WO1998055217A1 - A fluidized bed reactor for the ammoxidation of hydrocarbons - Google Patents

A fluidized bed reactor for the ammoxidation of hydrocarbons Download PDF

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Publication number
WO1998055217A1
WO1998055217A1 PCT/CN1998/000094 CN9800094W WO9855217A1 WO 1998055217 A1 WO1998055217 A1 WO 1998055217A1 CN 9800094 W CN9800094 W CN 9800094W WO 9855217 A1 WO9855217 A1 WO 9855217A1
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Prior art keywords
ammonia
fluidized bed
bed reactor
acrylonitrile
catalyst
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PCT/CN1998/000094
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English (en)
French (fr)
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WO1998055217A8 (en
Inventor
Xin Chen
Lianghua Wu
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China Petro-Chemical Corporation
Shangai Research Institute Of Petrochemical Technology, Sinopec
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Application filed by China Petro-Chemical Corporation, Shangai Research Institute Of Petrochemical Technology, Sinopec filed Critical China Petro-Chemical Corporation
Priority to EP98925385A priority Critical patent/EP1008382A4/en
Priority to BRPI9810414-4A priority patent/BR9810414B1/pt
Priority to JP50123099A priority patent/JP4047938B2/ja
Publication of WO1998055217A1 publication Critical patent/WO1998055217A1/zh
Publication of WO1998055217A8 publication Critical patent/WO1998055217A8/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/34—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00628—Controlling the composition of the reactive mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00823—Mixing elements
    • B01J2208/00831—Stationary elements
    • B01J2208/0084—Stationary elements inside the bed, e.g. baffles

Definitions

  • the present invention relates to a fluidized bed reactor for ammoxidation of hydrocarbons, and more particularly to a fluidized bed reactor in which an internal component capable of increasing gas-solid phase contact efficiency is installed near an upper part of a catalyst layer.
  • the gas dewatering absorption tower After removing the unreacted ammonia, the gas dewatering absorption tower absorbs all organic matters in the gas with low-temperature water.
  • the acrylonitrile recovery and refining process of the absorption liquid separates high-purity acrylonitrile, cyanuric acid, and crude acetonitrile.
  • acrylonitrile production process it is important to remove unreacted ammonia in the reaction gas with sulfuric acid in a neutralization column. Because acrylonitrile and cyanohydrin are easily polymerizable materials, they are easier to polymerize under neutral and slightly alkaline conditions. As a result, not only acrylonitrile and cyanuric acid products are lost, but also production equipment is polluted, and ammonium sulfate wastewater is produced.
  • composition of ammonium sulphate wastewater is very complex, and includes the following categories:
  • High polymer Since the pH of the circulating spray of the neutralization tower is controlled in the range of 2 to 7, there is a certain amount of reaction products, such as acrylonitrile, cyanic acid and acrolein, which polymerize to form high polymers. The polymerization loss is calculated based on the total production amount, 2-5% of acrylonitrile, 3 ⁇ 8% of cyanohydrin, and 40-80% of acrolein. It can be seen that the polymer content in ammonium sulfate wastewater is very high.
  • High-boiling matter The operating temperature of the neutralization tower is generally around, so The enoic acid is condensed and exists in the ammonium sulfate wastewater. Still others are high boiling point cyanohydrins produced by the condensation of carbonyl compounds with cyanic acid.
  • Low-boiling substances mainly acrylonitrile, acetonitrile, and cyanohydrin dissolved in ammonium sulphate sewage, the content of which is about 500 ⁇ 5000ppm depending on the temperature of the spray liquid.
  • Catalyst powder In the process of producing acrylonitrile in a fluidized bed reactor, the catalyst fine powder blown off the catalyst bed layer by the reaction gas is mostly recovered by the cyclone and returned to the bed layer. However, a small amount of fine catalyst powder was blown out of the reactor by the gas, and was washed away in the neutralization tower. The amount of catalyst blown out is about 0.2 to 0.7 kg per 1 ton of acrylonitrile produced.
  • ammonium sulfate wastewater it is very difficult to crystallize ammonium sulfate from ammonium sulfate wastewater. If ammonium sulphate is not recovered and burned, it will generate secondary pollution of the atmosphere caused by sulfur dioxide, and many countries do not allow direct emissions.
  • Another problem with the treatment of ammonium sulfate wastewater by the combustion method is that the combustion temperature needs to reach 850- ⁇ : before the cyanide in the wastewater can be burned, it consumes a large amount of fuel. Because the combustion gas contains sulfur dioxide, which corrodes the steel, it is also difficult to set up a waste heat boiler to recover heat. Direct venting of high-temperature gas also causes thermal pollution to the atmospheric environment.
  • the inventors have studied the basic process of synthesizing acrylonitrile in a fluidized bed reactor and found that the secondary reaction of propylene ammonia oxidation can eliminate unreacted ammonia in the reaction gas without adding any oxidizable organic matter.
  • the object of the present invention is to provide a fluidized bed ammonia reactor for the oxidation of hydrocarbons.
  • the reactor has the function of improving the ammonia conversion rate, thereby reducing the content of unreacted ammonia in the reaction gas. .
  • a hydrocarbon ammonia oxidation reactor an internal component installed in the upper part of a fluidized bed close to a catalyst layer to increase gas-solid phase contact efficiency.
  • the internal components in the above technical solution include a filler, a baffle, a screen, and the like. Internal components can be combined, Further reaction in the lean zone eliminates unreacted ammonia from the reaction gas.
  • the position of the internal components in the reactor starts from the surface of the catalyst fluidized layer in the reactor. If a baffle or screen is used, the next plate (net) should be below the surface of the catalyst and the depth should not be greater than the height of the fluidized bed. 20%.
  • the upper end is not larger than the entrance of the first-level cyclone, preferably at the Cyclone separator ash. If filler is used, its upper and lower ends are the same as above.
  • the filler used is made of sieve with 10 mesh or more mesh, its shape is round, cylindrical, square, rectangular or honeycomb, etc., the gap string is 20 ⁇ 80%, preferably 35% ⁇ 60%.
  • the packing can be piled up or discharged regularly in the reactor. Special methods can also be used, such as using springs to fix the filler so that it can vibrate under the action of the reactive gas stream to prevent the catalyst from being fixed to its surface.
  • the form of the baffle or screen used includes a perforated grid plate, a perforated plate, a perforated plate with a cone cap or a pyramidal cap, or a shutter type baffle.
  • the perforated plate can have many different shapes, such as rectangular, angular, round, or oval.
  • the porosity is 20-80%, preferably 35 ⁇ 65%.
  • the placement of the baffle or screen in the reactor can be level or inclined. The inclination should be greater than the angle of repose of the catalyst to prevent the catalyst from accumulating on its surface.
  • the spacing (L) of the baffles or screens of each layer can be the same or different, and the spacing can be between 0.2 and 2.0 L / D depending on the size of the inner diameter (D) of the reactor.
  • the present invention requires that the conversion of ammonia should be greater than 85%, preferably greater than 93%.
  • All olefin ammoxidation catalysts are suitable for the present invention, such as the catalyst described in CN / 021637C, but it is preferably a catalyst based on molybdenum oxide. If the catalyst has a higher conversion of ammonia, it is better.
  • the linear velocity of a fluidized bed reactor is related to the concentration of the catalyst in the dilute phase in the upper part of the reactor.
  • the linear velocity is required to be 0.5-0.8 m / s, preferably 0.6-0.75 m / s.
  • the temperature in the upper part of the reactor should be the same as or close to the temperature of the catalyst bed.
  • the reaction pressure depends on the activity of the catalyst used, and generally ranges from 0.05 to 0.2 mpa.
  • the present invention is the main part of an acrylonitrile process that does not produce ammonium sulfate.
  • the generated gas is cooled into a quench tower for cooling, and then the desorption tower absorbs all organic matter in the gas with low-temperature water.
  • the absorption liquid is used in the extraction tower to separate water from the acrylonitrile and acetonitrile.
  • the crude acrylonitrile distilled from the top of the tower contains cyanic acid and a small amount of water.
  • the present invention uses a secondary reaction carried out in the dilute phase of a fluidized bed reactor to eliminate unreacted ammonia in the reaction gas, but does not add any organic matter.
  • the reaction gas leaves the catalyst bed, in addition to the main by-products such as acrylonitrile, acetonitrile, acrolein, hydrocyanic acid, acrylic acid, carbon monoxide, and carbon dioxide, it also contains a small amount of unreacted propylene and ammonia.
  • the dilute phase is contacted with the catalyst for further reaction. Among them, unreacted ammonia reacts with by-product acrolein and residual propylene to form acrylonitrile, so it can also increase the yield of acrylonitrile and reduce the acrolein content. Profitable.
  • the fluidized-bed reactor of the present invention is completely applicable to the ammoxidation reactions of propane, propylene, isobutylene, and dimethylbenzene, and can be used not only for the modification of old equipment, but also for the development of new processes. '' For the ammoxidation process, it can enhance production, improve reaction efficiency, shorten the process flow, reduce environmental pollution, and have greater economic benefits.
  • Comparative Example 1 A catalyst consisting of CN 1021638 C Example 1 was used.
  • the fluidized bed reactor has an inner diameter of 38 mm and a height of about 2 m. Adding 550 g of catalyst, the fluidized layer of the catalyst is about 320 mm high.
  • the propylene conversion was 96.2%, the acrylonitrile yield was 80.1%, the acrylonitrile selectivity was 83.3%, and the ammonia conversion was 93%.
  • Example 1 The conditions were the same as those of Comparative Example 1, except that five multiwell plates were placed on the top of the reactor.
  • the height of the first piece from the air distribution board is 300 legs, and the height of the next four pieces is 350, 400, 450 and 500mm, respectively.
  • Multiwell plate has a pore diameter of 1 ⁇ 2m and a porosity of 40%.
  • the propylene conversion was 98.5%
  • the acrylonitrile yield was 81.7%
  • the acrylonitrile selectivity was 82.9%
  • the ammonia conversion was 96.2%.
  • Example 2 The conditions are the same as in Example 1, but 3 porous plates with the same pore size and opening ratio as those of Example 1 are added. The height of the first plate is unchanged, and the height of the second and third plates are 400 and 400, respectively. 500 wake up. Results The conversion of propylene was 97.8%, the acrylonitrile yield was 81.2%, the selectivity of acrylonitrile was 83.0%, and the ammonia conversion was 95.5%.
  • Example 3 The conditions were the same as in Example 2, but 8 porous plates with the same pore size and opening ratio as in Example 1 were added. The height of the first plate was unchanged, and the spacing between the next few plates was 30 strokes. The reaction result was a propylene conversion rate of 98. 8%, acrylonitrile single yield 81.7%, acrylonitrile selectivity 82.7%, ammonia conversion rate 96.5%.
  • Example 4 The conditions are the same as in Example 2, that is, three perforated plates are added, but the amount of catalyst added is 750 g, and the flow rate of the raw material mixed gas is increased to 6 liters / hour. Results The propylene conversion was 98.7%, the acrylonitrile yield was 81.8%, the selectivity of acrylonitrile was 82.9%, and the ammoniation rate was 97.5%.
  • Example 5 The conditions of Example 1 were used, but a 10 mesh, 6 ⁇ 6 leg stainless steel wire mesh cylindrical packing was charged into the reactor. The height of the bottom of the packing is 300mm from the air distribution plate, and the length is 20Qi. Results The propylene conversion was 98.8%, the acrylonitrile yield was 81.4%, the acrylonitrile selectivity was 82.4%, and the ammonia conversion was 97.2%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Description

烃类氨氧化流化床反应器
发明领域
本发明涉及烃类氨氧化流化床反应器， 特别是关于在靠近催化剂层 上部安装有可增加气固相接触效率的内部构件的流化床反应器。
背景技术
烃类氨氧化制不饱和腈生产是石油化学工业的一个重要课题， 其中 丙烯和异丁烯氨氧化制丙烯腈和甲基丙烯腈早已工业化， 烷烃的氨氧化 也正在开发之中。 但是存在一个共同问题， 即不饱和腈在碱性下是不稳 定的， 极易发生聚合。 因此无论何种氨氧化反应， 反应气体中的未反应 氨均需除去。 目前均采用硫酸急冷除去未反应氨。 此法将产生大量含腈 硫铵污水， 很难处理。 目前各国对三废处理要求很高， 因此解决副产硫 铵成为引人注目的问题。
以丙烯氨氧化制丙烯腈为例。 丙烯， 氨和空气通过流化床反应器氨 氧化生成主产品丙烯腈和副产品乙腈， 氰氢酸， 丙烯醛， 丙烯酸, 一氧 化碳和二氧化碳， 还有少量未反应丙烯和氨。 反应气体离开反应器后， 经冷却进入中和塔， 用硫酸水溶液吸收未反应氨生成硫铵。 由于反应气 体中部分水蒸汽也冷凝分出， 因此产生硫铵污水。 除去未反应氨后的气 体去水吸收塔， 用低温水将气体中全部有机物吸收下来。 吸收液去丙烯 腈回收精制工序分离出高纯度丙烯腈， 氰氢酸和粗乙腈。
在上述丙烯腈生产工艺中， 用硫酸在中和塔除去反应气体中的未反 应氨十分重要。 因为丙烯腈和氰氢酸均是易聚合的物料， 特别在中性和 微碱性条件下更易聚合。 因此不仅造成丙烯腈和氰氢酸产品的损失， 也 会对生产设备造成污染， 同时产生硫铵污水。
硫铵污水组成十分复杂， 大致包括以下几类：
1.高聚物： 由于中和塔循环喷淋液的 pH控制在 2 ~ 7范围， 因此有 一定量的反应产物， 如丙烯腈， 氰氢酸和丙烯醛发生聚合反应生成高聚 物. 各物料聚合损失量对总生成量计算， 丙烯腈 2 - 5 % , 氰氢酸为 3 ~ 8 % , 丙烯醛则高达 40 - 80 %， 可见硫铵污水中高聚物含量很高。 污水 中的高聚物还有一个特点， 即分子量分布很广， 一部分高聚物分子量较 小， 可溶于硫铵污水， 另一部分高聚物分子量较大， 成为不溶于水的黑 色固体， 这就为回收硫铵造成另一层困难。
2.高沸物： 中和塔搡作温度一般为 左右， 因此反应气体中的丙 烯酸被冷凝而存在于硫铵污水中。 还有一些是羰基化合物与氰氢酸缩合 产生的高沸点氰醇。
3.低沸物： 主要是溶解于硫铵污水中的丙烯腈， 乙腈和氰氢酸等， 其含量视喷淋液温度的不同， 大致在 500 ~ 5000ppm。
4.催化剂粉末： 在流化床反应器生产丙烯腈的过程中， 被反应气体 吹离催化剂床层的催化剂细粉， 绝大部分经旋风分离器回收并返回床 层。 但也有少量催化剂细粉被气体吹出反应器， 在中和塔被洗下。 催化 剂的吹出量以每生产 1吨丙烯腈计， 约为 0. 2 ~ 0. 7kg。
由以上说明可知， 从硫铵污水结晶硫铵十分困难。 如果不回收硫铵 而将其烧掉， 又会产生二氧化硫造成大气的二次污染， 许多国家不允许 直接排放。硫铵污水用燃烧法处理的另一问题是燃烧温度要求达到 850 - ιιοοχ:方能将污水中的氰化物烧掉， 因此要消耗大量燃料。 由于燃烧气 中含有二氧化硫对钢材有腐蚀， 设置废热锅炉回收热量也有困难， 高温 气体直接放空也对大气环境造成热污染。
综上所述， 丙烯腈生产中产生的硫铵污水造成很大问题， 已经严重 影响丙烯腈制造工业的发展。 因此开发不产生硫铵的丙烯腈生产工艺， 即所谓 "清洁工艺" 已引起国际上丙烯腈行业的极大重视。 该清洁工艺 的关键在于反应时能提高氨的转化率， 消除未反应氨。
消除未反应氨的基本方法有两个： 一是从催化剂着手， 提高催化剂 对氨的转化率， 另一方法是从氨氧化反应出发， 将丙烯氨氧化与消除未 反应氨两个反应分开进行.
提高丙烯氨氧化催化剂对氨的转化率有一定难度。 仅从氨化反应考 虑， 要求催化剂对氨的分解能力要小， 即采用较低的丙烯与氨的比例即 可得较高收率的丙烯腈。 如果催化剂对氨的分解能力强， 则氨的消耗将 上升是不经济的。 因此两种不同要求是互相矛盾。 但目前催化剂对氨的 转化率过低， 在不增加氨耗的前提下提高催化剂对氨的转化率到一定水 平也是值得关注的方向。 由于丙烯氨氧化时也生成一定量丙烯酸， 因此 并不需要使催化剂对氨的转化率达到 100 %， 如果达到 97 - 98 % , 基本 上也不加硫酸中和。 例如中国专利 96116456. 5 就是提高催化剂氨转化 率的实例。 本发明人认为： 从工厂长工期稳定生产考虑还应有其他措施 保证完全消除未反应氨。 因为一种催化剂对氨的分解能力与催化剂的新 旧程度有关， 反应器的操作条件也有影响。 工厂不可能保证搡作条件长 期不变。
利用丙烯氨氧化的二次反应除去未反应氨已有专利发表， US
5457223, US 5466857, JP 96— 27087 和 WO 9625391 报告在流化床反 应器中用钼铋铁系催化剂进行丙烯氨氧化合物丙烯腈， 在反应器上部稀 相送入甲醇， 乙腈或可被氧化的有机物， 与氨反应可生成氰氢酸， 同时 将氨除去。 在最佳条件下， 氨可被完全反应。 但是本发明人认为此方法 存在问题， 因为这些有机物与氨反应时需要氧气， 但反应器稀相气体中 残余氧很少， 因此催化剂将被过度还原。 其结果不仅丙烯腈单收会下降， 也将影响催化剂的稳定性。
W0 9623766 采用调节反应器进料的分子比， 使生成的丙烯酸等有 机酸与未反应氨的分子比为 0. 8 - 3. 0, 则未反应氨与有机酸化合生成相 应的铵盐而不需用硫酸。 此法的问题是生成有机酸的同时也会生成大量 不饱和羰基化合物， 不仅给丙烯腈的回收精制造成困难， 也会降低丙烯 腈单收.
发明概述
本发明人对流化床反应器合成丙烯腈的基本过程进行研究发现， 利 用丙烯氨氧化的二次反应， 不加任何可氧化的有机物也可消除反应气体 中的未反应氨。
为克服上述文献中存在的不足， 本发明的目的是提供一种烃类氨氧 化流化床从反应器， 该反应器具有能提高氨转化率的功能， 从而降低反 应气体中未反应氨的含量。
本发明的目的是通过以下的技术方案来实现的： 一种烃类氨氧化反 应器， 在流化床靠近催化剂层的上部安装可增加气固相接触效率的内部 构件.
上述技术方案中的内部构件包括填料、 挡板、 挡网等。 内部构件可 合，
Figure imgf000005_0001
的稀 区的 进一步反应， 消除反应气体的未反应氨。
发明详述
内部构件在反应器内的位置， 从反应器内催化剂流化层表面开始， 如果用挡板或挡网则最下一块板（网） 应在催化剂表面之下， 深度不大 于流化床层高度的 20 %。 最上端不大于一级旋风分离器入口处， 最好在 旋风分离器灰斗处。 如果用填料其上下端的位置与以上相同。
所用填料用 10 目以上筛网制成， 其形状为圆形， 圆筒形， 方形， 长方形或蜂巢形等， 空隙串为 20~ 80% , 最好为 35% ~ 60%。 填料在 反应器内可乱堆或有规则排放。 也可用特殊方法， 如用弹簧固定填料， 使其在反应气流作用下可振动防止催化剂固定在其表面。
所用挡板或挡网的形式包括多孔格子板， 多孔板， 具有圆锥帽或角 锥帽的多孔板， 或百页窗式挡板等。 多孔板的开孔型式可有多种不同形 状， 如长方形， 角形， 圆形或椭圆形等。 开孔率为 20- 80%， 最好为 35~ 65%。 挡板或挡网在反应器内的安放可成水平或有一定倾斜度。 倾斜度 应大于催化剂的休止角以防止催化剂堆积在其表面上。 各层挡板或挡网 的间距（ L)可以相同或不同， 间距视反应器内径（ D)大小可在 0.2~ 2.0 L/D之间。
由于氨在流化床催化剂层上部发生的二次反应， 因此也有热量产 生. 所以催化剂对氨的转化率不能过低， 防止反应器上部的温度过高。 本发明要求氨的转化率应大于 85%， 最好大于 93%。 所有烯烃氨氧化 催化剂均适用于本发明， 例如 CN/021637C 所述催化剂但最好为以氧化 鉬为主要成分的催化剂， 如果催化剂对氨有较高的转化率更佳.
流化床反应器的线速与反应器上部稀相中催化剂的浓度有关， 要求 线速为 0.5- 0.8米 /秒， 最好为 0.6- 0.75米 /秒。 反应器上部的温度 与催化剂床层温度应相同或接近。 反应压力决定于所用催化剂的活性， 一般在 0.05 ~ 0.2mpa.
本发明是不产生硫铵的丙烯腈工艺主要部分。 丙烯， 氨和空气通过 本发明的流化床反应器后， 生成气体经冷却进入急冷塔冷却， 再去吸收 塔用低温水将气体中全部有机物吸收下来。 吸收液去萃取塔用水为溶剂 将丙烯腈与乙腈分离。 由塔顶蒸出的粗丙烯腈含有氰氢酸和少量水， 再 经脱氰氢酸塔和脱水塔得高纯度丙烯腈产品，
本发明是利用在流化床反应器的稀相进行的二次反应消除反应气体 中的未反应氨， 但不加任何有机物。 反应气体离开催化剂床层后， 其中 除生成丙烯腈、 乙腈、 丙烯醛、 氢氰酸、 丙烯酸、 一氧化碳、 二氧化碳 等主副产物之外， 尚含有少量未反应的丙烯和氨， 在流化床的稀相与催 化剂接触进一步反应。 其中的未反应氨与副产的丙烯醛和残余丙烯反应 生成丙烯腈， 因此也可增加丙烯腈的产率和减少丙烯醛含量， 是十分有 利的。
由于反应气体离开催化剂层后并非均匀上升， 在流化床稀相加入内 部构件有利于使气体与催化剂均匀混合， 提高了其接触效率， 因而提高 了氨的转化率， 促成了反应气体中未反应氨含量的下降， 取得了很好的 效果。 本发明的流化床反应器完全适用于丙烷、 丙烯、 异丁烯和二甲笨 等的氨氧化反应， 不仅可用于旧有设备的改造， 亦可用于新工艺的开发。 ' 对氨氧化工艺来说， 可以强化生产， 提高反应效率， 缩短工艺流程， 减 少环境污染， 具有较大的经济效益， 下面通过实施例对本发明作进一步 阐述：
实施例
比较例 1。 用 CN 1021638 C例 1 组成的催化剂。 流化床反应器内 径 38mm, 高约 2m。 加入 550g催化剂， 催化剂流化层高约 320mm。 反应 温度 435X:, 反应压力 0.08mpa， 原料气配比为： 丙烯： 氨： 空气 = 1: 1.2： 9.8, 混合气流速 4.3升 /分。 结果丙烯转化率 96.2% , 丙烯腈单 收 80.1%， 丙烯腈选择性 83.3%， 氨转化率 93%。
实施例 1。 与比较例 1条件相同， 但在反应器上部加入 5块多孔板。 第 1块距空气分布板的高度为 300腿， 以后 4块高度分别为 350,400,450 和 500mm。 多孔板孔径 ½m， 开孔率 40%。 反应结果丙烯转化率 98.5%， 丙烯腈单收 81.7%, 丙烯腈选择性 82.9% , 氨转化率 96.2% .
实施例 2: 与实施例 1条件相同， 但加入 3块与实施例 1 多孔板孔 径和开孔率相同的多孔板， 第 1 块板高度不变， 第 2, 3 块板高度分别 为 400和 500醒。 结果丙烯转化 97.8% , 丙烯腈单收 81.2% , 丙烯腈 选择性 83.0 %， 氨转化率 95.5 %。
实施例 3。 与实施例 2条件相同， 但加入 8块与实施例 1 多孔板孔 径和开孔率相同的多孔板， 第 1块板高度不变， 以后几块间距均为 30画. 反应结果丙烯转化率 98， 8%， 丙烯腈单收 81.7% , 丙烯腈选择性 82.7 %, 氨转化率 96.5%.
实施例 4。 与实施例 2条件相同， 即加入 3块多孔板， 但催化剂加 入量 750g, 原料混合气流速增加到 6升 /小时。 结果丙烯转化率 98.7%， 丙烯腈单收 81.8%， 丙烯腈选择性 82.9% , 氨化率 97.5%。
实施例 5. 按实施例 1条件， 但反应器中加入 10 目， 6χ 6腿不锈 钢丝网圆筒形填料。 填料底部高度距空气分布板为 300mm， 长度 20Qi皿。 结果丙烯转化率 98.8%, 丙烯腈单收 81.4%， 丙烯腈选择性 82.4%， 氨转化率 97.2%。
从以上实例可见：
1.增加挡板或填料的内部构件的流化床反应器， 在保持丙烯腈单程 收率和选择性不变的情况下， 可使氨的转化率提高 4- 5% .
2.增加挡板（网）数目或填料高度， 以及适当提高气体线速， 可使 氨转化率达到更佳的效果。

Claims

权 利 要 求
1.一种烃类氨氧化流化床反应器， 其特征在于靠近催化剂层的上部 安装有可增加气固相接触效率的内部构件。
2.根据权利要求 1所述烃类氨氧化流化床反应器， 其特征在于内部 构件， 包括： 填料， 挡板， 挡网等装置。
3.根据权利要求 1所述烃类氨氧化流化床反应器， 其特征在于内部 构件的位置， 最下端在催化剂层表面之下， 深度不大于流化床层 高度的 20% , 最上端不大于一级旋风分离器进口高度。
4.根据权利要求 1 所述烃类流化床反应器， 其特征在于烃类为丙 烷、 丙烯、 异丁烯、 二甲苯。
PCT/CN1998/000094 1997-06-06 1998-06-05 A fluidized bed reactor for the ammoxidation of hydrocarbons WO1998055217A1 (en)

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EP98925385A EP1008382A4 (en) 1997-06-06 1998-06-05 FLUIDIZED LAYER REACTOR FOR AMMOXYDATION OF HYDROCARBONS
BRPI9810414-4A BR9810414B1 (pt) 1997-06-06 1998-06-05 processo para remoção de amÈnia não reagida de um efluente de um leito de catalisador usado em uma reação de amoxidação de hidrocarboneto.
JP50123099A JP4047938B2 (ja) 1997-06-06 1998-06-05 炭化水素のアンモ酸化のための流動層反応器

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BR9810414A (pt) 2000-10-17
EP1008382A4 (en) 2001-10-10
TW466222B (en) 2001-12-01
JP4047938B2 (ja) 2008-02-13
ZA984866B (en) 1999-01-04
CN1055916C (zh) 2000-08-30
BR9810414B1 (pt) 2009-12-01
CN1201783A (zh) 1998-12-16

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