WO2013067920A1 - 一种醋酸乙烯生产方法 - Google Patents

一种醋酸乙烯生产方法 Download PDF

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WO2013067920A1
WO2013067920A1 PCT/CN2012/084167 CN2012084167W WO2013067920A1 WO 2013067920 A1 WO2013067920 A1 WO 2013067920A1 CN 2012084167 W CN2012084167 W CN 2012084167W WO 2013067920 A1 WO2013067920 A1 WO 2013067920A1
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Prior art keywords
vinyl acetate
oxygen
reactor
gas
reaction
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PCT/CN2012/084167
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English (en)
French (fr)
Inventor
张敏华
董秀芹
陶敏莉
刘成
欧阳胜利
姜浩锡
马静
李桂明
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天津大学
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Application filed by 天津大学 filed Critical 天津大学
Priority to SG11201402164SA priority Critical patent/SG11201402164SA/en
Priority to JP2014540304A priority patent/JP5866025B2/ja
Priority to EP12847393.1A priority patent/EP2778153A4/en
Priority to BR112014011093A priority patent/BR112014011093A2/pt
Priority to US14/356,604 priority patent/US20140303398A1/en
Publication of WO2013067920A1 publication Critical patent/WO2013067920A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation

Definitions

  • the invention relates to a method for producing vinyl acetate.
  • the method expands the stable region by adding an inert gas to the circulating gas, increases the oxygen concentration at the inlet of the reactor, lowers the reaction temperature, prolongs the service life of the catalyst, improves the selectivity of vinyl acetate, reduces the production cost, and improves the market competition of vinyl acetate products. force. Background technique
  • Vinyl acetate (VAC) is an important organic chemical raw material.
  • PVA polyvinyl alcohol
  • EVA vinyl acetate-ethylene copolymer
  • PVAC polyvinyl acetate
  • a derivative such as vinyl acetate monovinyl chloride copolymer (EVC).
  • China's vinyl acetate production began in the 1960s. In 1965, the Beijing Organic Chemical Plant introduced acetylene fluidized bed technology from Japan, and then built several sets of similar devices in China. These vinyl acetate units are all supplied with Vinylon. In the 1970s and 1980s, about 90% of China's vinyl acetate was used for vinylon and polyvinyl alcohol. In recent years, with the development of polyvinyl alcohol, China's vinyl acetate market has continued to expand. As of the end of 2008, China's total production capacity of vinyl acetate was 1.4 million tons per year. It is expected that the demand for vinyl acetate in China will increase at a rate of 8% in the future.
  • the vinyl acetate production process has two methods: ethylene method and acetylene method. Acetylene is seriously polluted and has been eliminated in foreign countries. At present, only a few countries such as China adopt the acetylene method. Ethylene production dominates worldwide.
  • the ethylene vinyl acetate production process is to feed the raw materials of ethylene, oxygen and acetic acid into the reactor, and contact with the catalyst in the reactor, and react at a pressure of 0.1 6-1. IMPa and 130 ⁇ 200 ° C to form VA ( :, water and a small amount of by-products.
  • the high-temperature reaction gas is condensed in multiple stages, the condensate contains vinyl acetate, water and unreacted acetic acid, etc., and the mixed liquid is sent to the fine boring process for VAC refining. Unreacted ethylene gas is returned to the compressor cycle Used, it is called a circulating gas.
  • the increase in vinyl acetate production is related to the concentration of oxygen in the system. Properly increasing the oxygen concentration can lower the reaction temperature, prolong the life of the catalyst, increase the selectivity of vinyl acetate, thereby reducing the production cost of acetic acid and increasing the market competitiveness of vinyl acetate products.
  • the increase in oxygen concentration in the system is limited by the limits of the explosion and is often controlled in the lower range (6% mol%) in actual production.
  • the lower oxygen concentration has higher operational safety, the reaction temperature is higher, the ethylene single-pass conversion rate is lower, and it is economically disadvantageous.
  • the object of the present invention is to provide a method for producing vinyl acetate, which can increase the oxygen concentration at the inlet of the reactor, thereby lowering the reaction temperature, prolonging the service life of the catalyst, increasing the selectivity of vinyl acetate, reducing the production cost, and increasing the vinegar. Acid and ethylene production.
  • the ethylene vinyl acetate production process is to feed the raw materials ethylene, oxygen and acetic acid into the reactor, and contact with the catalyst in the reactor to form vinyl acetate, water and a small amount of by-products.
  • the reaction temperature was 13 CTC; in the middle of the catalyst, the reaction temperature was 17 CTC; at the later stage of the catalyst use, the reaction temperature was finally increased to 200 ° C as the activity of the catalyst was lowered.
  • the high-temperature reaction gas is condensed in multiple stages, and the condensate contains vinyl acetate, water, and unreacted acetic acid, and the mixed solution is sent to a fine boring process to purify vinyl acetate.
  • the uncondensed gas contains unreacted ethylene, oxygen, etc., and is returned to the compressor for recycling, which is called a circulating gas.
  • the increase in vinyl acetate production is related to the concentration of oxygen in the system.
  • Increasing the concentration of oxygen in the reactor over a range of concentrations can reduce the reaction temperature, extend the life of the catalyst, and increase the selectivity of the reaction.
  • the increase in oxygen concentration in the system is limited by the explosion limit.
  • the oxygen concentration is often controlled to a lower range, which leads to an increase in the reaction temperature and a decrease in the selectivity of vinyl acetate. Since the explosion limit of oxygen is a function of temperature, pressure, and composition of the mixture, the explosion limit of oxygen can be changed by changing the temperature, pressure, and composition of the mixture.
  • the lower limit of the explosion of oxygen can be increased by increasing the content of acetic acid in the system, thereby expanding the stability zone.
  • the acetic acid vapor in the system is obtained by heating with fresh steam. This method will result in an increase in system energy consumption and production cost.
  • a method for producing vinyl acetate according to the present invention by adding an inert gas to a circulating gas, increasing the lower explosion limit of oxygen, expanding a stable region of the reaction system, increasing the oxygen concentration of the reaction system, thereby lowering the reaction temperature, prolonging the service life of the catalyst, and increasing the acetic acid. Ethylene selectivity.
  • an inert gas is added to the cycle gas, and the inert gas concentration at the inlet of the reactor is 8 to 30 mol%.
  • the inert gas is nitrogen or a mixture of nitrogen and methane.
  • the inert gas to be added is a mixture of nitrogen and methane
  • the volume ratio of nitrogen to methane is 4:1 to 4:2.
  • the oxygen concentration of the inlet of the reactor can reach 10. 5-12mol%.
  • the invention has a reaction temperature of 110-18 CTC, a decrease of 5-2 CTC, and a vinyl acetate selectivity of 93.5-96%, an increase of 0.5-3%.
  • a method for producing vinyl acetate according to the present invention which has the advantage of improving the system.
  • the inert gas concentration increases the explosion limit of oxygen and expands the stable area of the reaction system, thereby increasing the actual concentration of oxygen at the reactor inlet during the production process. It avoids the expansion of the stable zone by increasing the acetic acid content in the system, reduces the acetic acid content in the recycle gas, reduces the steam consumption, reduces the production cost, and improves the market competitiveness of the vinyl acetate product.
  • Figure 1 Schematic diagram of the process of vinyl acetate production. detailed description
  • oxygen is mixed with a circulating gas containing ethylene and acetic acid through an oxygen mixer 4, and the mixed gas enters the reactor 1 for reaction.
  • the high-temperature reaction gas after the reaction is condensed by the condensing system 2, and the uncondensed gas phase is subjected to a circulating gas pressure.
  • the compressor 3 is boosted and recycled. Nitrogen gas was added to the recycle gas to control the inlet nitrogen concentration of the reactor to 30% (mol%). At this time, the oxygen concentration at the inlet of the reactor was increased to 12% (mol%).
  • the reaction temperature was 11 CTC; In the medium term, the reaction temperature is 15 CTC; at the end of the catalyst use, the reaction temperature is 180 °C. Reduced by 20 °C compared to the original process.
  • the selectivity to vinyl acetate was 96%, an increase of 3%.
  • oxygen is mixed with a circulating gas containing ethylene and acetic acid through an oxygen mixer 4, and the mixed gas enters the reactor 1 for reaction, and the high-temperature reaction gas after the reaction is condensed by the condensing system 2, and the uncondensed gas phase is passed through the circulating gas compressor. 3 is used after the boost.
  • the nitrogen gas is added to the recycle gas to control the inlet nitrogen concentration of the reactor to be 15% (mol%), and the oxygen concentration at the inlet of the reactor is increased to 11.4% (mol%).
  • the reaction temperature is 12 CTC; In the middle of the catalyst, the reaction temperature is 16 CTC; at the end of the catalyst use, the reaction temperature is 190 °C. 10 ° C lower than the original process.
  • the selectivity to vinyl acetate was 95%, an increase of 2%.
  • oxygen is mixed with a circulating gas containing ethylene and acetic acid through an oxygen mixer 4, and the mixed gas enters the reactor 1 for reaction, and the high-temperature reaction gas after the reaction is condensed by the condensing system 2, and the uncondensed gas phase is passed through the circulating gas compressor. 3 is used after the boost.
  • Nitrogen was added to the recycle gas to control the inlet nitrogen concentration of the reactor to be 8% (mol%), and the oxygen concentration at the inlet of the reactor was increased to 10.5% (mol%).
  • the reaction temperature was 125 °C. ; mid catalyst used, the reaction temperature was 165 ° C; late use of a catalyst, the reaction temperature was 195 ° C. 5 ° C lower than the original process. 5% ⁇
  • the selectivity of acetic acid was 93.5%, increased by 0.5%.
  • oxygen is mixed with a circulating gas containing ethylene and acetic acid through an oxygen mixer 4, and the mixed gas enters the reactor 1 for reaction, and the high-temperature reaction gas after the reaction is condensed by the condensing system 2, and the uncondensed gas phase is passed through the circulating gas compressor. 3 is used after the boost.
  • a mixed gas of nitrogen and methane is added to the circulating gas to control the concentration of the mixture of nitrogen and methane at the inlet of the reactor to be 15% (mol%), and the oxygen concentration at the inlet of the reactor is increased to ll% (mol%), at the initial stage of use of the catalyst.
  • the reaction temperature is 122 ° C ; in the middle of the catalyst, the reaction temperature is 162 ° C ; in the later stage of the catalyst use, the reaction temperature is 192 ° C, which is 8 ° C lower than the original process.
  • the selectivity for vinyl acetate was 94%, an increase of 1%.
  • the method for producing vinyl acetate disclosed and proposed by the present invention can be realized by those skilled in the art by appropriately changing the raw materials, process parameters, structural design and the like by referring to the contents of the paper.
  • the method and technology of the present invention have been described by way of a preferred embodiment, and it will be apparent to those skilled in the ⁇ Desc/Clms Page number> The technology of the present invention. It is to be understood that all such alternatives and modifications are obvious to those skilled in the art and are considered to be included in the spirit, scope and content of the invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明的一种醋酸乙烯生产方法，通过在循环气体中加入惰性气体，提高氧气的爆炸极限，扩大反应系统的稳定区域，提高反应系统氧气浓度，从而降低反应温度，延长催化剂使用寿命，提高醋酸乙烯的选择性。所述的惰性气体为氮气或氮气及甲烷的混合物。反应器入口惰性气体浓度为8-30mol%。反应器入口氧气摩尔浓度为10.5—12mol%。

Description

一种醋酸乙烯牛产方法 技术领域
本发明涉及一种醋酸乙烯生产方法。 该方法通过在循环气体中加入惰性气体， 扩大了稳 定区域， 提高反应器入口氧气浓度， 降低反应温度， 延长催化剂使用寿命， 提高醋酸乙烯的 选择性， 降低生产成本， 提高醋酸乙烯产品的市场竞争力。 背景技术
醋酸乙烯 (VAC)是一种重要的有机化工原料， 通过自身聚合或与其它单体共聚， 可以生成 聚乙烯醇 (PVA)、 醋酸乙烯一乙烯共聚物 (EVA)、 聚醋酸乙烯 (PVAC)、 醋酸乙烯一氯乙烯共聚 物 (EVC)等衍生物。 这些衍生物的用途十分广泛， 一般可用于粘接剂， 纸张或织物的上胶剂、 油漆、 墨水、 皮革加工、 乳化剂、 水溶性膜、 土壤改良剂等方面。 醋酸乙烯作为中间体， 随 着聚乙烯醇非纤维领域应用的拓展， 使得醋酸乙烯的需求不断增长， 提高。
我国醋酸乙烯生产开始于 20世纪 60年代。 1965年北京有机化工厂从日本引进乙炔法流化 床技术， 之后在国内建成多套同类装置。 这些醋酸乙烯装置均为维尼纶配套， 在 20世纪 70〜 80年代， 中国醋酸乙烯约有 90%用于维尼纶及聚乙烯醇。 近年来随着聚乙烯醇的发展， 中国 醋酸乙烯市场不断扩大。 截至到 2008年底， 中国醋酸乙烯总生产能力 140万吨 /年， 预计未来 我国醋酸乙烯的需求量将以 8%的速率增长。
醋酸乙烯生产工艺路线有乙烯法和乙炔法两种。 乙炔污染严重， 在国外已被淘汰， 目前 只有我国等少数国家采用乙炔法。 在世界范围内乙烯法生产占主导地位。 乙烯法醋酸乙烯生 产过程是将原料乙烯、 氧、 醋酸气体通入反应器， 在反应器内与催化剂接触， 在绝对压力 0. 6-1. IMPa和 130〜200°C温度下反应生成 VA (：、水及少量副产物。高温反应气体经多级冷凝， 冷凝液中含有醋酸乙烯、 水及未反应的醋酸等， 混合液送精镏工序进行 VAC的精制。 未反应 乙烯气体返回压缩机循环使用， 被成为循环气体。
乙烯气相氧化合成醋酸乙烯的生产过程中，醋酸乙烯产量的提高与系统中氧的浓度有关。 适当的提高氧浓度能降低反应温度， 延长催化剂寿命、 提高醋酸乙烯的选择性， 从而降低乙 酸降低生产成本， 提高醋酸乙烯产品的市场竞争力。 但是系统中氧浓度的提高受到了爆炸极 限的限制， 在实际生产中往往被控制在较低的范围 （ 6% mol%)。 较低的氧浓度虽然具有较 高操作安全性， 但反应温度较高， 乙烯单程转化率较低， 经济上不利。 因此， 在合成醋酸乙 烯的生产过程中， 在满足安全性的前提下， 开发新的工艺过程， 提高氧气浓度， 就能够降低 反应温度及提高醋酸乙烯的选择性， 从而降低反应成本。 发明内容
本发明的目的在于提供一种醋酸乙烯生产方法， 该方法能够提高反应器入口氧气浓度， 从而降低反应温度， 延长催化剂使用寿命， 提高醋酸乙烯的选择性， 降低生产成本， 提高醋 酸乙烯产量。
乙烯法醋酸乙烯生产过程是将原料乙烯、 氧、 醋酸气体通入反应器， 在反应器内与催化 剂接触， 反应生成醋酸乙烯、 水及少量副产物。 在催化剂使用初期， 反应温度为 13CTC ; 在 催化剂使用中期， 反应温度为 17CTC ; 在催化剂使用后期， 随着催化剂活性的降低， 反应温 度最终提高至 200°C。 高温反应气体经多级冷凝， 冷凝液中含有醋酸乙烯、 水及未反应的醋 酸等， 混合液送精镏工序进行醋酸乙烯的精制。 未冷凝的气体中含有未反应的乙烯、氧气等, 返回压缩机循环使用， 被称为循环气体。
在气相法醋酸乙烯的生产过程中， 醋酸乙烯产量的提高与系统中氧的浓度有关。 在一定 浓度范围内， 提高反应器中氧气的浓度， 能够降低反应温度， 延长催化剂使用寿命， 提高反 应选择性。 但是系统中氧浓度的提高受到了爆炸极限的限制， 在实际生产中氧气浓度往往被 控制在较低范围之内， 这将导致反应温度的增加及醋酸乙烯选择性的降低。 由于氧气的爆炸 极限是温度、 压力及混合物组成的函数， 因此可以通过改变温度、 压力及混合物组成来改变 氧气的爆炸极限。 如可以通过提高系统中醋酸的含量来提高氧气的爆炸下限， 起到扩大稳定 区的作用。 但是系统中的醋酸蒸汽是通过新鲜蒸汽加热获得的， 采用这种方法将造成体系能 耗、 生产成本的增加。
本发明的一种醋酸乙烯生产方法， 通过在循环气体中加入惰性气体， 提高氧气的爆炸下 限， 扩大反应系统的稳定区域， 提高反应系统氧气浓度， 从而降低反应温度， 延长催化剂使 用寿命， 提高醋酸乙烯的选择性。
本发明的一种醋酸乙烯生产方法， 在循环气体中加入惰性气体， 反应器入口惰性气体浓 度为 8_30mol%。
所述的惰性气体为氮气或氮气及甲烷的混合物。
当加入的惰性气体为氮气及甲烷的混合物时， 氮气与甲烷体积比为 4 : 1〜4 : 2。
通过采取上述手段， 实际生产过程中反应器入口氧气摩尔浓度可以达到 10. 5-12mol%。 本发明的反应温度为 110-18CTC，降低 5-2CTC，醋酸乙烯选择性为 93. 5_96%，提高 0. 5-3% 0 本发明的一种醋酸乙烯生产方法， 其优点在于通过提高系统中惰性气体浓度， 提高氧气 的爆炸极限， 扩大反应系统的稳定区域， 从而提高生产过程中反应器入口氧气的实际浓度。 避免了通过提高系统中醋酸含量来扩大稳定区， 降低了循环气中醋酸含量， 降低蒸汽消耗， 降低生产成本,提高醋酸乙烯产品的市场竞争力。
附图说明
图 1 : 醋酸乙烯生产过程流程示意图。 具体实施方式
以下结合具体实施例进一步说明本发明的实施过程。 下述反应压力为绝对压力 0. 6-1. lMPa0
实施例 1 :
醋酸乙烯生产中氧气通过氧气混合器 4与含有乙烯、 醋酸的循环气体混合， 混合气体进 入反应器 1进行反应， 反应后的高温反应气体经冷凝系统 2冷凝， 未凝的气相经循环气体压 缩机 3升压后循环使用。 在循环气体中加入氮气， 控制反应器入口氮气浓度为 30% (mol%)， 此时反应器入口氧气浓度提高至 12% (mol%)， 在催化剂使用初期， 反应温度为 11CTC ; 在催化 剂使用中期， 反应温度为 15CTC ; 在催化剂使用后期， 反应温度为 180 °C。 较原工艺降低 20 °C。 醋酸乙烯选择性为 96%， 提高 3%。
实施例 2:
醋酸乙烯生产中氧气通过氧气混合器 4与含有乙烯、 醋酸的循环气体混合， 混合气体进 入反应器 1进行反应， 反应后的高温反应气体经冷凝系统 2冷凝， 未凝的气相经循环气体压 缩机 3升压后循环使用。 在循环气体中加入氮气， 控制反应器入口氮气浓度为 15% (mol%)， 此时反应器入口氧气浓度提高至 11. 4% (mol%)， 在催化剂使用初期， 反应温度为 12CTC ; 在催 化剂使用中期， 反应温度为 16CTC ; 在催化剂使用后期， 反应温度为 190 °C。 较原工艺降低 10°C。 醋酸乙烯选择性为 95%， 提高 2%。
实施例 3:
醋酸乙烯生产中氧气通过氧气混合器 4与含有乙烯、 醋酸的循环气体混合， 混合气体进 入反应器 1进行反应， 反应后的高温反应气体经冷凝系统 2冷凝， 未凝的气相经循环气体压 缩机 3升压后循环使用。 在循环气体中加入氮气， 控制反应器入口氮气浓度为 8% (mol%)， 此 时反应器入口氧气浓度提高至 10. 5% (mol%)， 在催化剂使用初期， 反应温度为 125°C ; 在催化 剂使用中期， 反应温度为 165°C ; 在催化剂使用后期， 反应温度为 195°C。较原工艺降低 5°C。 醋酸乙烯选择性为 93. 5%， 提高 0. 5%。
实施例 4:
醋酸乙烯生产中氧气通过氧气混合器 4与含有乙烯、 醋酸的循环气体混合， 混合气体进 入反应器 1进行反应， 反应后的高温反应气体经冷凝系统 2冷凝， 未凝的气相经循环气体压 缩机 3升压后循环使用。 在循环气体中加入氮气及甲烷的混合气体， 控制反应器入口氮气及 甲烷的混合物浓度为 15% (mol%)， 此时反应器入口氧气浓度提高至 l l% (mol%)， 在催化剂使用 初期， 反应温度为 122°C ; 在催化剂使用中期， 反应温度为 162°C ; 在催化剂使用后期， 反应 温度为 192°C， 较原工艺降低 8°C。； 醋酸乙烯选择性为 94%， 提高 1%。
本发明公开和提出的一种醋酸乙烯生产方法， 本领域技术人员可通过借鉴本文内容， 适 当改变原料、 工艺参数、 结构设计等环节实现。 本发明的方法与技术已通过较佳实施例子进 行了描述， 相关技术人员明显能在不脱离本发明内容、 精神和范围内对本文所述的方法和技 术进行改动或适当变更与组合， 来实现本发明技术。 特别需要指出的是， 所有相类似的替换 和改动对本领域技术人员来说是显而易见的， 他们都被视为包括在本发明精神、 范围和内容 中。

Claims

1. 一种醋酸乙烯生产方法， 其特征为在循环气体中加入惰性气体， 反应器入口惰性气 体浓度为 8-30mol%。
2. 如权利要求 1所述的醋酸乙烯生产方法， 其特征是所述的惰性气体为氮气或氮气及 甲烷的混合物。
3. 如权利要求 2所述的醋酸乙烯生产方法， 其特征为加入的惰性气体为氮气及甲烷的 混合物时， 氮气与甲烷体积比为 4 : 1〜4 : 2。
4. 如权利要求 1所述的醋酸乙烯生产方法， 其特征为反应器入口氧气浓度为
10. 5- 12mol%。
5. 如权利要求 1所述的方法， 其特征是反应器的反应温度为 110-180°C。
PCT/CN2012/084167 2011-11-11 2012-11-06 一种醋酸乙烯生产方法 WO2013067920A1 (zh)

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