WO2020216115A1 - 一种苯并三氮唑合成液连续化后处理的方法和装置 - Google Patents

一种苯并三氮唑合成液连续化后处理的方法和装置 Download PDF

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WO2020216115A1
WO2020216115A1 PCT/CN2020/084965 CN2020084965W WO2020216115A1 WO 2020216115 A1 WO2020216115 A1 WO 2020216115A1 CN 2020084965 W CN2020084965 W CN 2020084965W WO 2020216115 A1 WO2020216115 A1 WO 2020216115A1
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continuous
bta
water
extraction
treatment
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French (fr)
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王根林
丁克鸿
徐林
王刚
许越
郭玉秀
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江苏扬农化工集团有限公司
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Priority to DE112020002120.3T priority patent/DE112020002120T5/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0488—Flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D2011/002—Counter-current extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous processes

Definitions

  • the invention belongs to the technical field of petrochemical industry, and relates to a method for continuous post-treatment of benzotriazole (abbreviated BTA) synthetic liquid, and more specifically, to continuous acidification, water washing, extraction, and back extraction of the BTA synthetic liquid , Dehydration, distillation and other post-processing steps, the method of synthesizing BTA.
  • BTA benzotriazole
  • Benzotriazole (CAS: 95-14-7) is white and light brown needle-like crystals. It is an important fine chemical product. It has a wide range of uses and is mainly used for metals (silver, copper, lead, nickel, Zinc, etc.) rust and corrosion inhibitors, can also be used as paint additives, synthetic detergent preservatives, anticoagulants, synthetic dye intermediates, etc., with a wide range of downstream applications.
  • a Chinese patent application (CN105237488A) reported a kettle-type batch synthesis method of BTA, in which BTA was synthesized in one step by the pressure method of o-phenylenediamine. This method all adopts intermittent operation, the production efficiency is low, and the recovery method of BTA in the water layer is not mentioned.
  • the invention provides a method for continuous post-treatment of BTA synthetic liquid.
  • the BTA synthesis solution is subjected to post-treatment steps such as continuous acidification, water washing, extraction, back extraction, dehydration, and distillation to synthesize BTA.
  • the method utilizes the difference in solubility of BTA in water at different pHs to realize extraction and separation without consuming a large amount of evaporation energy, simple operation, low environmental pollution, strong economy, low energy consumption, and easy to realize industrialization.
  • a method for continuous post-treatment of BTA synthetic liquid including the following steps:
  • the acidification temperature is 40 to 100°C, 40 to 90°C, 40 to 80°C, 40 to 70°C, or preferably 50 to 100°C, 50 to 90°C, 50 to 80°C, 50 to 70°C, or Preferably it is 60-100 degreeC, 60-90 degreeC, 60-80 degreeC, 60-70 degreeC.
  • the pH value of the acidification end point is 3-6, or the pH value of the acidification end point is 3, 4, 5 or 6.
  • the residence time of acidification is 30min ⁇ 300min, more preferably 60min ⁇ 300min, 60min ⁇ 200min, or 60min ⁇ 100min, or preferably 70min ⁇ 300min, 70min ⁇ 200min, or 70min ⁇ 100min, or preferably 100min ⁇ 300min or 100min ⁇ 200min or 200 ⁇ 300min.
  • the water washing temperature is 40°C to 90°C, 40°C to 80°C, 40°C to 70°C, 40°C to 60°C, or 40°C to 50°C; or preferably 50°C to 90°C, 50°C to 80°C, 50°C to 70°C or 50°C to 60°C; or preferably 60°C to 90°C, 60°C to 80°C, 60°C to 70°C; or preferably 70°C to 90°C, 70°C to 80°C.
  • the ratio of water washing volume flow rate to water: acidified oil layer 0.5:1-20:1, 1:1-20:1, 5:1-20:1 or 1:1-10:1; or preferably 0.5: 1 ⁇ 10:1, 1:1 ⁇ 10:1 or 5:1 ⁇ 10:1.
  • the residence time of water washing is 15min ⁇ 300min, 30min ⁇ 300min, 50min ⁇ 300min, 60min ⁇ 300min, 100min ⁇ 300min, 200min ⁇ 300min; or preferably 15min ⁇ 250min, 30min ⁇ 250min, 50min ⁇ 250min, 60min ⁇ 250min , 100min ⁇ 250min, 200min ⁇ 250min; or preferably 15min ⁇ 200min, 30min ⁇ 200min, 50min ⁇ 200min, 60min ⁇ 200min, 100min ⁇ 200min; or preferably 15min ⁇ 100min, 30min ⁇ 100min, 50min ⁇ 100min, 60min ⁇ 100min .
  • the extraction temperature is 50 to 100°C, 50 to 90°C, 50 to 80°C, 50 to 65°C; or 60 to 100°C, 60 to 90°C, 60 to 80°C; or 65 to 100°C, 65 ⁇ 90°C, 65 ⁇ 80°C; or 80°C ⁇ 90°C.
  • the ratio of extraction volume flow rate extractant: (washed water layer + acidified water layer) 1:1-20:1, 1:1-15:1, 1:1-10:1, 1:1-5 :1; or preferably 5:1-20:1, 5:1-15:1, 5:1-10:1; or preferably 10:1-20:1, 10:1-15:1.
  • the residence time is 5min ⁇ 300min, 5min ⁇ 200min, 5min ⁇ 100min, 5min ⁇ 60min, 5min ⁇ 50min; or 50min ⁇ 300min, 60min ⁇ 300min, 100min ⁇ 300min, 200min ⁇ 300min; or preferably 50min ⁇ 200min , 60min ⁇ 200min, 100min ⁇ 200min.
  • the extractant is chlorobenzene, dichlorobenzene, nitrochlorobenzene, toluene, xylene, benzene, MIBK, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, acetic acid One or more mixtures of ethyl esters.
  • the above-mentioned stripping temperature is 40 ⁇ 90°C, 50 ⁇ 90°C, 60 ⁇ 90°C, 65 ⁇ 90°C; or preferably 40 ⁇ 80°C, 50 ⁇ 80°C, 60 ⁇ 80°C, 65 ⁇ 80°C Or preferably 40-70°C, 50-70°C, 60-70°C, 65-70°C; or preferably 40-65°C, 50-65°C, 60-65°C.
  • the stripping agent is the same as the acidifying reagent in step (1), and is one or more of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid;
  • the temperature of the continuous dehydration kettle material is 100-200°C, preferably 150-180°C, more preferably 170°C, absolute pressure 5-50kPa, preferably 5-30kPa, 5-20kPa, 5 ⁇ 10kPa, more preferably 5kPa.
  • the continuous distillation absolute pressure is 0-2 kPa, preferably 1 kPa, and the corresponding gas phase temperature is 140-190°C, preferably 150-180°C, more preferably 180°C.
  • the present invention also provides a system for continuous post-treatment of BTA synthetic liquid, which is sequentially connected to acidification reactor, water washing equipment, dehydration equipment, distillation equipment, and forming equipment; the water washing equipment is also sequentially connected to extractor 1 and extractor 2, and The acidification reactor is connected through the extractor 2.
  • the acidification reactor and the extractor 1 are connected by an acidification water pipeline.
  • the extractor 2 returns to the extractor 1 through the back extraction oil pipeline.
  • the dehydration equipment returns to the washing equipment through the steaming water pipeline.
  • BTA is synthesized by subjecting the BTA synthetic liquid to continuous acidification, water washing, extraction, back extraction, dehydration, distillation and other post-processing steps.
  • the method utilizes the difference in solubility of BTA in water at different pHs to achieve extraction and separation without consuming a large amount of evaporation energy, and has the advantages of simple operation, low environmental pollution, strong economy, low energy consumption, and easy realization of industrialization.
  • Figure 1 is a flow chart of continuous post-treatment.
  • 1 is an acidification reactor
  • 2 is a water washing device
  • 3 is a dehydration device
  • 4 is a distillation device
  • 5 is a forming device
  • 6 is an extractor 1
  • 7 is an extractor 2.
  • BTA synthesis Put 295kg of o-phenylenediamine, 213kg of sodium nitrite, and 370kg of water in a 1000L autoclave, replace with nitrogen, stir evenly, and raise the temperature to 260°C for 3h. After the heat preservation, the temperature was reduced and the pressure was relieved, and 877 kg of brown clear liquid was released. The analysis showed that the conversion rate of o-phenylenediamine was 100% and the yield of BTA was 98.94%. BTA synthesis is carried out with this process, and the synthetic liquid is subjected to continuous post-treatment.
  • the acidified liquid is continuously stratified, the obtained acidified oil layer enters the continuous water washing step, and the acidified water layer enters the continuous extraction step.
  • the obtained water-washed water layer is continuously extracted, and the water-washed oil layer is continuously dehydrated.
  • Continuous back-extraction use 25% hydrochloric acid as the back-extraction agent, control 65°C, and hold time for 1 h, and extract the oil layer and 25% hydrochloric acid according to the volume flow ratio.
  • BTA content in the stripping oil layer obtained at the time is less than 0.1%.
  • the obtained stripped oil layer is reused as the recovery extractant to the continuous extraction step, and the stripped water layer is BTA hydrochloride, which is reused to the continuous acidification step.
  • Continuous dehydration Dehydrate the oil layer with continuous water washing, control the absolute pressure of 5kPa, and the kettle temperature at 170°C. At this time, the water content of the kettle material is less than 0.1%.
  • the dewatered water is reused to the continuous water washing step, and the dehydrated kettle material enters the continuous distillation step.
  • Continuous distillation Continuously enter the dehydration kettle material into the distillation tower, control an absolute pressure of 1kPa, and the top temperature of the tower is about 180°C.
  • the continuous extraction of the tower top fraction is the BTA product, and the appearance of the product after cooling is white solid.
  • Example 2 On the basis of Example 2, the extractant was changed to MIBK, the stripping agent and acid were changed to sulfuric acid, other conditions were unchanged, and the application of materials was carried out.
  • the results are as follows:
  • Example number Apply number Product color Product yield/%
  • Example 3 First batch 20 81.2
  • Example 4 Set 1 20 97.4
  • Example 5 Set of 2 15 97.8
  • Example 6 Set of 3 15 98.1
  • Example 2 of the present invention is processed by an existing batch type post-treatment process.
  • the washing conditions refer to Example 2, the washing temperature is 60°C, the water-oil ratio is 1:1, and the holding time is 1h.
  • the treatment results are as follows:
  • Example number Product color Product purity/% Product yield/% Wastewater TOC/ppm Example 7 15 99.95 98.16 489
  • Example 8 13 99.91 98.54 455
  • Example 9 10 99.96 97.96 468
  • Example 10 12 99.89 98.33 473
  • Example 11 14 99.81 98.12 485
  • Example 12 15 99.79 98.59 476
  • Example 13 12 99.92 98.15 464
  • Example 15 Greater than 150 98.12 50.61 - Example 16 Greater than 150 95.01 5.13 -
  • Example 17 twenty two 99.86 98.96 486 Comparative example 1 25 99.79 97.85 4325 Comparative example 2 30 99.52 95.56 5230 Comparative example 3 Greater than 150 97.96 42.27 - Comparative example 4 Greater than 150 94.89 5.05 -
  • the pH at the end of acidification has a greater impact on product quality and yield, and pH 5-6 is preferred.
  • the continuous process has stable product quality. Compared with the intermittent process, the color of the product is reduced by 30-50%, and the quality is better.
  • the TOC of wastewater is reduced by about 90% year-on-year, and the pressure of wastewater treatment is significantly reduced.
  • the water-to-oil ratio of the water washing step also has an effect on the color of the product. Compared with intermittent, continuous use can achieve the desired effect with less water.
  • the current BTA post-treatment in the world adopts intermittent treatment methods, mainly intermittent acidification, intermittent water washing, and recovery of BTA in water through cooling and crystallization.
  • intermittent treatment methods mainly intermittent acidification, intermittent water washing, and recovery of BTA in water through cooling and crystallization.
  • the present invention adopts continuous post-processing, with simple operation process, high process reliability and high efficiency; before dehydration, the post-processed material has the same temperature, which reduces heat exchange and reduces energy consumption; through continuous acidification, dehydration, and rectification, continuous Produce high-quality BTA products.
  • the energy consumption is reduced, there is no intermittent treatment frequent temperature rising and falling crystallization process and a large number of solid-liquid separation processes, and the TOC in the wastewater obtained from the continuous treatment is less than 500ppm, and the wastewater treatment pressure is also significantly reduced .
  • the content of the present invention is not limited to the content of the embodiments of the present invention.

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Abstract

本发明属于石油化工的技术领域，涉及一种苯并三氮唑(简称BTA)合成液连续化后处理的方法，更具体地，涉及将BTA合成液经连续化酸化、水洗、萃取、反萃取、脱水、蒸馏等后处理步骤，合成BTA的方法。该方法利用BTA在不同pH下在水中的溶解度的差异，实现萃取分离，无需消耗大量的蒸发能耗，操作简单、环境污染小、经济性强、能耗低、易于实现工业化。

Description

一种苯并三氮唑合成液连续化后处理的方法和装置 技术领域
本发明属于石油化工的技术领域，涉及一种苯并三氮唑(简称BTA)合成液连续化后处理的方法，更具体地，涉及将BTA合成液经连续化酸化、水洗、萃取、反萃取、脱水、蒸馏等后处理步骤，合成BTA的方法。
背景技术
苯并三氮唑(CAS:95-14-7)为白色浅褐色针状结晶，是一种重要的精细化工产品，它的用途很广，主要用于金属(银、铜、铅、镍、锌等)的防锈剂和缓蚀剂，也可以用作涂料添加剂、合成洗涤剂的防腐剂、抗凝剂、合成染料中间体等，下游应用广泛。
中国专利申请(CN105237488A)报道了一种BTA的釜式间歇化合成方法，通过邻苯二胺加压法一步合成BTA。该方法全部采用间歇化操作，生产效率低，未提及水层中BTA的回收方法。
发明内容
本发明提供了一种BTA合成液连续化后处理的方法。具体的，是将BTA合成液经连续化酸化、水洗、萃取、反萃取、脱水、蒸馏等后处理步骤，合成BTA。该方法利用BTA在不同pH下在水中的溶解度的差异，实现萃取分离，无需消耗大量的蒸发能耗，操作简单、环境污染小、经济性强、能耗低、易于实现工业化。
一种BTA合成液连续化后处理的方法，包括下列步骤：
(1)将BTA合成液与酸化试剂连续进入酸化反应器中连续化酸化，采出酸化水层和酸化油层；
(2)将(1)中酸化油层进入水洗设备中连续化水洗，采出水洗油层和水洗水层；
(3)将(1)中酸化水层和(2)中水洗水层合并，进入萃取塔连续化萃取，采出萃取水层和萃取油层；
(4)将(3)中萃取油层进入反萃取塔中连续化反萃取，采出反萃取油层和反萃取水层，实现萃取剂和水层中BTA回用；
(5)将(2)中水洗油层经过连续化脱水、连续化蒸馏步骤，获得BTA产品。
上述步骤(1)中，所述酸化条件为：酸化试剂为盐酸、硫酸、硝酸、醋酸中的一种或多种，酸化温度20～100℃，pH＝3～8，优选为3～7或3～6，进一步优选为4～6或3～5或5～6；
停留时间1min～300min；
优选地，酸化温度为40～100℃、40～90℃、40～80℃、40～70℃、或者优选为50～100℃、50～90℃、50～80℃、50～70℃、或者优选为60～100℃、60～90℃、60～80℃、60～70℃。
优选地、酸化终点的pH值为3～6、或者酸化终点的pH值为3、4、5或6。
优选地、酸化的停留时间30min～300min、更优选为60min～300min、60min～200min、或者60min～100min、或者优选为70min～300min、70min～200min、或者70min～100min、或者优选为100min～300min或100min～200min或200～300min。
上述步骤(2)中，所述水洗条件为：水洗温度为20～100℃，水洗体积流量之比水：酸化油层＝0.1:1～20:1，停留时间1min～300min；
优选地，水洗温度为40℃～90℃、40℃～80℃40℃～70℃、40℃～60℃或40℃～50℃；或者优选为50℃～90℃、50℃～80℃、50℃～70℃或50℃～60℃；或者优选为60℃～90℃、60℃～80℃、60℃～70℃；或者优选为70℃～90℃、70℃～80℃。
优选地，水洗体积流量之比水：酸化油层＝0.5:1～20:1、1:1～20:1、5:1～20:1或1:1～10:1；或者优选为0.5:1～10:1、1:1～10:1或5:1～10:1。
优选地，水洗的停留时间为15min～300min、30min～300min、50min～300min、60min～300min、100min～300min、200min～300min；或者优选为15min～250min、30min～250min、50min～250min、60min～250min、100min～250min、200min～250min；或者优选为15min～200min、30min～200min、50min～200min、60min～200min、100min～200min；或者优选为15min～100min、30min～100min、50min～100min、60min～100min。
上述步骤(3)中，所述萃取条件为：萃取温度为20～100℃，萃取体积流量之比萃取剂：(水洗水层+酸化水层)＝0.1:1～20:1，停留时间1min～300min。
优选地，萃取温度为50～100℃、50～90℃、50～80℃、50～65℃；或者为60～100℃、60～90℃、60～80℃；或者为65～100℃、65～90℃、65～80℃；或80℃～90℃。
优选地，萃取体积流量之比萃取剂：(水洗水层+酸化水层)＝1:1～20:1、1:1～15:1、1:1～10:1、1:1～5:1；或者优选为5:1～20:1、5:1～15:1、5:1～10:1；或者优选为10:1～20:1、10:1～15:1。
优选地，停留时间为5min～300min、5min～200min、5min～100min、5min～60min、5min～50min；或者为50min～300min、60min～300min、100min～300min、200min～300min；或者优选为50min～200min、60min～200min、100min～200min。
上述步骤(3)中，所述萃取剂为氯苯、二氯苯、硝基氯苯、甲苯、二甲苯、苯、MIBK、二氯甲烷、二氯乙烷、氯仿、四氯化碳、乙酸乙酯中的一种或多种混合物。
上述步骤(4)中，所述反萃取条件为：反萃取温度为20～100℃，反萃取体积流量之比反萃取剂：萃取油层＝0.1:1～20:1，停留时间1min～300min，较优条件下反萃取油层中BTA残留量低于0.5％。
优选地，上述反萃取温度为40～90℃、50～90℃、60～90℃、65～90℃；或者优选为40～80℃、50～80℃、60～80℃、65～80℃；或者优选为40～70℃、50～70℃、60～70℃、65～70℃；或者优选为40～65℃、50～65℃、60～65℃。
优选地，反萃取体积流量之比反萃取剂：萃取油层＝0.5:1～20:1、1:1～20:1、5:1～20:1、10:1～20:1；或者优选为0.5:1～10:1、1:1～10:1、5:1～10:1；或者优选为0.5:1～15:1、1:1～15:1、5:1～15:1、10:1～15:1。
上述步骤(4)中，所述反萃取剂与步骤(1)酸化试剂相同，为盐酸、硫酸、硝酸、醋酸中的一种或多种；
上述步骤(5)中，所述连续化脱水釜料温度100～200℃，优选为150～180℃，更优选为170℃，绝压5～50kPa，优选为5～30kPa，5～20kPa，5～10kPa，更优选为5kPa。连续化蒸馏绝压0～2kPa、优选为1kPa，对应气相温度140～190℃，优选为150～180℃，更优选为180℃。
本发明还提供一种用于BTA合成液连续化后处理的系统，依次连接酸化反应器，水洗设备，脱水设备，蒸馏设备，成型设备；水洗设备还依次连接萃取器1和萃取器2，并通过萃取器2连接酸化反应器。
进一步地，酸化反应器与萃取器1通过酸化水管道连接。
进一步地，萃取器2通过反萃取油管道返回萃取器1中。
进一步地，脱水设备通过蒸出水管道返回水洗设备中。
利用本发明的方案，提供了一种BTA合成液连续化后处理的方法，通过将BTA合成液经连续化酸化、水洗、萃取、反萃取、脱水、蒸馏等后处理步骤，合成BTA。该方法利用BTA在不同pH下在水中的溶解度的差异，实现萃取分离，无需消耗大量的蒸发能耗，具有操作简单、环境污染小、经济性强、能耗低、易于实现工业化的优点。
附图说明
图1为连续化后处理流程图，1为酸化反应器，2为水洗设备，3为脱水设备，4为蒸馏设备，5为成型设备，6为萃取器1，7为萃取器2。
具体实施方式
下面的实施例是对本发明进行更详细的阐述，而不是对本发明的进一步限定。除非另有说明，其中的“％”均为“质量％”。
实施例1
BTA合成：将295kg邻苯二胺，213kg亚硝酸钠，370kg水置于1000L高压釜中，氮气置换，搅拌均匀后升温至260℃，保温反应3h。保温结束后，降温泄压，放出褐色澄清液体877kg，分析得邻苯二胺转化率100％，BTA收率98.94％。以此工艺开展BTA合成，合成液开展连续化后处理。
实施例2
连续化酸化：将实施例1合成液与25％盐酸按照重量比约2:1的比例连续进入酸化釜，控制酸化温度65℃，停留时间1h，酸化终点pH＝5～6。酸化液连续化分层，所得酸化油层进入连续化水洗步骤，酸化水层进入连续化萃取步骤。
连续化水洗：控制水洗温度60℃，进料体积流量之比水：油＝0.95:1～1.05:1，停留时间1h。所得水洗水层去连续化萃取，水洗油层去连续化脱水。
连续化萃取：将水洗水层和酸化水层合并，进入萃取步骤。以氯苯为萃取剂，控制萃取温度60℃，进料体积流量之比水：油＝1:0.45～1:0.55，停留时间1h。所得萃取油层去连续化反萃，萃取水层作为废水处理。
连续化反萃取：以25％盐酸为反萃取剂，控制65℃，停留时间1h，将萃取油层与25％盐酸按照体积流量之比盐酸：萃取油层＝0.2:1～0.25:1反萃取，此时所得反萃取油层中BTA含量<0.1％。所得反萃取油层作为回收萃取剂回用到连续化萃取步骤，反萃取水层为BTA盐酸盐，回用到连续化酸化步骤。
连续化脱水：将连续化水洗油层进行脱水，控制绝压5kPa，釜温170℃，此时釜料水分小于0.1％，脱出水回用到连续化水洗步骤，脱水釜料进入连续化蒸馏步骤。
连续化蒸馏：将脱水釜料连续化进入蒸馏塔，控制绝压1kPa，塔顶温度约180℃，连续化采出塔顶馏分即为BTA产品，冷却后产品外观为白色固体。
实施例3-6
在实施例2基础上，将萃取剂改为MIBK，反萃取剂、酸改成硫酸，其它条件不变，并开展物料套用，结果如下：
表1；
实施例编号 套用编号 产品色度 产品收率/％
实施例3 首批 20 81.2
实施例4 套1 20 97.4
实施例5 套2 15 97.8
实施例6 套3 15 98.1
实施例7-17
在实施例2基础上，改变后处理条件，结果如下：
表2：
Figure PCTCN2020084965-appb-000001
对比例1-4
将本发明实施例2的物料采用现有的间歇式后处理工艺处理。水洗条件参照实施例2，水洗温度60℃，水油比1:1，保温时间1h，处理结果如下：
表3：
Figure PCTCN2020084965-appb-000002
Figure PCTCN2020084965-appb-000003
对上述实施例7-14和对比例的产品的性能进行了检测，产品色度、产品纯度和产品收率均按照HG/T 3824-2014质量标准方法测得，产品色度、纯度和废水检测结果如下：
表4：
实施例编号 产品色度 产品纯度/％ 产品收率/％ 废水TOC/ppm
实施例7 15 99.95 98.16 489
实施例8 13 99.91 98.54 455
实施例9 10 99.96 97.96 468
实施例10 12 99.89 98.33 473
实施例11 14 99.81 98.12 485
实施例12 15 99.79 98.59 476
实施例13 12 99.92 98.15 464
实施例14 10 99.90 98.21 433
实施例15 大于150 98.12 50.61 -
实施例16 大于150 95.01 5.13 -
实施例17 22 99.86 98.96 486
对比例1 25 99.79 97.85 4325
对比例2 30 99.52 95.56 5230
对比例3 大于150 97.96 42.27 -
对比例4 大于150 94.89 5.05 -
从表3和表4可以看出：酸化终点pH对产品质量和收率影响较大，优选pH5～6。连续化工艺产品质量稳定，与间歇化工艺相比，产品色度降低了30～50％，质量更好，废水TOC同比约降低90％，废水处理压力显著降低。此外，水洗步骤的水油比也对产品色度有影响，连续化与间歇化相比，可以用更少的水量达到所需效果。
从上述描述可以看出，目前世界上BTA后处理采用的都是间歇化处理方式，主要是间歇化酸化，再间歇化水洗，并通过降温析晶的方式回收水中BTA，设备多、能耗高。而本发明采用连续化后处理，操作过程简单、工艺可靠性高、效率高；脱水前，后处理物料温度相同，减少换热，降低能耗；通过连续化酸化、脱水、精馏，连续化生产高品质的BTA产品。与间歇化后处理工艺相比，降低了能耗，没有间歇化处理频繁的升降温析晶过程和大量的固液分离过程，且连续化处理所得废水中TOC不足500ppm，废水处理压力也显著降低。
本发明所述内容并不仅限于本发明所述实施例内容。
本文中应用了具体个例对本发明结构及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (12)

  1. 一种BTA合成液连续化后处理的方法，其特征在于，包括下列步骤：
    (1)将BTA合成液与酸化试剂连续送入酸化反应器中连续化酸化，采出酸化水层和酸化油层；
    (2)将(1)中所述酸化油层送入水洗设备中连续化水洗，采出水洗油层和水洗水层；
    (3)将(1)中所述酸化水层和(2)中所述水洗水层合并，并送入萃取设备连续化萃取，采出萃取水层和萃取油层；
    (4)将(3)中所述萃取油层送入反萃取设备中连续化反萃取，采出反萃取油层和反萃取水层，实现萃取剂和水层中BTA回用；
    (5)将(2)中所述水洗油层依次进行连续化脱水、连续化蒸馏步骤，并在成型设备中成型，获得BTA产品。
  2. 根据权利要求1所述的BTA合成液连续化后处理的方法，其特征在于，所述步骤(1)中，所述酸化试剂为盐酸、硫酸、硝酸、醋酸中的一种或多种，
    优选地，所述连续酸化的温度为20～100℃，
    优选地，所述连续酸化的pH＝3～8，更优选为3～6，进一步优选为4～6或3～5或5～6；
    优选地，所述连续酸化的停留时间为1min～300min。
  3. 根据权利要求1所述的BTA合成液连续化后处理的方法，其特征在于，上述步骤(2)中，所述水洗条件为：水洗温度为20～100℃，
    优选地，水洗体积流量之比水：酸化油层＝0.1:1～20:1；
    优选地，水洗的停留时间1min～300min，
    优选地，所述水洗设备为水洗塔或水洗釜。
  4. 根据权利要求1所述的BTA合成液连续化后处理的方法，其特征在于，上述步骤(3)中，所述萃取条件为：萃取温度为20～100℃；
    优选地，萃取体积流量之比萃取剂：(水洗水层+酸化水层)＝0.1:1～20:1；
    优选地，萃取的停留时间1min～300min。
  5. 根据权利要求1所述的BTA合成液连续化后处理的方法，其特征在于，上述步骤(3)中，所述萃取剂为氯苯、二氯苯、硝基氯苯、甲苯、二甲苯、苯、MIBK、二氯甲烷、二氯乙烷、氯仿、四氯化碳、乙酸乙酯中的一种或多种混合物。
  6. 根据权利要求1所述的BTA合成液连续化后处理的方法，其特征在于，上述步骤(4)中，所述反萃取条件为：反萃取温度为20～100℃；
    优选地，反萃取体积流量之比反萃取剂：萃取油层＝0.1:1～20:1；
    优选地，反萃取的停留时间1min～300min；
    优选地，反萃取油层中BTA残留量低于0.5％。
  7. 根据权利要求1所述的BTA合成液连续化后处理的方法，其特征在于，上述步骤(4)中，所述反萃取剂为盐酸、硫酸、硝酸、醋酸中的一种或多种。
  8. 根据权利要求1所述的BTA合成液连续化后处理的方法，其特征在于，上述步骤(5)中，所述连续化脱水温度100～200℃；
    优选地，绝压5～50kPa；
    优选地，连续化蒸馏绝压0～2kPa；
    优选地，对应气相温度140～190℃。
  9. 根据权利要求1所述的用于BTA合成液连续化后处理的方法的系统，其特征在于，依次连接酸化反应器(1)，水洗设备(2)，脱水设备(3)，蒸馏设备(4)和成型设备(5)；其中，所述水洗设备(2)还依次连接萃取器1(6)和萃取器2(7)，并通过所述萃取器2(7)连接酸化反应器(1)。
  10. 根据权利要求9所述的系统，其特征在于，所述酸化反应器(1)与所述萃取器1(6)通过酸化水管道连接。
  11. 根据权利要求9所述的系统，其特征在于，所述萃取器2(7)通过反萃取油管道返回所述萃取器1(6)中。
  12. 根据权利要求9所述的系统，其特征在于，所述脱水设备(3)通过蒸出水管道返回所述水洗设备(2)中。
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