一、 順酐工藝概況
1、 Overview of maleic anhydride production process
順酐工藝按原料路線可分為苯氧化法、正丁烷氧化法兩種主要方法。按工藝技術(shù)氧化反應(yīng)部分分為固定床與流化床，后處理回收部分分為水吸收與溶劑吸收。
According to the raw material route, maleic anhydride production process can be divided into two main production methods: benzene oxidation method and n-butane oxidation method. According to the production technology, the oxidation reaction part is divided into fixed bed and fluidized bed, and the post-treatment recovery part is divided into water absorption and solvent absorption.
1.原料路線
1. Raw material route
順酐原料路線可分為苯氧化法、正丁烷氧化法。國(guó)外目前占主要地位的是以正丁烷為原料的路線，國(guó)內(nèi)裝置以苯法為主。由于我國(guó)資源的特殊性，煤資源較豐富，焦炭產(chǎn)量大，煤化工的下游產(chǎn)品焦化苯供應(yīng)充足， 使苯法順酐具有資源優(yōu)勢(shì)。正丁烷法制順酐工藝資源利用方面比苯法合理，環(huán)境污染程度比苯法輕。隨著我國(guó)石化行業(yè)快速發(fā)展和煉油能力提高，C4資源逐步得到綜合利用，正丁烷法順酐裝置近幾年發(fā)展較快。
The raw material route of maleic anhydride production can be divided into benzene oxidation method and n-butane oxidation method. At present, the production line with n-butane as raw material is the main one abroad, and the domestic production unit is mainly benzene process. Due to the particularity of China's resources, rich coal resources, large coke output and sufficient supply of coking benzene, the downstream product of coal chemical industry, the production of maleic anhydride by benzene method has resource advantages. The resource utilization of n-butane maleic anhydride process is more reasonable than that of benzene process, and the degree of environmental pollution is lighter than that of benzene process. With the rapid development of China's petrochemical industry and the improvement of oil refining capacity, C4 resources are gradually comprehensively utilized, and n-butane maleic anhydride unit has developed rapidly in recent years.
2.氧化工藝
2. Oxidation process
2.1正丁烷法流化床
2.1 n-butane fluidized bed
正丁烷進(jìn)料濃度通常為 4.0 mol～4.3 mol%，流化床反應(yīng)器上部設(shè)有催化劑分離裝置，外部設(shè)有催化劑過(guò)濾裝置。反應(yīng)器操作溫度為 400～430 ℃，熱量通過(guò)反應(yīng)器內(nèi)安裝的蒸汽盤(pán)管產(chǎn)生蒸汽供裝置使用。反應(yīng)生成氣體冷卻后進(jìn)入回收工序。
The feed concentration of n-butane is usually 4.0 mol ~ 4.3 mol%. The upper part of the fluidized bed reactor is equipped with a catalyst separation device and the outside is equipped with a catalyst filtration device. The operating temperature of the reactor is 400 ~ 430 ℃, and the heat generates steam through the steam coil installed in the reactor for the use of the device. After the reaction gas is cooled, it enters the recovery process.
2.2正丁烷法固定床
2.2 n-butane fixed bed
原料正丁烷與空氣按一定比例充分混合后進(jìn)入反應(yīng)器，在裝填了一定數(shù)量催化劑的列管內(nèi)發(fā)生反應(yīng)，正丁烷與空氣的混合比例通常為 1.6 mol～2.0 mol%。反應(yīng)器熱點(diǎn)溫度通常在 440～470 ℃。反應(yīng)熱由熔鹽冷卻器和氣體冷卻器移出，產(chǎn)生蒸汽供裝置使用。反應(yīng)生成氣體冷卻后進(jìn)入回收工序。
The raw material n-butane is fully mixed with air in a certain proportion and then enters the reactor. It reacts in the column filled with a certain amount of catalyst. The mixing ratio of n-butane and air is usually 1.6 mol ~ 2.0 mol%. The hot spot temperature of the reactor is usually 440 ~ 470 ℃. The reaction heat is removed from the molten salt cooler and gas cooler to produce steam for use by the unit. After the reaction gas is cooled, it enters the recovery process.
二、正丁烷法順酐工藝現(xiàn)狀
2、 Present situation of n-butane maleic anhydride production process
正丁烷法與苯法在工藝流程上近似，區(qū)別就是氧化反應(yīng)催化劑不同，丁烷法氧化反應(yīng)器反應(yīng)管比苯法長(zhǎng)一些，長(zhǎng)達(dá)到 6 500 mm，后處理既可以采用水吸收也可以采用溶劑吸收。
The process flow of n-butane process is similar to that of benzene process. The difference is that the oxidation reaction catalyst is different. The reaction tube of butane oxidation reactor is longer than that of benzene process, up to 6500mm. The post-treatment can be absorbed by water or solvent.
1.氧化反應(yīng)部分（固定床反應(yīng)器）
1. Oxidation reaction part (fixed bed reactor)
國(guó)內(nèi)運(yùn)行的正丁烷法順酐裝置全部為國(guó)產(chǎn)化技術(shù)固定床工藝。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)。為使反應(yīng)穩(wěn)定進(jìn)行，關(guān)鍵是反應(yīng)器載熱體熔鹽的溫度控制。國(guó)內(nèi)在固定床反應(yīng)器設(shè)計(jì)方面已經(jīng)相當(dāng)成熟，國(guó)產(chǎn)反應(yīng)器技術(shù)水平已經(jīng)達(dá)到了水平。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，自成一體，且催化劑性能穩(wěn)定，順酐收率高。
The domestic n-butane maleic anhydride units are all domestic fixed bed processes. Fixed bed reactors are mostly tubular structures with large heat transfer area, which is conducive to strong exothermic reaction. In order to make the reaction stable, the key is the temperature control of the molten salt of the reactor heat carrier. The design of fixed bed reactor has been quite mature in China, and the technical level of domestic reactor has reached the international advanced level. The fixed bed reactor is characterized by relatively simple equipment structure, easy installation, self integration, stable catalyst performance and high maleic anhydride yield.
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