WO2020051885A1 - Preparation method for carbon-10 heavy aromatics low-naphthalene high-boiling-point aromatics solvent - Google Patents

Preparation method for carbon-10 heavy aromatics low-naphthalene high-boiling-point aromatics solvent Download PDF

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WO2020051885A1
WO2020051885A1 PCT/CN2018/105752 CN2018105752W WO2020051885A1 WO 2020051885 A1 WO2020051885 A1 WO 2020051885A1 CN 2018105752 W CN2018105752 W CN 2018105752W WO 2020051885 A1 WO2020051885 A1 WO 2020051885A1
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stage
column
aromatics
solvent
temperature
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PCT/CN2018/105752
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French (fr)
Chinese (zh)
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吴义彪
许飞
王长青
吴建亮
万春平
徐�明
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江苏华伦化工有限公司
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Priority to PCT/CN2018/105752 priority Critical patent/WO2020051885A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils

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  • the invention relates to a method for preparing a low naphthalene and high boiling point aromatic hydrocarbon solvent.
  • Naphthalene-free, low-naphthalene, high-boiling aromatic solvents are widely used in various low-naphthalene content coatings, silver pastes, pharmaceuticals and other industries. They can also be used in high-grade paint solvents, insecticide emulsions, and rubber resin solvents. With stricter environmental protection requirements The naphthalene content in naphthalene-free and low-naphthalene high-boiling aromatic solvents is also required to be lower and lower.
  • the production process of the low-naphthalene high-boiling aromatic hydrocarbon solvent is too complicated, and the produced aromatic hydrocarbon solvent has a high naphthalene content. Even after a series of complicated processes, the aromatic hydrocarbon solvent with low naphthalene content cannot be obtained, and the production cost is high.
  • the purpose of the present invention is to disclose a method for preparing a carbon decadecene aromatic low-naphthalene high-boiling aromatic solvent, which can solve the shortcomings of high aromatic naphthalene content of existing aromatic solvents.
  • the method for preparing a carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent includes the following steps:
  • step (1) The product obtained in step (1) is sequentially passed through a crystallization device and a liquid-solid separation device to obtain the carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent;
  • the invention provides a method for producing a low-naphthalene and high-boiling-point environmentally friendly aromatic hydrocarbon solvent by multi-stage distillation.
  • the naphthalene content in the aromatic solvent obtained by this method is lower than the enterprise standard, has no pollution to the environment, and has good environmental protection performance.
  • the prepared S-200 low naphthalene solvent has the characteristics of strong solubility, low toxicity, low odor, high boiling point, slow volatility, no water and olefins, no chlorine and heavy metals, stable chemical and physical properties, and good leveling.
  • Excellent solvent performance especially in the later stage of evaporation, it can exert high dissolving power, make the coating film smooth without orange peel, good gloss, improve the use safety of aromatic solvents, can be used as high-grade baking solvent, pesticide emulsifiable concentrate Solvents, solvents and plasticizers for polyurethane waterproof grouting materials.
  • FIG. 1 is a schematic structural diagram of a device used in the present invention
  • FIG. 2 is a schematic structural diagram of a rectification device.
  • FIG. 3 is a schematic structural diagram of a condensation device.
  • FIG. 4 is a schematic structural diagram of a crystallization device.
  • the method for preparing a carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent includes the following steps:
  • step (2) The product obtained in step (1) is sequentially passed through the crystallization device 200 and the liquid-solid separation device 300.
  • the mother liquor obtained is the carbon decadecene aromatic low naphthalene high boiling point aromatic solvent, which is low naphthalene S-200.
  • Solvent oil, crystals are naphthalene;
  • the crystallization temperature is -5 ⁇ -26 °C;
  • the raw carbon deca aromatics is introduced into a four-stage sequential vacuum distillation device, and then the product with a distillation range of 260-290 ° C. is collected in a final distillation device, which is a high-boiling aromatic hydrocarbon.
  • Solvent
  • the multi-stage rectification device includes a first-stage rectification tower 1, a second-stage rectification tower 2, a third-stage rectification tower 3, and a fourth-stage rectification tower 4 connected in series in sequence;
  • each stage of the distillation column is provided with a condensing reflux device 10, the bottom of the column is provided with a heater 7, the side of each stage of the distillation column is provided with a feed port 5, and the middle of the fourth stage of the distillation column 4 A discharge opening 6 is provided on the side;
  • the bottom material outlet of the upper distillation column is connected to the feed inlet 5 of the adjacent lower distillation column through a connection line 40;
  • a discharge valve 8 and a feed pump 9 are provided on the connection line 40;
  • the first-stage distillation column 1 has a theoretical plate number of 60-80, a top temperature of 100-130 ° C, a pressure of 25-40Kpa, a bottom temperature of 165-185 ° C, a pressure of 30-50Kpa, and a reflux ratio of 7: 1-9: 1;
  • the theoretical plate number of the second stage distillation column 2 is 70-90, the top temperature is 110-140 ° C, the pressure is 20-30Kpa, the temperature at the bottom of the column is 180-200 ° C, the pressure is 25-40Kpa, and the second stage
  • the reflux ratio of the rectification column 2 is controlled at 5: 1-7: 1;
  • the third stage distillation column 3 has a theoretical plate number of 75-95, a top temperature of 100-120 ° C, a pressure of 5-20Kpa, a bottom temperature of 150-180 ° C, a pressure of 10-30Kpa, and the third stage
  • the reflux ratio of the rectification column 3 is 4: 1-6: 1;
  • the fourth stage distillation column 4 has a theoretical plate number of 80-100, a top temperature of 90-130 ° C, a pressure of 1-15Kpa, a bottom temperature of 170-200 ° C, a pressure of 5-20Kpa, and a fourth stage
  • the reflux ratio of the rectification column 4 is controlled at 8: 1-10: 1;
  • the condensation reflux device 10 includes a reflux tank 11, a reflux pump 12, a primary condenser 13, a secondary condenser 14, a vacuum buffer tank 15, and a vacuum pump 16;
  • the return liquid outlet at the lower end of the reflux tank 11 is connected to the pump inlet of the reflux pump 12 through a return line, and the pump outlet of the return pump 12 is connected to the return liquid inlet in the upper part of the rectification column through a line;
  • the gas phase outlet 18 at the top of the rectification column is connected to the condensate gas inlet of the primary condenser 13 through a pipeline.
  • the secondary condensate gas outlet of the stage condenser 14 is connected to the vacuum buffer tank 15 through a pipeline, and the vacuum gas outlet of the vacuum buffer tank 15 is connected to the vacuum pump 16;
  • step (2) the crystallization process is performed in the following crystallization apparatus:
  • the crystallization device includes: a columnar mold housing 20, a crystallization tube 21, a tube sheet 22, and an aging section 24;
  • the tube sheet 22 is arranged in the mold case 20, and the outer edge is tightly connected with the inner wall of the mold case, and the mold cavity is divided into 5 to 8 cooling sections 23.
  • the tube 21 passes through the tube sheet 22, and its upper and lower ends are fixedly connected to the first tube sheet and the last tube sheet;
  • the aging section 24 is disposed at the lower part of the mold shell 20;
  • the upper part of the mold shell 20 is provided with a crystalline material inlet 25, and the bottom of the aging section 24 is provided with a aging material outlet 28;
  • the cooling section 23 is provided with a cooling medium inlet 26 and a cooling medium outlet 27, respectively;
  • step (1) The product of step (1) is pre-cooled to -5 ° C to -10 ° C, and then sent to the crystallizer through the crystallization material inlet 25, and flows downstream through the crystallization tube 21, and the crystallization is cooled through the cooling section 23, and enters the aging section 24, Make the crystals mature;
  • the temperature of the last cooling section 23 is -23 to 28 ° C, preferably -25 to 2-6 ° C;
  • the residence time of the product in step (1) in the crystallizer is 15 to 30 minutes, and the linear velocity in the crystallizing tube 21 is 1 to 5 meters, preferably 1 to 3 meters;
  • the liquid-solid separation device is conventional, such as a centrifuge and the like;
  • naphthalene in the obtained carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent ie, low naphthalene S-200 solvent oil
  • the raw carbon decaaromatic hydrocarbon is a by-product of a petroleum catalytic reforming aromatics plant (xylene), and its main composition includes mesitylene, metatetramethylbenzene, ditetramethylbenzene, naphthalene, and methylnaphthalene.
  • Terminology "S-100 Solvent Oil, S-150 Solvent Oil, S-200A Solvent Oil, S-200B Solvent Oil, Low Naphthalene S-200 Solvent Oil, S-100 Solvent Oil, S-150 Solvent Oil, S-200A
  • solvent oil, S-200B solvent oil, and low naphthalene S-200 solvent oil are respectively defined in the enterprise standard: Enterprise Standard of Jiangsu Hualun Chemical Co., Ltd., Q / 321088GYF001-2016.
  • the raw carbon deca aromatics is sent to the device shown in Figures 1 to 4, and the distillation range collected from the fourth-stage distillation column is The product at 260-290 ° C is then passed through the crystallization device 200 and the liquid-solid separation device 300 in order.
  • the mother liquor obtained is
  • the carbon decadecene aromatic naphthalene low naphthalene high boiling point aromatic hydrocarbon solvent is low naphthalene S-200 solvent oil, and the crystal is naphthalene;
  • the mold cavity is divided into 5 cooling sections 23;
  • the temperature of the last cooling section 23 is -25 ° C;
  • the residence time of the product in step (1) in the crystallizer is 15 minutes, and the linear velocity in the crystallization tube 21 is 1 m / s;
  • the raw carbon deca aromatics contains the following percentages of components:
  • the raw carbon deca aromatics is sent to the device shown in FIG. 1 to FIG. 4, and the product with a distillation range of 260 to 290 ° C. is collected from the fourth-stage rectification column, and then passed through the crystallization device 200 and the liquid-solid separation device 300 in order to obtain
  • the mother liquor is the carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent, that is, low naphthalene S-200 solvent oil, and the crystal is naphthalene;
  • the mold cavity is divided into 8 cooling sections 23;
  • the temperature of the last cooling section 23 is -25 ° C;
  • the residence time of the product in step (1) in the crystallizer is 30 minutes, and the linear velocity in the crystallization tube 21 is 3 m / s;
  • the raw carbon deca aromatics contains the following percentages of components:
  • Raw material components and content 6% of mesitylene, 10% of metatetramethylbenzene, 5% of tetramethylbenzene, 2% of naphthalene, 6% of methylnaphthalene, and the balance of impurities.
  • the naphthalene content of the low naphthalene S-200 prepared by the preparation method of the present invention is low.

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Abstract

A preparation method for a carbon-10 heavy aromatics low-naphthalene high-boiling-point aromatics solvent, comprising the following steps: (1) separating carbon-10 heavy aromatics using a multistage distillation device by means of a distillation method, and collecting a product having a distillation range of 260-290℃; (2) treating the product obtained in step (1) sequentially by means of a crystallization device and a liquid-solid separation device to obtain the carbon-10 heavy aromatics low-naphthalene high-boiling-point aromatics solvent. The crystallization temperature ranges from -5℃ to -26℃. The content of naphthalene in the obtained aromatics solvent is lower than enterprise standards, and the aromatics solvent is environment-friendly and excellent in properties, and in particular, high dissolving capacity can be exerted in the post evaporation phase, so that a coating is good in flatness and luster and free from orange peel, use safety of the aromatics solvent is improved, and the aromatics solvent can be used as an advanced varnish baking solvent, a pesticide emulsifiable concentrate solvent, a polyurethane waterproof grouting material solvent, a plasticizer and the like.

Description

碳十重芳烃低萘高沸点芳烃溶剂的制备方法Preparation method of carbon decadecene aromatic low naphthalene high boiling point aromatic solvent 技术领域Technical field
本发明涉及低萘高沸点芳烃溶剂的制备方法。The invention relates to a method for preparing a low naphthalene and high boiling point aromatic hydrocarbon solvent.
背景技术Background technique
无萘、低萘高沸点芳烃溶剂广泛用于各种低萘含量的涂料、银浆、医药等行业，也可用于高级烤漆溶剂、杀虫乳剂及橡胶树脂溶剂，随着环保要求越来越严格，无萘、低萘高沸点芳烃溶剂中的萘含量也被要求越来越低。Naphthalene-free, low-naphthalene, high-boiling aromatic solvents are widely used in various low-naphthalene content coatings, silver pastes, pharmaceuticals and other industries. They can also be used in high-grade paint solvents, insecticide emulsions, and rubber resin solvents. With stricter environmental protection requirements The naphthalene content in naphthalene-free and low-naphthalene high-boiling aromatic solvents is also required to be lower and lower.
然而现有技术中，低萘高沸点芳烃溶剂的生产工艺过于复杂，生产得到的芳烃溶剂中萘含量高，即使在经过一系列复杂工艺后依然无法得到萘含量低的芳烃溶剂，生产成本高。However, in the prior art, the production process of the low-naphthalene high-boiling aromatic hydrocarbon solvent is too complicated, and the produced aromatic hydrocarbon solvent has a high naphthalene content. Even after a series of complicated processes, the aromatic hydrocarbon solvent with low naphthalene content cannot be obtained, and the production cost is high.
发明内容Summary of the Invention
本发明的目的是公开一种碳十重芳烃低萘高沸点芳烃溶剂的制备方法，能够解决现有芳烃溶剂萘含量高的缺点。The purpose of the present invention is to disclose a method for preparing a carbon decadecene aromatic low-naphthalene high-boiling aromatic solvent, which can solve the shortcomings of high aromatic naphthalene content of existing aromatic solvents.
所述的碳十重芳烃低萘高沸点芳烃溶剂的制备方法，包括如下步骤：The method for preparing a carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent includes the following steps:
(1)将原料碳十重芳烃，采用多级精馏装置，通过精馏方法分离，收集馏程为260～290℃的产物；(1) Separating the raw material carbon deca aromatics by a rectification method using a multi-stage rectification device to collect products having a distillation range of 260 to 290 ° C;
(2)将步骤(1)获得的产物，依次通过结晶装置和液固分离装置，获得所述的碳十重芳烃低萘高沸点芳烃溶剂；(2) The product obtained in step (1) is sequentially passed through a crystallization device and a liquid-solid separation device to obtain the carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent;
结晶温度为-5～-26℃；The crystallization temperature is -5 ～ -26 ℃;
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明提供了一种采用多级精馏生产低萘高沸点环保型芳烃溶剂的方法，采用此方法得到的芳烃溶剂中的萘含量低于企业标准，对环境无污染，环保性能好，本发明制得的S-200低萘溶剂具有溶解力强、毒性低、气味小、沸点高、挥发慢、不含水和烯烃、不含氯和重金属、化学物理性能稳定及流平性好等特点，其溶剂性能优良，特别是在蒸发的后阶段能发挥高溶解力，使涂膜的平整度好而无桔皮，光泽好，提高了芳烃溶剂的使用安全性，可用作高级烤漆溶剂，农药乳油溶剂，聚氨酯防水灌浆材料溶剂及增塑剂等。The invention provides a method for producing a low-naphthalene and high-boiling-point environmentally friendly aromatic hydrocarbon solvent by multi-stage distillation. The naphthalene content in the aromatic solvent obtained by this method is lower than the enterprise standard, has no pollution to the environment, and has good environmental protection performance. The prepared S-200 low naphthalene solvent has the characteristics of strong solubility, low toxicity, low odor, high boiling point, slow volatility, no water and olefins, no chlorine and heavy metals, stable chemical and physical properties, and good leveling. Excellent solvent performance, especially in the later stage of evaporation, it can exert high dissolving power, make the coating film smooth without orange peel, good gloss, improve the use safety of aromatic solvents, can be used as high-grade baking solvent, pesticide emulsifiable concentrate Solvents, solvents and plasticizers for polyurethane waterproof grouting materials.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是本发明所用装置的结构示意图；FIG. 1 is a schematic structural diagram of a device used in the present invention;
图2是精馏装置结构示意图。FIG. 2 is a schematic structural diagram of a rectification device.
图3为冷凝装置结构示意图。FIG. 3 is a schematic structural diagram of a condensation device.
图4为结晶装置结构示意图。FIG. 4 is a schematic structural diagram of a crystallization device.
具体实施方式detailed description
参见图1、图2和图3，所述的碳十重芳烃低萘高沸点芳烃溶剂的制备方法，包括如下步骤：Referring to FIG. 1, FIG. 2 and FIG. 3, the method for preparing a carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent includes the following steps:
(1)将原料碳十重芳烃，采用多级精馏装置100，通过精馏方法分离，收集馏程为260～290℃的产物；(1) Separating the raw material carbon deca aromatics by a multi-stage rectification device 100 through a rectification method, and collecting a product having a distillation range of 260 to 290 ° C;
(2)将步骤(1)获得的产物，依次通过结晶装置200和液固分离装置300，获得的母液即为所述的碳十重芳烃低萘高沸点芳烃溶剂，即为低萘S-200溶剂油，结晶物为萘；(2) The product obtained in step (1) is sequentially passed through the crystallization device 200 and the liquid-solid separation device 300. The mother liquor obtained is the carbon decadecene aromatic low naphthalene high boiling point aromatic solvent, which is low naphthalene S-200. Solvent oil, crystals are naphthalene;
结晶温度为-5～-26℃；The crystallization temperature is -5 ～ -26 ℃;
优选的，将所述的原料碳十重芳烃引入四级依次串联的减压精馏装置中，然后在末级精馏装置收集所述的馏程为260～290℃的产物，为高沸点芳烃溶剂；Preferably, the raw carbon deca aromatics is introduced into a four-stage sequential vacuum distillation device, and then the product with a distillation range of 260-290 ° C. is collected in a final distillation device, which is a high-boiling aromatic hydrocarbon. Solvent
所述的多级精馏装置，包括依次串联连接的第一级精馏塔1、第二级精馏塔2、第三级精馏塔3和第四级精馏塔4；The multi-stage rectification device includes a first-stage rectification tower 1, a second-stage rectification tower 2, a third-stage rectification tower 3, and a fourth-stage rectification tower 4 connected in series in sequence;
每一级精馏塔的塔顶，均设有冷凝回流装置10，塔底设有加热器7，每一级精馏塔的侧面设有进料口5，第四级精馏塔4的中部侧面设有有出料口6；The top of each stage of the distillation column is provided with a condensing reflux device 10, the bottom of the column is provided with a heater 7, the side of each stage of the distillation column is provided with a feed port 5, and the middle of the fourth stage of the distillation column 4 A discharge opening 6 is provided on the side;
上一级精馏塔的塔底物料出口通过连接管线40与相邻下一级精馏塔的进料口5相连接；The bottom material outlet of the upper distillation column is connected to the feed inlet 5 of the adjacent lower distillation column through a connection line 40;
优选的，在所述的连接管线40上设有放料阀8及送料泵9；Preferably, a discharge valve 8 and a feed pump 9 are provided on the connection line 40;
第一级精馏塔1的理论板数为60-80，塔顶温度为100-130℃，压力为25-40Kpa，塔底的温度为165-185℃，压力为30-50Kpa，回流比为7:1-9:1；The first-stage distillation column 1 has a theoretical plate number of 60-80, a top temperature of 100-130 ° C, a pressure of 25-40Kpa, a bottom temperature of 165-185 ° C, a pressure of 30-50Kpa, and a reflux ratio of 7: 1-9: 1;
第二级精馏塔2的理论板数为70-90，塔顶温度为110-140℃，压力为20-30Kpa，塔底的温度为180-200℃，压力为25-40Kpa，第二级精馏塔2的回流比控制在5:1-7:1；The theoretical plate number of the second stage distillation column 2 is 70-90, the top temperature is 110-140 ° C, the pressure is 20-30Kpa, the temperature at the bottom of the column is 180-200 ° C, the pressure is 25-40Kpa, and the second stage The reflux ratio of the rectification column 2 is controlled at 5: 1-7: 1;
第三级精馏塔3的理论板数为75-95，塔顶温度为100-120℃，压力为5-20Kpa，塔底的温度为150-180℃，压力为10-30Kpa，第三级精馏塔3的回流比为4:1-6:1；The third stage distillation column 3 has a theoretical plate number of 75-95, a top temperature of 100-120 ° C, a pressure of 5-20Kpa, a bottom temperature of 150-180 ° C, a pressure of 10-30Kpa, and the third stage The reflux ratio of the rectification column 3 is 4: 1-6: 1;
第四级精馏塔4的理论板数为80-100，塔顶温度为90-130℃，压力为1-15Kpa， 塔底的温度为170-200℃，压力为5-20Kpa，第四级精馏塔4的回流比控制在8:1-10:1；The fourth stage distillation column 4 has a theoretical plate number of 80-100, a top temperature of 90-130 ° C, a pressure of 1-15Kpa, a bottom temperature of 170-200 ° C, a pressure of 5-20Kpa, and a fourth stage The reflux ratio of the rectification column 4 is controlled at 8: 1-10: 1;
所述的冷凝回流装置10，包括回流罐11、回流泵12、一级冷凝器13、二级冷凝器14、真空缓冲罐15及真空泵16；The condensation reflux device 10 includes a reflux tank 11, a reflux pump 12, a primary condenser 13, a secondary condenser 14, a vacuum buffer tank 15, and a vacuum pump 16;
所述的回流罐11的下端回流液出口通过回流管线与回流泵12的泵入口相连接，所述回流泵12的泵出口通过管线与精馏塔上部的回流液入口相连接；The return liquid outlet at the lower end of the reflux tank 11 is connected to the pump inlet of the reflux pump 12 through a return line, and the pump outlet of the return pump 12 is connected to the return liquid inlet in the upper part of the rectification column through a line;
精馏塔顶部的气相出口18通过管线与一级冷凝器13的冷凝气入口相连接，一级冷凝器13的冷凝气出口通过管线与二级冷凝器14的二级冷凝气入口相连接，二级冷凝器14的二级冷凝气出口通过管线与所述的真空缓冲罐15相连接，真空缓冲罐15的真空气出口与真空泵16相连接；The gas phase outlet 18 at the top of the rectification column is connected to the condensate gas inlet of the primary condenser 13 through a pipeline. The secondary condensate gas outlet of the stage condenser 14 is connected to the vacuum buffer tank 15 through a pipeline, and the vacuum gas outlet of the vacuum buffer tank 15 is connected to the vacuum pump 16;
优选的，步骤(2)中，所述的结晶过程是在如下的结晶装置进行的：Preferably, in step (2), the crystallization process is performed in the following crystallization apparatus:
参见图3，所述的结晶装置包括：柱状的结晶器外壳20、结晶管21、管板22和熟化段24；Referring to FIG. 3, the crystallization device includes: a columnar mold housing 20, a crystallization tube 21, a tube sheet 22, and an aging section 24;
所述的管板22设置在所述的结晶器外壳20中，外缘与所述的结晶器外壳的内壁密封连接，将结晶器内腔分隔为5～8个冷却段23，所述的结晶管21穿过所述的管板22，其上下两端与第一块管板和最后一块管板固定连接；The tube sheet 22 is arranged in the mold case 20, and the outer edge is tightly connected with the inner wall of the mold case, and the mold cavity is divided into 5 to 8 cooling sections 23. The crystals The tube 21 passes through the tube sheet 22, and its upper and lower ends are fixedly connected to the first tube sheet and the last tube sheet;
所述的熟化段24设置在所述的结晶器外壳20的下部；The aging section 24 is disposed at the lower part of the mold shell 20;
所述的结晶器外壳20的上部设有结晶物料入口25，熟化段24的底部设有熟化料出口28；The upper part of the mold shell 20 is provided with a crystalline material inlet 25, and the bottom of the aging section 24 is provided with a aging material outlet 28;
所述的冷却段23分别设有冷却介质入口26和冷却介质出口27；The cooling section 23 is provided with a cooling medium inlet 26 and a cooling medium outlet 27, respectively;
将步骤(1)的产物预冷至-5℃～-10℃，然后通过结晶物料入口25送入结晶器，通过结晶管21顺流而下，通过冷却段23冷却结晶，进入熟化段24，使得结晶物熟化；The product of step (1) is pre-cooled to -5 ° C to -10 ° C, and then sent to the crystallizer through the crystallization material inlet 25, and flows downstream through the crystallization tube 21, and the crystallization is cooled through the cooling section 23, and enters the aging section 24, Make the crystals mature;
最后一个冷却段23的温度为-23～28℃，优选-25～2-6℃；The temperature of the last cooling section 23 is -23 to 28 ° C, preferably -25 to 2-6 ° C;
至上而下，每个冷却段23的温差均匀分布；From top to bottom, the temperature difference of each cooling section 23 is evenly distributed;
步骤(1)的产物在结晶器中的停留时间为15～30分钟，在结晶管21中的线速度为1～5米，优选的为1～3米；The residence time of the product in step (1) in the crystallizer is 15 to 30 minutes, and the linear velocity in the crystallizing tube 21 is 1 to 5 meters, preferably 1 to 3 meters;
所述的液固分离装置为常规的，如离心机等；The liquid-solid separation device is conventional, such as a centrifuge and the like;
所获得的碳十重芳烃低萘高沸点芳烃溶剂中，(即低萘S-200溶剂油)，萘的含量低于企业标准；The content of naphthalene in the obtained carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent (ie, low naphthalene S-200 solvent oil) is lower than the enterprise standard;
所述的原料碳十重芳烃为石油催化重整芳烃装置(二甲苯)的副产物，其主要组成 包括均四甲苯、偏四甲苯、连四甲苯、萘及甲基萘等。The raw carbon decaaromatic hydrocarbon is a by-product of a petroleum catalytic reforming aromatics plant (xylene), and its main composition includes mesitylene, metatetramethylbenzene, ditetramethylbenzene, naphthalene, and methylnaphthalene.
以重量计：By weight:
Figure PCTCN2018105752-appb-000001
Figure PCTCN2018105752-appb-000001
优选的，以重量计：Preferably, by weight:
Figure PCTCN2018105752-appb-000002
Figure PCTCN2018105752-appb-000002
术语：“S-100溶剂油、S-150溶剂油、S-200A溶剂油、S-200B溶剂油、低萘S-200溶剂油、S-100溶剂油、S-150溶剂油、S-200A溶剂油、S-200B溶剂油、低萘S-200溶剂油”的定义，分别在企业标准：江苏华伦化工有限公司企业标准，Q/321088GYF001-2016中有详细的定义。Terminology: "S-100 Solvent Oil, S-150 Solvent Oil, S-200A Solvent Oil, S-200B Solvent Oil, Low Naphthalene S-200 Solvent Oil, S-100 Solvent Oil, S-150 Solvent Oil, S-200A The definitions of “solvent oil, S-200B solvent oil, and low naphthalene S-200 solvent oil” are respectively defined in the enterprise standard: Enterprise Standard of Jiangsu Hualun Chemical Co., Ltd., Q / 321088GYF001-2016.
实施例1Example 1
将原料碳十重芳烃送入图1～图4所示的装置，从第四级精馏塔采集馏程为The raw carbon deca aromatics is sent to the device shown in Figures 1 to 4, and the distillation range collected from the fourth-stage distillation column is 260～290℃的产物，然后依次通过结晶装置200和液固分离装置300，获得的母液即为The product at 260-290 ° C is then passed through the crystallization device 200 and the liquid-solid separation device 300 in order. The mother liquor obtained is 所述的碳十重芳烃低萘高沸点芳烃溶剂，即为低萘S-200溶剂油，结晶物为萘；The carbon decadecene aromatic naphthalene low naphthalene high boiling point aromatic hydrocarbon solvent is low naphthalene S-200 solvent oil, and the crystal is naphthalene;
其中，结晶装置结构参数：Among them, the structure parameters of the crystallization device:
结晶器内腔分隔为5个冷却段23；The mold cavity is divided into 5 cooling sections 23;
将步骤(1)的产物预冷至-5℃；Pre-cooling the product of step (1) to -5 ° C;
至上而下，最后一个冷却段23的温度为-25℃；From top to bottom, the temperature of the last cooling section 23 is -25 ° C;
步骤(1)的产物在结晶器中的停留时间为15分钟，在结晶管21中的线速度为1米/秒；The residence time of the product in step (1) in the crystallizer is 15 minutes, and the linear velocity in the crystallization tube 21 is 1 m / s;
原料碳十重芳烃含有如下百分比的组分：The raw carbon deca aromatics contains the following percentages of components:
均四甲苯10％，偏四甲苯18％，连四甲苯14％，萘4％，甲基萘4％，杂质余量。各精馏塔采用如表1所示的操作参数进行精馏，产物检测结果如表2所示。10% mesitylene, 18% metatetramethylbenzene, 14% tetramethylbenzene, 4% naphthalene, 4% methylnaphthalene, the balance of impurities. Each distillation column uses the operating parameters shown in Table 1 for rectification, and the product detection results are shown in Table 2.
表1Table 1
Figure PCTCN2018105752-appb-000003
Figure PCTCN2018105752-appb-000003
表2Table 2
Figure PCTCN2018105752-appb-000004
Figure PCTCN2018105752-appb-000004
Figure PCTCN2018105752-appb-000005
Figure PCTCN2018105752-appb-000005
实施例2Example 2
将原料碳十重芳烃送入图1～图4所示的装置，从第四级精馏塔采集馏程为 260～290℃的产物，然后依次通过结晶装置200和液固分离装置300，获得的母液即为所述的碳十重芳烃低萘高沸点芳烃溶剂，即为低萘S-200溶剂油，结晶物为萘； The raw carbon deca aromatics is sent to the device shown in FIG. 1 to FIG. 4, and the product with a distillation range of 260 to 290 ° C. is collected from the fourth-stage rectification column, and then passed through the crystallization device 200 and the liquid-solid separation device 300 in order to obtain The mother liquor is the carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent, that is, low naphthalene S-200 solvent oil, and the crystal is naphthalene;
其中，结晶装置结构参数：Among them, the structure parameters of the crystallization device:
结晶器内腔分隔为8个冷却段23；The mold cavity is divided into 8 cooling sections 23;
将步骤(1)的产物预冷至-10℃；Pre-cooling the product of step (1) to -10 ° C;
最后一个冷却段23的温度为-25℃；The temperature of the last cooling section 23 is -25 ° C;
步骤(1)的产物在结晶器中的停留时间为30分钟，在结晶管21中的线速度为3米/秒；The residence time of the product in step (1) in the crystallizer is 30 minutes, and the linear velocity in the crystallization tube 21 is 3 m / s;
原料碳十重芳烃含有如下百分比的组分：The raw carbon deca aromatics contains the following percentages of components:
原料组分和含量：均四甲苯6％，偏四甲苯10％，连四甲苯5％，萘2％，甲基萘6％，杂质余量。Raw material components and content: 6% of mesitylene, 10% of metatetramethylbenzene, 5% of tetramethylbenzene, 2% of naphthalene, 6% of methylnaphthalene, and the balance of impurities.
各精馏塔采用如表3所示的反应参数进行精馏，产物检测结果如表4所示。Each distillation column uses the reaction parameters shown in Table 3 for rectification, and the product detection results are shown in Table 4.
表3table 3
Figure PCTCN2018105752-appb-000006
Figure PCTCN2018105752-appb-000006
表4Table 4
Figure PCTCN2018105752-appb-000007
Figure PCTCN2018105752-appb-000007
Figure PCTCN2018105752-appb-000008
Figure PCTCN2018105752-appb-000008
由上述实施例可见，采用本发明制备方法制得的低萘S-200的萘含量低。It can be seen from the above examples that the naphthalene content of the low naphthalene S-200 prepared by the preparation method of the present invention is low.
综上所述，仅为本发明的较佳实施例而已，并非用来限定本发明实施的范围，凡依本发明权利要求范围所述的形状、构造、特征及精神所为的均等变化与修饰，均应包括于本发明的权利要求范围内。In summary, it is only a preferred embodiment of the present invention and is not intended to limit the scope of implementation of the present invention. Any equivalent changes and modifications to the shape, structure, characteristics, and spirit described in the scope of the claims of the present invention Shall be included in the scope of claims of the present invention.

Claims (10)

  1. 碳十重芳烃低萘高沸点芳烃溶剂的制备方法，其特征在于，包括如下步骤：The method for preparing a carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent is characterized in that it includes the following steps:
    (1)将原料碳十重芳烃，采用多级精馏装置(100)，通过精馏方法分离，收集馏程为260～290℃的产物；(1) Separating the raw material carbon deca aromatics by a rectification method using a multi-stage rectification device (100), and collecting a product having a distillation range of 260 to 290 ° C;
    (2)将步骤(1)获得的产物，依次通过结晶装置(200)和液固分离装置(300)，获得的母液即为所述的碳十重芳烃低萘高沸点芳烃溶剂，结晶温度为-5～-26℃。(2) The product obtained in step (1) is sequentially passed through a crystallization device (200) and a liquid-solid separation device (300). The mother liquor obtained is the carbon decadecene aromatic low naphthalene high boiling point aromatic hydrocarbon solvent, and the crystallization temperature is -5 ～ -26 ℃.
  2. 根据权利要求1所述的方法，其特征在于，将所述的原料碳十重芳烃引入四级依次串联的减压精馏装置中，然后在末级精馏装置收集所述的馏程为260～29℃的产物。The method according to claim 1, characterized in that said raw carbon deca aromatics is introduced into a four-stage sequential vacuum distillation device, and then collected in a final distillation device to obtain a distillation range of 260. ~ 29 ° C product.
  3. 根据权利要求2所述的方法，其特征在于，所述的多级精馏装置，包括依次串联连接的第一级精馏塔(1)、第二级精馏塔(2)、第三级精馏塔(3)和第四级精馏塔(4)；The method according to claim 2, characterized in that the multi-stage rectification device comprises a first-stage rectification tower (1), a second-stage rectification tower (2), and a third stage connected in series in sequence. Rectification column (3) and fourth-stage rectification column (4);
    每一级精馏塔的塔顶，均设有冷凝回流装置(10)，塔底设有加热器(7)，每一级精馏塔的侧面设有进料口(5)，第四级精馏塔(4)的中部侧面连接有出料口(6)；The top of each stage of the rectification column is provided with a condensing reflux device (10), the bottom of the column is provided with a heater (7), and the side of each stage of the rectification column is provided with a feed port (5). The middle side of the rectification tower (4) is connected with a discharge port (6);
    上一级精馏塔的塔底物料出口通过连接管线(40)与相邻下一级精馏塔的进料口(5)相连接。The bottom material outlet of the upper distillation column is connected to the feed inlet (5) of the adjacent lower distillation column through a connecting line (40).
  4. 根据权利要求3所述的方法，其特征在于，在所述的连接管线(40)上设有放料阀(8)及送料泵(9)。The method according to claim 3, characterized in that a discharge valve (8) and a feed pump (9) are provided on the connection line (40).
  5. 根据权利要求3所述的方法，其特征在于，第一级精馏塔塔顶温度为100-130℃，压力为25-40Kpa，塔底的温度为165-185℃，压力为30-50Kpa；The method according to claim 3, wherein the temperature at the top of the first-stage distillation column is 100-130 ° C, the pressure is 25-40Kpa, the temperature at the bottom of the column is 165-185 ° C, and the pressure is 30-50Kpa;
    第二级精馏塔塔顶温度为110-140℃，压力为20-30Kpa，塔底的温度为180-200℃，压力为25-40Kpa；The temperature at the top of the second-stage distillation column is 110-140 ° C, the pressure is 20-30Kpa, the temperature at the bottom of the column is 180-200 ° C, and the pressure is 25-40Kpa;
    第三级精馏塔塔顶温度为100-120℃，压力为5-20Kpa，塔底的温度为150-180℃，压力为10-30Kpa；The temperature at the top of the third-stage distillation column is 100-120 ° C, the pressure is 5-20Kpa, the temperature at the bottom of the column is 150-180 ° C, and the pressure is 10-30Kpa;
    第四级精馏塔塔顶温度为90-130℃，压力为1-15Kpa，塔底的温度为170-200℃，压力为5-20Kpa。The temperature at the top of the fourth-stage distillation column is 90-130 ° C, the pressure is 1-15Kpa, the temperature at the bottom of the column is 170-200 ° C, and the pressure is 5-20Kpa.
  6. 根据权利要求3所述的方法，其特征在于，所述的冷凝回流装置，包括回流 罐、回流泵、一级冷凝器、二级冷凝器、真空缓冲罐及真空泵；The method according to claim 3, wherein the condensation reflux device comprises a reflux tank, a reflux pump, a primary condenser, a secondary condenser, a vacuum buffer tank and a vacuum pump;
    所述的回流罐的下端回流液出口通过回流管线与回流泵的泵入口相连接，所述回流泵的泵出口通过管线与精馏塔上部的回流液入口相连接；The return liquid outlet at the lower end of the reflux tank is connected to the pump inlet of the return pump through a return line, and the pump outlet of the return pump is connected to the return liquid inlet in the upper part of the rectification column through a line;
    精馏塔顶部的气相出口通过管线与一级冷凝器的冷凝气入口相连接，一级冷凝器的冷凝气出口通过管线与二级冷凝器的二级冷凝气入口相连接，二级冷凝器的二级冷凝气出口通过管线与所述的真空缓冲罐相连接，真空缓冲罐的真空气出口与真空泵相连接。The gas phase outlet at the top of the rectification column is connected to the condensate gas inlet of the primary condenser through a pipeline. The condensate gas outlet of the primary condenser is connected to the secondary condenser gas inlet of the secondary condenser through a pipeline. The secondary condensate gas outlet is connected to the vacuum buffer tank through a pipeline, and the vacuum gas outlet of the vacuum buffer tank is connected to a vacuum pump.
  7. 根据权利要求1～6任一项所述的方法，其特征在于，步骤(2)中，所述的结晶过程是在如下的结晶装置进行的：The method according to any one of claims 1 to 6, wherein in the step (2), the crystallization process is performed in the following crystallization device:
    所述的结晶装置包括柱状的结晶器外壳(20)、结晶管(21)、管板(22)和熟化段(24)；The crystallizing device includes a columnar crystallizer shell (20), a crystallizing tube (21), a tube sheet (22), and an aging section (24);
    所述的管板设置在所述的结晶器外壳中，外缘与所述的结晶器外壳的内壁密封连接，将结晶器内腔分隔为5～8个冷却段(23)，所述的结晶管(21)穿过所述的管板，其上下两端与第一块管板和最后一块管板固定连接；The tube sheet is arranged in the mold shell, and the outer edge is sealedly connected with the inner wall of the mold shell, and the mold cavity is divided into 5 to 8 cooling sections (23). The tube (21) passes through the tube sheet, and its upper and lower ends are fixedly connected to the first tube sheet and the last tube sheet;
    所述的熟化段设置在所述的结晶器外壳的下部；The ripening section is arranged at the lower part of the mold shell;
    所述的结晶器外壳的上部设有结晶物料入口，熟化段的底部设有熟化料出口；The upper part of the mold shell is provided with a crystalline material inlet, and the bottom of the aging section is provided with a aging material outlet;
    所述的冷却段(23)分别设有冷却介质入口(26)和冷却介质出口(27)。The cooling section (23) is provided with a cooling medium inlet (26) and a cooling medium outlet (27), respectively.
  8. 根据权利要求7所述的方法，其特征在于，将步骤(1)的产物预冷至-5℃～-10℃，然后通过结晶物料入口送入结晶器，通过结晶管顺流而下，通过冷却段冷却结晶，进入熟化段，使得结晶物熟化；The method according to claim 7, characterized in that the product of step (1) is pre-cooled to -5 ° C to -10 ° C, and then sent to the crystallizer through the inlet of the crystallization material, and flows down through the crystallization tube, and passes through The cooling section cools the crystals and enters the aging section, so that the crystals mature.
    最后一个冷却段的温度为-23～28℃；The temperature of the last cooling section is -23 ～ 28 ℃;
    步骤(1)的产物在结晶器中的停留时间为15～30分钟，在结晶管中的线速度为1～5米。The residence time of the product in step (1) in the crystallizer is 15 to 30 minutes, and the linear velocity in the crystallizing tube is 1 to 5 meters.
  9. 根据权利要求8所述的方法，其特征在于，最后一个冷却段的温度为-25～2-6℃；至上而下，每个冷却段的温差均匀分布；The method according to claim 8, characterized in that the temperature of the last cooling section is -25 to 2-6 ° C; from top to bottom, the temperature difference of each cooling section is evenly distributed;
  10. 根据权利要求1所述的方法，其特征在于，所述的原料碳十重芳烃为石油催化重整芳烃装置(二甲苯)的副产物，其主要组成包括均四甲苯、偏四甲苯、连四甲苯、萘及甲基萘。The method according to claim 1, characterized in that said raw carbon decaaromatic hydrocarbon is a by-product of a petroleum catalytic reforming aromatics unit (xylene), and its main composition includes mesitylene, metatetramethylbenzene, and tetramethylene Toluene, naphthalene and methylnaphthalene.
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