CN116078339A - Continuous reaction system for glyphosate API - Google Patents
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Abstract
Description
技术领域Technical Field
本发明涉及草甘膦生产技术领域,具体为一种草甘膦的连续化酸解脱醇过程中的草甘膦原料药连续化反应系统。The invention relates to the technical field of glyphosate production, in particular to a continuous reaction system for a glyphosate raw material drug in a continuous acidolysis and de-alcoholization process of glyphosate.
背景技术Background Art
草甘膦是一种高效、低毒、广谱、灭生性、非选择性除草剂,具有优良的生物特性,是全球产量最大的除草剂品种。目前,国内草甘磷主流生产工艺有两条路线:烷基酯法(甘氨酸法)和亚氨基二乙酸法(IDA法)。国外的生产工艺则主要是美国孟山都公司的亚氨基二乙酸法。我国草甘膦70%的产能是采用以甘氨酸和亚磷酸二甲酯为主要原料的烷基酯法生产,该方法以甲醇为反应溶剂,在催化剂三乙胺的存在下,甘氨酸、多聚甲醛、亚磷酸二甲酯反应得到合成液(草甘膦合成液)。一定比例的合成液与酸混合后制得混酸液(行业内又称混合液、酸解液、水解液),使用蒸汽升温至反应终点温度,随温度升高发生水解、酸解反应,生成草甘膦以及副产物甲缩醛和氯甲烷,甲缩醛、甲醇、氯甲烷等蒸汽自反应器中蒸出。酸解反应结束后剩余的液相为草甘膦料浆,经结晶、分离、洗涤、干燥得符合国标的草甘膦原药。Glyphosate is a highly efficient, low-toxic, broad-spectrum, lethal, non-selective herbicide with excellent biological properties. It is the largest herbicide variety in the world. At present, there are two mainstream production processes for glyphosate in China: the alkyl ester method (glycine method) and the iminodiacetic acid method (IDA method). The production process abroad is mainly the iminodiacetic acid method of Monsanto Company in the United States. 70% of my country's glyphosate production capacity is produced by the alkyl ester method with glycine and dimethyl phosphite as the main raw materials. This method uses methanol as the reaction solvent. In the presence of the catalyst triethylamine, glycine, polyformaldehyde, and dimethyl phosphite react to obtain a synthetic liquid (glyphosate synthetic liquid). A certain proportion of the synthetic liquid is mixed with acid to obtain a mixed acid liquid (also known as a mixed liquid, acidolysis liquid, and hydrolysis liquid in the industry). Steam is used to heat the mixture to the reaction end temperature. As the temperature rises, hydrolysis and acidolysis reactions occur to generate glyphosate and by-products methylal and chloromethane. Methylal, methanol, chloromethane and other vapors are evaporated from the reactor. The remaining liquid phase after the acid hydrolysis reaction is glyphosate slurry, which is crystallized, separated, washed and dried to obtain glyphosate technical that meets national standards.
酸解反应的气相尾气(即被风机抽离的轻组分)主要成分为水、甲缩醛、甲醇、氯化氢及氯甲烷混合物,该尾气去往气相尾气回收装置回收处理,回收过程在草甘膦行业简称为溶剂回收和氯甲烷回收:蒸馏出的混合气体经多级冷凝,冷凝液(稀甲醇)去溶剂回收装置,不凝气去氯甲烷回收装置处理;或将高温段尾气单独冷凝或吸收回收稀盐酸;或先将蒸馏出的混合气体经中和塔中和,中和后的气体去回收甲醇、甲缩醛,不凝气去氯甲烷回收装置处理。甲醇作为溶剂回用至草甘膦合成环节,甲缩醛、氯甲烷作为副产品销售。The gaseous tail gas of the acidolysis reaction (i.e., the light component extracted by the fan) is mainly composed of water, methylal, methanol, hydrogen chloride and methyl chloride mixture. The tail gas is sent to the gaseous tail gas recovery device for recovery and treatment. The recovery process is referred to as solvent recovery and methyl chloride recovery in the glyphosate industry: the distilled mixed gas is condensed in multiple stages, the condensate (diluted methanol) is sent to the solvent recovery device, and the non-condensable gas is treated by the methyl chloride recovery device; or the high-temperature tail gas is condensed or absorbed to recover dilute hydrochloric acid; or the distilled mixed gas is first neutralized in a neutralization tower, and the neutralized gas is used to recover methanol and methylal, and the non-condensable gas is treated by the methyl chloride recovery device. Methanol is reused as a solvent in the glyphosate synthesis process, and methylal and methyl chloride are sold as by-products.
甘氨酸法草甘膦生产已有30余年生产历史,溶剂回收、三乙胺回收、氯甲烷回收等工序在工业上已实现连续化,由于受草甘膦酸解反应特点等因素的限制,酸解脱醇工艺仍为间歇搅拌釜法。The production of glyphosate by the glycine method has a history of more than 30 years. The processes of solvent recovery, triethylamine recovery, and methyl chloride recovery have been realized continuously in the industry. Due to the limitations of factors such as the characteristics of the glyphosate acidolysis reaction, the acidolysis alcoholization process is still an intermittent stirred tank method.
草甘膦间歇式水解工艺存在以下问题:1.生产效率低下,综合能耗高,工人劳动强度高。2.单套装置能力小,单位产能的反应釜数量多、仪表控制点多,前后缺乏有效的连贯性,操作存在人为因素导致产品质量不稳定等问题,还制约了生产装置的放大和本质安全的提升。而连续化生产草甘膦则可以通过自动化控制,完全克服这些缺点。因此草甘膦连续酸解脱醇装置开发是草甘膦生产企业主要研究方向之一。The intermittent hydrolysis process of glyphosate has the following problems: 1. Low production efficiency, high comprehensive energy consumption, and high labor intensity of workers. 2. The capacity of a single set of equipment is small, the number of reactors per unit production capacity is large, and there are many instrument control points. There is a lack of effective continuity before and after, and there are problems such as unstable product quality caused by human factors in operation, which also restricts the expansion of production equipment and the improvement of intrinsic safety. Continuous production of glyphosate can completely overcome these shortcomings through automated control. Therefore, the development of a continuous acid-dehydrolysis device for glyphosate is one of the main research directions of glyphosate production enterprises.
专利CN 111205319 A公开了一种甘氨酸法草甘膦的连续化合成方法及系统,合成液经酸化得到的草甘膦混酸液进行一级水解反应和二级水解反应,二级水解反应后的浆料经结晶得到草甘膦。所述一级水解反应装置包括一级水解反应塔和一级水解反应釜;所述二级水解反应装置包括二级水解反应釜,所述二级水解反应装置的气体出口与水解尾气冷凝器相连。一级水解反应装置的尾气和一级水解反应装置的冷凝液、尾气去往甲醇回收装置处理。该方法的水解反应装置分为多级,装置复杂,流程长,酸解反应时间长,且收率不高。而且本方法同样仍然依赖搪瓷釜作为反应器。Patent CN 111205319 A discloses a continuous synthesis method and system of glyphosate by glycine method, wherein the glyphosate mixed acid liquid obtained by acidification of the synthetic liquid is subjected to primary hydrolysis reaction and secondary hydrolysis reaction, and the slurry after the secondary hydrolysis reaction is crystallized to obtain glyphosate. The primary hydrolysis reaction device comprises a primary hydrolysis reaction tower and a primary hydrolysis reaction kettle; the secondary hydrolysis reaction device comprises a secondary hydrolysis reaction kettle, and the gas outlet of the secondary hydrolysis reaction device is connected to a hydrolysis tail gas condenser. The tail gas of the primary hydrolysis reaction device and the condensate and tail gas of the primary hydrolysis reaction device are sent to a methanol recovery device for treatment. The hydrolysis reaction device of the method is divided into multiple stages, the device is complex, the process is long, the acidolysis reaction time is long, and the yield is not high. Moreover, the method still relies on an enamel kettle as a reactor.
发明内容Summary of the invention
针对上述技术问题,本发明提供了一种草甘膦原料药连续化反应系统,草甘膦混酸液储罐与酸解脱醇反应器连接,酸解脱醇反应器自上而下设置有2-10段功能反应段,第一反应功能段为填料段,功能反应段为3段以上时,相邻反应功能段之间经隔板隔开,所述隔板不能实现物料上下移动。In view of the above technical problems, the present invention provides a continuous reaction system for glyphosate raw materials, wherein a glyphosate mixed acid liquid storage tank is connected to an acid dealcoholization reactor, and the acid dealcoholization reactor is provided with 2-10 functional reaction sections from top to bottom, the first reaction functional section is a packing section, and when the functional reaction sections are more than 3 sections, adjacent reaction functional sections are separated by partitions, and the partitions cannot realize the up and down movement of materials.
所述的功能反应段为3、4、5、6、7、8、9、10、段时,均能实现本案的技术方案。作为本申请的一个实施例,本申请将所述的功能反应段设计为4段,即第一反应功能段、第二反应功能段、第三反应功能段、第四反应功能段,第一反应功能段为填料段,其他相邻反应功能段之间经隔板隔开,所述隔板不能实现物料上下移动。When the functional reaction section is 3, 4, 5, 6, 7, 8, 9, 10, the technical solution of this case can be realized. As an embodiment of the present application, the functional reaction section is designed as 4 sections, namely the first reaction functional section, the second reaction functional section, the third reaction functional section, and the fourth reaction functional section. The first reaction functional section is a packing section, and other adjacent reaction functional sections are separated by partitions, and the partitions cannot realize the up and down movement of materials.
第二反应功能段下部经液相管道与循环泵连接后再连接至第二反应功能段中部。The lower part of the second reaction functional section is connected to the circulation pump through a liquid phase pipeline and then connected to the middle part of the second reaction functional section.
第三反应功能段下部经液相管道与循环泵连接后再与加热器一连接,加热器一连接至第三反应功能段中部。The lower part of the third reaction functional section is connected to the circulation pump through a liquid phase pipeline and then connected to the heater 1, and the heater 1 is connected to the middle part of the third reaction functional section.
第四反应功能段底部设置有料浆出料口,料浆出料口经液相管道与循环泵连接,循环泵经液相管道分两路,一路连接至结晶器,一路经加热器二连接至第四反应功能段中部。A slurry discharge port is provided at the bottom of the fourth reaction functional section, and the slurry discharge port is connected to a circulation pump via a liquid phase pipeline. The circulation pump is divided into two paths through the liquid phase pipeline, one path is connected to the crystallizer, and the other path is connected to the middle of the fourth reaction functional section via
第二反应功能段上端1/5-2/5处经液相管道与第三反应功能段上部3/5-4/5处连接。The upper end 1/5-2/5 of the second reaction functional section is connected to the
第三反应功能段上端1/5-2/5处经液相管道与第四反应功能段上部3/5-4/5处连接。The upper end 1/5-2/5 of the third reaction functional section is connected to the
第四反应功能段液面上层经气相管道与第三反应功能段上端3/5-4/5处连接。The upper layer of the liquid surface of the fourth reaction functional section is connected to the 3/5-4/5 position of the upper end of the third reaction functional section through a gas phase pipeline.
第三反应功能段液面上层经气相管道与第二反应功能段上端3/5-4/5处连接。The upper layer of the liquid surface of the third reaction functional section is connected to the
所述的隔板还可以为溢流板。The partition plate may also be an overflow plate.
在溢流板或筛板得到情况下,第四反应功能段液面上层经气相管道与第三反应功能段上端3/5-4/5处连接;第三反应功能段液面上层经气相管道与第二反应功能段上端3/5-4/5处连接,第一反应功能段经气相管道连接至气体回收装置。When the overflow plate or sieve plate is obtained, the upper layer of the liquid surface of the fourth reaction functional section is connected to the
在筛板的情况下,第四反应功能段液面上层经气相管道连接至气体回收装置;第三反应功能段液面上层经气相管道连接至气体回收装置,第一反应功能段经气相管道连接至气体回收装置。In the case of the sieve plate, the upper layer of the liquid surface of the fourth reaction functional section is connected to the gas recovery device via a gas phase pipeline; the upper layer of the liquid surface of the third reaction functional section is connected to the gas recovery device via a gas phase pipeline, and the first reaction functional section is connected to the gas recovery device via a gas phase pipeline.
在溢流板的情况下,第四反应功能段液面上层经气相管道与第三反应功能段上端3/5-4/5处及气体回收装置连接;第三反应功能段液面上层经气相管道与第二反应功能段上端3/5-4/5处及气体回收装置连接;In the case of an overflow plate, the upper layer of the liquid surface of the fourth reaction functional section is connected to the 3/5-4/5 position of the upper end of the third reaction functional section and the gas recovery device through a gas phase pipeline; the upper layer of the liquid surface of the third reaction functional section is connected to the 3/5-4/5 position of the upper end of the second reaction functional section and the gas recovery device through a gas phase pipeline;
第一反应功能段经气相管道连接至气体回收装置。The first reaction functional section is connected to the gas recovery device via a gas phase pipeline.
在各功能段,脱除了轻组分的液相靠重力自上而下溢流至下一段。来自塔下部第二级反应功能段的物料蒸汽与自塔顶进入的混酸液在第一级反应功能段内逆流接触,进行传质、换热、反应和脱气。经第一级反应功能段预热升温和初步脱醇后液相进入第二级反应功能段,该段温度由下一级反应功能段产生的较高温度的不凝气和饱和蒸汽带入的热能维持,并与该段甲醇及水汽化所消耗的热能达到平衡,易挥发的甲缩醛、甲醇组分得到汽化随上升不凝气离开反应器。反应液再依次通过溢流、底流进入第三、第四级反应功能段升温反应。第三级反应功能段的温度由第四级反应功能段产生的较高温度的不凝气和饱和蒸汽带入的热能和在外循环管路上的加热器共同维持控制;第四级反应功能段的温度由外循环管路上的加热器维持控制。In each functional section, the liquid phase with light components removed overflows from top to bottom to the next section by gravity. The material vapor from the second-stage reaction functional section at the bottom of the tower contacts the mixed acid liquid entering from the top of the tower in the first-stage reaction functional section in countercurrent to carry out mass transfer, heat exchange, reaction and degassing. After preheating and preliminary dealcoholization in the first-stage reaction functional section, the liquid phase enters the second-stage reaction functional section. The temperature of this section is maintained by the heat energy brought in by the higher-temperature non-condensable gas and saturated steam generated in the next-stage reaction functional section, and is balanced with the heat energy consumed by the vaporization of methanol and water in this section. The volatile methylal and methanol components are vaporized and leave the reactor with the rising non-condensable gas. The reaction liquid then enters the third and fourth-stage reaction functional sections through overflow and underflow in turn to heat up and react. The temperature of the third-stage reaction functional section is jointly maintained and controlled by the higher-temperature non-condensable gas and saturated steam generated in the fourth-stage reaction functional section and the heater on the external circulation pipeline; the temperature of the fourth-stage reaction functional section is maintained and controlled by the heater on the external circulation pipeline.
可选地,或将部分液相通过底流管道自流至下一段,作为辅助液流,使用自控阀调节流量大小以平衡各反应功能区液位和压力。作为特例,当底流管道阀门开度为0%时或反应器本级不设置底流通路时,液流全部通过溢流管道进入下一级反应功能段。Alternatively, part of the liquid phase can flow to the next stage through the underflow pipe as an auxiliary liquid flow, and the flow rate can be adjusted by an automatic valve to balance the liquid level and pressure of each reaction functional area. As a special case, when the underflow pipe valve opening is 0% or the reactor is not provided with an underflow passage at this stage, all the liquid flows through the overflow pipe into the next stage reaction functional section.
在使用筛板进行分割功能区的情形下,少部分液体通过塔板筛孔自流至下一段。When sieve plates are used to divide functional areas, a small amount of liquid flows through the sieve holes of the tower plate to the next section.
在各功能段,各级气相靠压力差自下而上流向上一段,并在上一段保持一定高度的气液接触进行传质、传热,通过汽提和曝气作用加强气液传质、传热,并起到气提作用,快速祛除物料中的甲醛、甲缩醛、氯甲烷等物料。In each functional section, the gas phase of each level flows from bottom to top to the upper section by pressure difference, and maintains a certain height of gas-liquid contact in the upper section for mass transfer and heat transfer. The gas-liquid mass transfer and heat transfer are enhanced through stripping and aeration, and the gas stripping effect is played to quickly remove formaldehyde, methylal, methyl chloride and other materials in the material.
反应液中的轻组分(甲醇、水、氯化氢以及酸解反应过程中生成的甲缩醛、氯甲烷)形成气相,分别自第一级反应功能段、第二级反应功能段、第三级反应功能段和第四级反应功能段上部气相管排出。其中,第一反应功能段上部即塔顶部。第二级反应功能段产生的气相尾气经由第一级反应功能段传质、传热后由塔顶排出。The light components in the reaction liquid (methanol, water, hydrogen chloride, and methylal and chloromethane generated during the acidolysis reaction) form a gas phase and are discharged from the gas phase pipes at the top of the first reaction functional section, the second reaction functional section, the third reaction functional section, and the fourth reaction functional section. Among them, the top of the first reaction functional section is the top of the tower. The gas phase tail gas generated in the second reaction functional section is discharged from the top of the tower after mass transfer and heat transfer in the first reaction functional section.
可选地,或将部分气相通过气相管道直接去往气相总管,作为辅助气流,使用自控阀调节流量大小以平衡各反应功能区压力。作为特例,当本级反应段辅助气流管道阀门开度为0%时或反应器本级不设置辅助气流通路时,气流全部靠压力差自下而上流向上一反应功能段。Alternatively, part of the gas phase can be directly sent to the gas phase main pipe through the gas phase pipeline as an auxiliary gas flow, and the flow rate can be adjusted by an automatic control valve to balance the pressure of each reaction functional zone. As a special case, when the valve opening of the auxiliary gas flow pipeline of the current reaction stage is 0% or the reactor is not provided with an auxiliary gas flow passage, the gas flow all flows from bottom to top to the next reaction functional stage by the pressure difference.
解决了在连间歇搅拌釜工艺改续化过程中所面临的“返混”问题,解决了原有连续化技术反应不彻底(出现生料)等问题。因此,酸解水解化学反应过程充分彻底,连续化操作稳定可靠,在一台反应器内完成全部酸解反应,不需要搪瓷釜进一步辅助反应;相对于原间歇搅拌工艺,收率高,热量梯级利用、蒸汽能源耗量低。The "re-mixing" problem faced in the process of continuous batch stirring tank process improvement has been solved, and the problems of incomplete reaction (raw materials) of the original continuous technology have been solved. Therefore, the acid hydrolysis and hydrolysis chemical reaction process is fully and thoroughly, the continuous operation is stable and reliable, and the entire acid hydrolysis reaction is completed in one reactor, and no enamel kettle is required for further auxiliary reaction; compared with the original batch stirring process, the yield is high, the heat is cascaded, and the steam energy consumption is low.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1的草甘膦原料药连续化反应系统,其中,1.草甘膦混酸液储罐,2.酸解脱醇反应器,3.第一反应功能段,4.第二反应功能段,5.第三反应功能段,6.第四反应功能段,7.加热器一,8.加热器二,9.气体回收装置,10.结晶器,11-1、11-2、11-3、11-4、11-5、11-6均为循环泵,12.隔板。Figure 1 is a continuous reaction system for glyphosate API of Example 1, wherein: 1. glyphosate mixed acid liquid storage tank, 2. acid dealcoholization reactor, 3. first reaction functional section, 4. second reaction functional section, 5. third reaction functional section, 6. fourth reaction functional section, 7.
图2为隔板的结构图。Figure 2 is a structural diagram of the partition.
图3为实施例2的草甘膦原料药连续化反应系统,其中,1’.草甘膦混酸液储罐,2’.酸解脱醇反应器,3’.第一反应功能段,4’.第二反应功能段,5’.第三反应功能段,6’.第四反应功能段,7’.加热器一,8’.加热器二,9’.气体回收装置,10’.结晶器,11-1’、11-2’、11-3’、11-4’、11-5’、11-6’均为循环泵,12’.隔板。Fig. 3 is a continuous reaction system of glyphosate API of Example 2, wherein: 1'. glyphosate mixed acid liquid storage tank, 2'. acid deethanolation reactor, 3'. first reaction functional section, 4'. second reaction functional section, 5'. third reaction functional section, 6'. fourth reaction functional section, 7'.
图4为实施例3的草甘膦原料药连续化反应系统,其中,1”.草甘膦混酸液储罐,2”.酸解脱醇反应器,3”.第一反应功能段,4”.第二反应功能段,5”.第三反应功能段,6”.第四反应功能段,7”.加热器一,8”.加热器二,9”.气体回收装置,10”.结晶器,11-1”、11-2”、11-3”、11-4”、11-5”、11-6”均为循环泵,12”.隔板。Fig. 4 is a continuous reaction system of glyphosate API of Example 3, wherein: 1". glyphosate mixed acid liquid storage tank; 2". acid deethanolation reactor; 3". first reaction functional section; 4". second reaction functional section; 5". third reaction functional section; 6". fourth reaction functional section; 7". heater 1; 8".
图5为实施例4的草甘膦原料药连续化反应系统,其中,1”’.草甘膦混酸液储罐,2”’.酸解脱醇反应器,3”’.第一反应功能段,4”’.第二反应功能段,5”’.第三反应功能段,6”’.第四反应功能段,7”’.加热器一,8”’.加热器二,9”’.气体回收装置,10”’.结晶器,11-1”’、11-2”’、11-3”’、11-4”’、11-5”’、11-6”’均为循环泵,12”’.隔板。Fig. 5 is a continuous reaction system of glyphosate API of Example 4, wherein 1"'. glyphosate mixed acid liquid storage tank, 2"'. acid deethanolation reactor, 3"'. first reaction functional section, 4"'. second reaction functional section, 5"'. third reaction functional section, 6"'. fourth reaction functional section, 7"'. heater one, 8"'. heater two, 9"'. gas recovery device, 10"'. crystallizer, 11-1"', 11-2"', 11-3"', 11-4"', 11-5"', 11-6"' are all circulation pumps, 12"'. partition.
图6为隔板的溢流图。Figure 6 is a diagram of the overflow of the partition.
具体实施方式DETAILED DESCRIPTION
草甘膦混酸液为甘氨酸法草甘膦的连续化合成过程中,合成液经酸化得到的混酸液,如参考文献CN1037396A、CN111205319A等,均是得到了草甘膦混酸液,这一草甘膦混酸液是本领域技术人员所通晓的难以处理的混合性酸溶液。Glyphosate mixed acid solution is a mixed acid solution obtained by acidifying a synthetic liquid during the continuous synthesis of glyphosate by the glycine method. For example, references CN1037396A and CN111205319A all obtained glyphosate mixed acid solution. This glyphosate mixed acid solution is a mixed acid solution that is difficult to handle and is well known to those skilled in the art.
实施例1Example 1
草甘膦原料药连续化反应系统,草甘膦混酸液储罐1与酸解脱醇反应器2连接,酸解脱醇反应器2自上而下设置有第一反应功能段3、第二反应功能段4、第三反应功能段5、第四反应功能段6,第一反应功能段3为填料段,其他相邻反应功能段之间经隔板12隔开,所述隔板12不能实现物料上下移动。The invention relates to a continuous reaction system for glyphosate raw materials. A glyphosate mixed acid liquid storage tank 1 is connected to an
第二反应功能段4下部经液相管道与循环泵连接后再连接至第二反应功能段4中部。The lower part of the second reaction
第三反应功能段5下部经液相管道与循环泵连接后再与加热器一7连接,加热器一7连接至第三反应功能段5中部。The lower part of the third reaction
第四反应功能段6底部设置有料浆出料口,料浆出料口经液相管道与循环泵连接,循环泵经液相管道分两路,一路连接至结晶器10,一路经加热器二8连接至第四反应功能段6中部。A slurry discharge port is provided at the bottom of the fourth reaction
第二反应功能段4上端1/5处经液相管道与第三反应功能段5上部3/5处连接。The upper 1/5 of the second reaction
第三反应功能段5上端1/5处经液相管道与第四反应功能段6上部3/5处连接。The upper 1/5 of the third reaction
第四反应功能段6液面上层经气相管道与第三反应功能段5上端3/5处连接。The upper layer of the liquid surface of the fourth reaction
第三反应功能段5液面上层经气相管道与第二反应功能段4上端3/5处连接。The upper layer of the liquid surface of the third reaction
第一反应功能段3经气相管道连接至气体回收装置9。The first reaction
草甘膦混酸液按4m3/h进入酸解脱醇反应器的第一反应功能段后,液相经第一反应功能段的填料进入第二反应功能段,待反应液在第二反应段反应约半小时后,通过溢流管进入第三反应功能段,流量为3.0m3/h左右;待反应液在第三反应段反应约1小时后,通过溢流管进入第四反应功能段,流量为1.6m3/h左右;控制第二、三、四段循环泵流量为10m3/h进行第二、三、四段反应液的全循环;通过控制加热器的蒸汽量,控制第三、四段温度为100℃、130℃,测得第一、二段温度为46℃、72℃;反应液在酸解脱醇反应器内停留时间1-4小时;反应器第一、二级反应功能段气相操作压力控制范围在-10kPa;反应器第三反应功能段的操作压力0~50kPa,DCS应设置超高限报警;反应器第四反应功能段的操作压力10-50kPa,DCS应设置超高限报警,实现第四反应功能段的气相进入第三反应功能段,第三反应功能段进入第二反应功能段,第二反应功能段气相通过第一反应功能段经气相管道连接至气体回收装置。35d时,采出草甘膦料浆流量为1.09m3/h,草甘膦含量为22.61%,总收率84.94%。After the glyphosate mixed acid solution enters the first reaction functional section of the acid de-alcoholization reactor at a rate of 4m 3 /h, the liquid phase enters the second reaction functional section through the filler of the first reaction functional section. After the reaction liquid reacts in the second reaction section for about half an hour, it enters the third reaction functional section through the overflow pipe with a flow rate of about 3.0m 3 /h; after the reaction liquid reacts in the third reaction section for about 1 hour, it enters the fourth reaction functional section through the overflow pipe with a flow rate of about 1.6m 3 /h; the flow rates of the second, third and fourth circulation pumps are controlled to be 10m 3 /h for the full circulation of the second, third and fourth stage reaction liquid; by controlling the steam volume of the heater, the temperature of the third and fourth stages is controlled to 100℃ and 130℃, and the temperature of the first and second stages is measured to be 46℃ and 72℃; the reaction liquid stays in the acid de-alcoholization reactor for 1-4 hours; the gas phase operating pressure control range of the first and second reaction functional sections of the reactor is -10kPa; the operating pressure of the third reaction functional section of the reactor is 0~50kPa, and the DCS should be set with an ultra-high limit alarm; the operating pressure of the fourth reaction functional section of the reactor is 10-50kPa, and the DCS should be set with an ultra-high limit alarm to achieve the gas phase of the fourth reaction functional section entering the third reaction functional section, the third reaction functional section entering the second reaction functional section, and the gas phase of the second reaction functional section is connected to the gas recovery device through the gas phase pipeline through the first reaction functional section. At 35 days, the flow rate of glyphosate slurry produced was 1.09m3 /h, the glyphosate content was 22.61%, and the total recovery rate was 84.94%.
实施例2Example 2
草甘膦原料药连续化反应系统,草甘膦混酸液储罐1’与酸解脱醇反应器2’连接,酸解脱醇反应器2’自上而下设置有第一反应功能段3’、第二反应功能段4’、第三反应功能段5’、第四反应功能段6’,第一反应功能段3’为填料段,其他相邻反应功能段之间经隔板12’隔开,所述隔板12’不能实现物料上下移动。The invention discloses a continuous reaction system for glyphosate raw materials, wherein a glyphosate mixed acid liquid storage tank 1' is connected to an acid decoholization reactor 2', and the acid decoholization reactor 2' is provided with a first reaction functional section 3', a second reaction functional section 4', a third reaction functional section 5', and a fourth reaction functional section 6' from top to bottom, wherein the first reaction functional section 3' is a packing section, and other adjacent reaction functional sections are separated by a partition 12', and the partition 12' cannot realize the up and down movement of materials.
第二反应功能段4’下部经液相管道与循环泵连接后再连接至第二反应功能段4’中部。The lower part of the second reaction functional section 4' is connected to the circulation pump through a liquid phase pipeline and then connected to the middle part of the second reaction functional section 4'.
第三反应功能段5’下部经液相管道与循环泵连接后再与加热器一7’连接,加热器一7’连接至第三反应功能段5’中部。The lower part of the third reaction functional section 5' is connected to the circulation pump through the liquid phase pipeline and then connected to the heater 7', and the heater 7' is connected to the middle part of the third reaction functional section 5'.
第四反应功能段6’底部设置有料浆出料口,料浆出料口经液相管道与循环泵连接,循环泵经液相管道分两路,一路连接至结晶器10’,一路经加热器二8’连接至第四反应功能段6’中部。A slurry discharge port is provided at the bottom of the fourth reaction functional section 6', and the slurry discharge port is connected to a circulation pump via a liquid phase pipeline. The circulation pump is divided into two paths through the liquid phase pipeline, one path is connected to the crystallizer 10', and the other path is connected to the middle of the fourth reaction functional section 6' via the
第二反应功能段4’上端1/5处经液相管道与第三反应功能段5’上部4/5处连接。The upper 1/5 of the second reaction functional section 4' is connected to the upper 4/5 of the third reaction functional section 5' via a liquid phase pipeline.
第三反应功能段5’上端1/5处经液相管道与第四反应功能段6’上部4/5处连接。The upper 1/5 of the third reaction functional section 5' is connected to the upper 4/5 of the fourth reaction functional section 6' via a liquid phase pipeline.
第四反应功能段6’液面上层经气相管道连接至气体回收装置9’;第三反应功能段5’液面上层经气相管道连接至气体回收装置9’。The upper layer of the liquid surface of the fourth reaction functional section 6' is connected to the gas recovery device 9' via a gas phase pipeline; the upper layer of the liquid surface of the third reaction functional section 5' is connected to the gas recovery device 9' via a gas phase pipeline.
第一反应功能段3’经气相管道连接至气体回收装置9’。The first reaction functional section 3' is connected to the gas recovery device 9' via a gas phase pipeline.
草甘膦混酸液按4m3/h进入酸解脱醇反应器的第一反应功能段后,液相经第一反应功能段的填料进入第二反应功能段,待反应液在第二反应段反应约半小时后,通过溢流管进入第三反应功能段,流量为3.2m3/h左右;待反应液在第三反应段反应约1小时后,通过溢流管进入第四反应功能段,流量为1.7m3/h左右;控制第二、三、四段循环泵流量为10m3/h进行第二、三、四段反应液的全循环;通过控制加热器的蒸汽量,控制第三、四段温度为100℃、130℃,测得第一、二段温度为44℃、70℃;反应液在酸解脱醇反应器内停留时间1-4小时;反应器第一、二级反应功能段气相操作压力控制范围在-10kPa;反应器第三反应功能段的操作压力0~50kPa,DCS应设置超高限报警;反应器第四反应功能段的操作压力10-50kPa,DCS应设置超高限报警,第一、三、四反应功能段的气相经气相管道连接至气体回收装置。35d时,采出草甘膦料浆流量为1.10m3/h,草甘膦含量为22.00%,总收率83.48%。After the glyphosate mixed acid solution enters the first reaction functional section of the acid de-alcoholization reactor at a rate of 4m 3 /h, the liquid phase enters the second reaction functional section through the filler of the first reaction functional section. After the reaction liquid reacts in the second reaction section for about half an hour, it enters the third reaction functional section through the overflow pipe with a flow rate of about 3.2m 3 /h; after the reaction liquid reacts in the third reaction section for about 1 hour, it enters the fourth reaction functional section through the overflow pipe with a flow rate of about 1.7m 3 /h; the flow rates of the second, third and fourth circulation pumps are controlled to be 10m 3 /h for the full circulation of the second, third and fourth stage reaction liquid; by controlling the steam volume of the heater, the temperature of the third and fourth stages is controlled to 100℃ and 130℃, and the temperature of the first and second stages is measured to be 44℃ and 70℃; the reaction liquid stays in the acid de-alcoholization reactor for 1-4 hours; the gas phase operating pressure control range of the first and second reaction functional sections of the reactor is -10kPa; the operating pressure of the third reaction functional section of the reactor is 0~50kPa, and the DCS should be set with an ultra-high limit alarm; the operating pressure of the fourth reaction functional section of the reactor is 10-50kPa, and the DCS should be set with an ultra-high limit alarm, and the gas phase of the first, third and fourth reaction functional sections is connected to the gas recovery device through the gas phase pipeline. At 35 days, the flow rate of glyphosate slurry produced is 1.10m3 /h, the glyphosate content is 22.00%, and the total recovery rate is 83.48%.
实施例3Example 3
草甘膦原料药连续化反应系统,草甘膦混酸液储罐1”与酸解脱醇反应器2”连接,酸解脱醇反应器2自上而下设置有第一反应功能段3”、第二反应功能段4”、第三反应功能段5”、第四反应功能段6”,第一反应功能段3为填料段,其他相邻反应功能段之间经溢流板12”隔开,所述溢流板12”实现物料自而上下移动,不能实现自下而上的移动。The invention discloses a continuous reaction system for glyphosate raw materials. A glyphosate mixed acid liquid storage tank 1" is connected to an
第二反应功能段4”下部经液相管道与循环泵连接后再连接至第二反应功能段4”中部。The lower part of the second reaction
第三反应功能段5”下部经液相管道与循环泵连接后再与加热器一7”连接,加热器一7”连接至第三反应功能段5”中部。The lower part of the third reaction
第四反应功能段6”底部设置有料浆出料口,料浆出料口经液相管道与循环泵连接,循环泵经液相管道分两路,一路连接至结晶器10”,一路经加热器二8”连接至第四反应功能段6”中部。A slurry discharge port is provided at the bottom of the fourth reaction
第二反应功能段4”上端2/5处经液相管道与第三反应功能段5”上部3/5处连接。The upper 2/5 portion of the second reaction
第三反应功能段5”上端2/5处经液相管道与第四反应功能段6”上部3/5处连接。The third reaction
第四反应功能段6”液面上层经气相管道与第三反应功能段5”上端3/5处连接。The upper layer of the liquid surface of the fourth reaction
第三反应功能段5”液面上层经气相管道与第二反应功能段4”上端3/5处连接。The upper layer of the liquid surface of the third reaction
第一反应功能段3”经气相管道连接至气体回收装置9”。The first reaction
草甘膦混酸液按2.5m3/h速度进入酸解脱醇反应器的第一反应功能段后,液相经第一反应功能段的填料进入第二反应功能段,并通过溢流板进第三、四反应功能段,待反应液在第二反应段反应约1.5小时后,液面升至降液管进入第三反应功能段,流量为1.5m3/h左右;待反应液在第三反应段反应约3小时后,通过降液管进入第四反应功能段,流量为1m3/h左右;控制第二、三、四段循环泵流量为8m3/h进行第二、三、四段反应液的全循环;通过控制加热器的蒸汽量,控制第三、四段温度为100℃、130℃,测得第一、二段温度为48℃、73℃;反应液在酸解脱醇反应器内停留时间5-7小时;第四反应功能段的气相进入第三反应功能段,第三反应功能段气相进入第二反应功能段,第二反应功能段气相通过第一反应功能段经气相管道连接至气体回收装置。35d时,采出草甘膦料浆流量为0.81m3/h,草甘膦含量为23.31%,总收率87.04%。After the glyphosate mixed acid solution enters the first reaction functional section of the acido-dealcoholization reactor at a rate of 2.5 m 3 /h, the liquid phase enters the second reaction functional section through the filler of the first reaction functional section, and enters the third and fourth reaction functional sections through the overflow plate. After the reaction liquid reacts in the second reaction section for about 1.5 hours, the liquid level rises to the downcomer and enters the third reaction functional section with a flow rate of about 1.5 m 3 /h; after the reaction liquid reacts in the third reaction section for about 3 hours, it enters the fourth reaction functional section through the downcomer with a flow rate of about 1 m 3 /h; the flow rate of the second, third and fourth circulation pumps is controlled to be 8 m 3 /h for the full circulation of the second, third and fourth stage reaction liquids; by controlling the steam volume of the heater, the temperature of the third and fourth stages is controlled to 100℃ and 130℃, and the temperature of the first and second stages is measured to be 48℃ and 73℃; the reaction liquid stays in the acid de-alcoholization reactor for 5-7 hours; the gas phase of the fourth reaction functional stage enters the third reaction functional stage, the gas phase of the third reaction functional stage enters the second reaction functional stage, and the gas phase of the second reaction functional stage is connected to the gas recovery device through the gas phase pipeline through the first reaction functional stage. At 35 days, the flow rate of glyphosate slurry produced is 0.81m3 /h, the glyphosate content is 23.31%, and the total yield is 87.04%.
实施例4Example 4
草甘膦原料药连续化反应系统,草甘膦混酸液储罐1”’与酸解脱醇反应器2”’连接,酸解脱醇反应器2”’自上而下设置有第一反应功能段3”’、第二反应功能段4”’、第三反应功能段5”’、第四反应功能段6”’,第一反应功能段3”’为填料段,其他相邻反应功能段之间经溢流板12”’隔开,所述溢流板12”’实现物料自而上下移动,不能实现自下而上的移动。The invention discloses a continuous reaction system for glyphosate raw materials, wherein a glyphosate mixed acid liquid storage tank 1'' is connected to an acid decoholization reactor 2'', wherein the acid decoholization reactor 2'' is provided with a first reaction functional section 3''', a second reaction functional section 4'', a third reaction functional section 5'', and a fourth reaction functional section 6'' from top to bottom, wherein the first reaction functional section 3'' is a packing section, and other adjacent reaction functional sections are separated by an overflow plate 12'', wherein the overflow plate 12'' enables the material to move up and down, but cannot achieve movement from bottom to top.
第二反应功能段4”’下部经液相管道与循环泵连接后再连接至第二反应功能段4”’中部。The lower part of the second reaction functional section 4'' is connected to the circulation pump via a liquid phase pipeline and then connected to the middle part of the second reaction functional section 4''.
第三反应功能段5”’下部经液相管道与循环泵连接后再与加热器一7”’连接,加热器一7”’连接至第三反应功能段5”’中部。The lower part of the third reaction functional section 5'' is connected to the circulation pump through the liquid phase pipeline and then connected to the heater 7''. The heater 7'' is connected to the middle part of the third reaction functional section 5''.
第四反应功能段6”’底部设置有料浆出料口,料浆出料口经液相管道与循环泵连接,循环泵经液相管道分两路,一路连接至结晶器10”’,一路经加热器二8”’连接至第四反应功能段6”’中部。A slurry discharge port is provided at the bottom of the fourth reaction
第二反应功能段4”’上端2/5处经液相管道与第三反应功能段5”’上部4/5处连接。The second reaction functional section 4' ...
第三反应功能段5”’上端2/5处经液相管道与第四反应功能段6”’上部4/5处连接。The third reaction functional section 5' ...
第四反应功能段6”’液面上层气相管道与第三反应功能段5”’上端4/5处及气体回收装置9”’连接;第三反应功能段5”’液面上层经气相管道与第二反应功能段4”’上端4/5处及气体回收装置9”’连接;The gas phase pipeline of the upper layer of the liquid surface of the fourth reaction
第一反应功能段3”’经气相管道连接至气体回收装置9”’。The first reaction functional section 3'' is connected to a gas recovery device 9'' via a gas phase pipeline.
草甘膦混酸液按2.5m3/h速度进入酸解脱醇反应器的第一反应功能段后,液相经第一反应功能段的填料进入第二反应功能段,并通过溢流板进第三、四反应功能段,待反应液在第二反应段反应约1.5小时后,液面升至降液管进入第三反应功能段,流量为1.7m3/h左右;待反应液在第三反应段反应约3小时后,通过降液管进入第四反应功能段,流量为1.2m3/h左右;控制第二、三、四段循环泵流量为8m3/h进行第二、三、四段反应液的全循环;通过控制加热器的蒸汽量,控制第三、四段温度为100℃、130℃,测得第一、二段温度为45℃、70℃;反应液在酸解脱醇反应器内停留时间5-7小时;第四反应功能段的气相进入第三反应功能段,第三反应功能段气相进入第二反应功能段,第二反应功能段气相通过第一反应功能段经气相管道连接至气体回收装置,第三、四反应功能段气相经气相管道连接至气体回收装置。35d时,采出草甘膦料浆流量为0.80m3/h,草甘膦含量为22.75%,总收率85.42%。After the glyphosate mixed acid solution enters the first reaction functional section of the acido-dealcoholization reactor at a rate of 2.5m 3 /h, the liquid phase enters the second reaction functional section through the filler of the first reaction functional section, and enters the third and fourth reaction functional sections through the overflow plate. After the reaction liquid reacts in the second reaction section for about 1.5 hours, the liquid level rises to the downcomer and enters the third reaction functional section with a flow rate of about 1.7m 3 /h; after the reaction liquid reacts in the third reaction section for about 3 hours, it enters the fourth reaction functional section through the downcomer with a flow rate of about 1.2m 3 /h; the flow rate of the second, third and fourth circulation pumps is controlled to be 8m 3 /h for the full circulation of the second, third and fourth stage reaction liquids; by controlling the steam volume of the heater, the temperature of the third and fourth stages is controlled to be 100℃ and 130℃, and the temperature of the first and second stages is measured to be 45℃ and 70℃; the reaction liquid stays in the acid de-alcoholization reactor for 5-7 hours; the gas phase of the fourth reaction functional stage enters the third reaction functional stage, the gas phase of the third reaction functional stage enters the second reaction functional stage, the gas phase of the second reaction functional stage is connected to the gas recovery device through the gas phase pipeline through the first reaction functional stage, and the gas phase of the third and fourth reaction functional stages is connected to the gas recovery device through the gas phase pipeline. At 35 days, the flow rate of glyphosate slurry produced is 0.80m3 /h, the glyphosate content is 22.75%, and the total yield is 85.42%.
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