热介质出口管道接入污水处理系统，所述干燥机 喷淋塔的喷淋液排放口连接精制系统循环溶剂管道。
8. 如权利要求 6或 7所述的高效回收利用 PTA装置精制母液的简易系统， 其特征在于所述超滤系统优选错流浓缩结构，并设有多个用于错流浓缩的循环 泵，所用滤材优选烧结金属涂附 Ti02膜结构滤材，其过滤精度为 50 - 100纳米。
9. 如权利要求 8所述的高效回收利用 PTA装置精制母液的简易系统， 其 特征在于所述超滤系统设有超滤浓缩液罐和超滤滤出液罐，所述超滤浓缩液罐 内带有搅拌器，所述超滤系统的超滤滤出液出口和所述第一离子交换单元进口 之间的连接管道上设有加热器， 所述加热器为低压蒸汽加热器。
10. 如权利要求 9所述的高效回收利用 PTA装置精制母液的简易系统， 其 特征在于所述离子交换系统为连续离子交换系统，所述第一离子交换单元是选 择吸附 Co、 Mn离子的离子交换单元， 所述第二离子交换单元是广谱吸附 Fe、 Ni、 Na 等各种金属离子的离子交换单元， 所述第一离子交换单元设有脱吸液 罐，所述第一离子交换单元和第二离子交换单元分别设有用于离子交换树脂再 生的 HBr输入管口和 HC 1输入管口等漂洗和再生用液体的输入管口。
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