顺酐是三大有机酸酐之一,其化学性质活泼,可以通过加成反应、酰胺化反应、酯化反应、加氢反应等生产众多产品。顺酐下游工业化的应用领域主要包括不饱和聚酯树脂(UPR)、有机酸、水处理、固化剂、BDO等产品和方向。截2022年国内BDO产量约100万吨。国内产能约130万吨。不饱和聚酯树脂是顺酐的大下游,占下游消费比例约47%,UPR主要应用于人造石、玻璃钢等行业。
Maleic anhydride is one of the three major organic anhydrides, with active chemical properties. It can be used to produce numerous products through addition reactions, amidation reactions, esterification reactions, hydrogenation reactions, etc. The application fields of downstream industrialization of maleic anhydride mainly include unsaturated polyester resin (UPR), organic acids, water treatment, curing agents, BDO and other products and directions. As of 2022, the domestic BDO production is approximately 1 million tons. The domestic production capacity is about 1.3 million tons. Unsaturated polyester resin is the largest downstream of maleic anhydride, accounting for about 47% of downstream consumption. UPR is mainly used in industries such as artificial stone and fiberglass.
除了用于生产不饱和聚酯树脂之外,顺酐还可以通过加氢生产BDO、四氢呋喃、GBL、丁二酸等产品;也可以通过氧化生产富马酸/苹果酸、富马酸二甲酯等产品;也可以在涂料行业用于生产醇酸醋酸树脂等。
In addition to being used for the production of unsaturated polyester resin, maleic anhydride can also be hydrogenated to produce products such as BDO, tetrahydrofuran, GBL, succinic acid, etc; Products such as fumaric acid/malic acid, dimethyl fumarate, etc. can also be produced through oxidation; It can also be used in the paint industry to produce alkyd acetic acid resin, etc.
2、生产工艺正丁烷路线逐渐成为主流。
2. The production process of n-butane has gradually become the mainstream.
顺酐生产原料路线主要分为苯氧化法和丁烷氧化法,分别以纯苯和正丁烷作为原料,近年来正丁烷路线逐渐成为主流路线。
The raw material routes for the production of maleic anhydride are mainly divided into benzene oxidation method and butane oxidation method, using pure benzene and n-butane as raw materials, respectively. In recent years, the n-butane route has gradually become the mainstream route.
苯氧化法以苯蒸气和空气在以V2O5-MnO3等为活性组分,α-Al2O3为载体的催化剂上发生气相氧化反应生成顺酐。苯氧化法是生产顺酐的传统生产方法,工艺技术成熟可靠,以SD法应用更为普及。但由于苯的毒性和苯与顺酐较低的产出比,苯法顺酐装置逐渐退出运行。
The benzene oxidation method uses benzene vapor and air as active components, such as V2O5-MnO3, α- Gas phase oxidation reaction occurs on the catalyst supported by Al2O3 to generate maleic anhydride. The benzene oxidation method is a traditional production method for maleic anhydride, with mature and reliable process technology, and the SD method is the most widely used. However, due to the toxicity of benzene and the low output ratio of benzene to maleic anhydride, the benzene based maleic anhydride plant has gradually withdrawn from operation.
正丁烷氧化工艺是以正丁烷为原料,在V2O5-P2O5系催化剂作用下发生气相氧化反应生成顺酐。该工艺自1974年由美国孟山都等公司实现工业化以来,由于原料价廉、对环境污染小以及欧美等正丁烷资源丰富等原因而得到迅速的发展。目前国外以正丁烷为原料生产顺酐的比较典型和的工艺技术路线有美国Lummus公司和意大利Alusuisle公司联合开发的正丁烷流化床溶剂吸收工艺,即ALMA工艺;英国BP公司开发的正丁烷流化床水吸收工艺,即BP工艺;美国SD公司开发的正丁烷固定床水吸收工艺,即SD工艺等;Huntsman开发了固定床溶剂吸收法工艺;天津市化工设计院也开发了正丁烷固定床溶剂吸收法工艺。正丁烷法顺酐更核心的在于其反应器和溶剂吸收工艺。
The n-butane oxidation process takes n-butane as the raw material and undergoes a gas-phase oxidation reaction to produce maleic anhydride under the action of V2O5-P2O5 catalyst. Since the industrialization of this process by companies such as Monsanto in the United States in 1974, it has developed rapidly due to the low cost of raw materials, low environmental pollution, and abundant n-butane resources in European and American countries. At present, the typical and advanced process technology routes for producing maleic anhydride using n-butane as raw material abroad include the n-butane fluidized bed solvent absorption process jointly developed by Lummus Company in the United States and Alusuisle Company in Italy, namely the ALMA process; The n-butane fluidized bed water absorption process developed by BP Company in the UK, also known as the BP process; The n-butane fixed bed water absorption process developed by SD Company in the United States, namely the SD process, etc; Huntsman developed a fixed bed solvent absorption process; Tianjin Chemical Design Institute has also developed the n-butane fixed bed solvent absorption process. The core of the n-butane method for maleic anhydride lies in its reactor and solvent absorption process.
顺酐生产技术的核心为原料与空气在反应器中发生的高温氧化放热反应。所以一般顺酐装置除了产出顺酐产品外,还将外送6-10吨蒸汽/吨顺酐,在部分中小化工园区,顺酐装置甚是园区蒸汽的非常重要的来源,这也导致部分中小顺酐装置长期无法实现有效产能退出。顺酐氧化工艺通常分为固定床工艺和流化床工艺。流化床反应器中固体催化剂颗粒与气体之间接触面积大,气固间传热速率快,对于强放热氧化反应来说更易于热量的移出。由于其进料浓度大大高于固定床反应器,对生产能力相同的顺酐装置来讲,空气送风系统一次投资及操作费用也比固定床工艺低。固定床反应器多为列管式结构,传热面积大,有利于强放热反应。固定床反应器的特点是设备结构相对简单,安装容易,且催化剂性能稳定,顺酐收率高。近年来国内新上顺酐装置大多采用Huntsman和Conser等进口技术。
The core of maleic anhydride production technology is the high-temperature oxidation exothermic reaction between raw materials and air in the reactor. So, in addition to producing maleic anhydride products, general maleic anhydride plants will also send 6-10 tons of steam/ton of maleic anhydride. In some small and medium-sized chemical parks, maleic anhydride plants are even a very important source of steam in the park, which has also led to some small and medium-sized maleic anhydride plants being unable to achieve effective production capacity withdrawal for a long time. The oxidation process of maleic anhydride is usually divided into fixed bed process and fluidized bed process. In a fluidized bed reactor, the contact area between solid catalyst particles and gas is large, and the heat transfer rate between gas and solid is fast, making it easier for heat to be removed for strong exothermic oxidation reactions. Due to its significantly higher feed concentration than the fixed bed reactor, the primary investment and operating costs of the air supply system for maleic anhydride plants with the same production capacity are also lower than those of the fixed bed process. Fixed bed reactors are mostly tubular structures with large heat transfer areas, which are conducive to strong exothermic reactions. The characteristics of fixed bed reactors are relatively simple equipment structure, easy installation, stable catalyst performance, and high yield of maleic anhydride. In recent years, most of the new maleic anhydride plants in China have adopted imported technologies such as Huntsman and Conser.
This article is a friendly contribution from maleic anhydride manufacturers. For more relevant knowledge, please click on: http://www.jnjhhg.cn Sincere attitude. We will provide you with comprehensive services. We will gradually contribute more relevant knowledge to everyone. Stay tuned