順酐是三大有機(jī)酸酐之一，其化學(xué)性質(zhì)活潑，可以通過(guò)加成反應(yīng)、酰胺化反應(yīng)、酯化反應(yīng)、加氫反應(yīng)等眾多產(chǎn)品。順酐下游工業(yè)化的應(yīng)用領(lǐng)域主要包括不飽和聚酯樹(shù)脂（UPR）、有機(jī)酸、水處理、固化劑、BDO等產(chǎn)品和方向。截2022年國(guó)內(nèi)BDO產(chǎn)量約100萬(wàn)噸。國(guó)內(nèi)產(chǎn)能約130萬(wàn)噸。不飽和聚酯樹(shù)脂是順酐的大下游，占下游消費(fèi)比例約47%，UPR主要應(yīng)用于人造石、玻璃鋼等行業(yè)。
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.
除了用于不飽和聚酯樹(shù)脂之外，順酐還可以通過(guò)加氫BDO、四氫呋喃、GBL、丁二酸等產(chǎn)品；也可以通過(guò)氧化富馬酸/蘋(píng)果酸、富馬酸二甲酯等產(chǎn)品；也可以在涂料行業(yè)用于醇酸醋酸樹(shù)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、工藝正丁烷路線逐漸成為主流。
2. The production process of n-butane has gradually become the mainstream.
順酐原料路線主要分為苯氧化法和丁烷氧化法，分別以純苯和正丁烷作為原料，近年來(lái)正丁烷路線逐漸成為主流路線。
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.
苯氧化法以苯蒸氣和空氣在以V2O5-MnO3等為活性組分，α-Al2O3為載體的催化劑上發(fā)生氣相氧化反應(yīng)生成順酐。苯氧化法是順酐的傳統(tǒng)方法，工藝技術(shù)成熟可靠，以SD法應(yīng)用更為普及。但由于苯的毒性和苯與順酐較低的產(chǎn)出比，苯法順酐裝置逐漸退出運(yùn)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.
正丁烷氧化工藝是以正丁烷為原料，在V2O5-P2O5系催化劑作用下發(fā)生氣相氧化反應(yīng)生成順酐。該工藝自1974年由美國(guó)孟山都等公司實(shí)現(xiàn)工業(yè)化以來(lái)，由于原料價(jià)廉、對(duì)環(huán)境污染小以及歐美等正丁烷資源豐富等原因而得到迅速的發(fā)展。目前國(guó)外以正丁烷為原料順酐的比較典型和的工藝技術(shù)路線有美國(guó)Lummus公司和意大利Alusuisle公司聯(lián)合開(kāi)發(fā)的正丁烷流化床溶劑吸收工藝，即ALMA工藝；英國(guó)BP公司開(kāi)發(fā)的正丁烷流化床水吸收工藝，即BP工藝；美國(guó)SD公司開(kāi)發(fā)的正丁烷固定床水吸收工藝，即SD工藝等；Huntsman開(kāi)發(fā)了固定床溶劑吸收法工藝；天津市化工設(shè)計(jì)院也開(kāi)發(fā)了正丁烷固定床溶劑吸收法工藝。正丁烷法順酐更核心的在于其反應(yīng)器和溶劑吸收工藝。
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.
順酐技術(shù)的核心為原料與空氣在反應(yīng)器中發(fā)生的高溫氧化放熱反應(yīng)。所以一般順酐裝置除了產(chǎn)出順酐產(chǎn)品外，還將外送6-10噸蒸汽/噸順酐，在部分中小化工園區(qū)，順酐裝置甚是園區(qū)蒸汽的非常重要的來(lái)源，這也導(dǎo)致部分中小順酐裝置長(zhǎng)期無(wú)法實(shí)現(xiàn)有效產(chǎn)能退出。順酐氧化工藝通常分為固定床工藝和流化床工藝。流化床反應(yīng)器中固體催化劑顆粒與氣體之間接觸面積大，氣固間傳熱速率快，對(duì)于強(qiáng)放熱氧化反應(yīng)來(lái)說(shuō)更易于熱量的移出。由于其進(jìn)料濃度大大高于固定床反應(yīng)器，對(duì)能力相同的順酐裝置來(lái)講，空氣送風(fēng)系統(tǒng)一次投資及操作費(fèi)用也比固定床工藝低。固定床反應(yīng)器多為列管式結(jié)構(gòu)，傳熱面積大，有利于強(qiáng)放熱反應(yīng)。固定床反應(yīng)器的特點(diǎn)是設(shè)備結(jié)構(gòu)相對(duì)簡(jiǎn)單，安裝容易，且催化劑性能穩(wěn)定，順酐收率高。近年來(lái)國(guó)內(nèi)新上順酐裝置大多采用Huntsman和Conser等進(jìn)口技術(shù)。
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.
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