CHLOROBENZENE PHIL. CORP. PROCESS SELECTION Production of monochlorobenzene (MCB) can be done in many ways. Selection of the appropriate process is very critical because all of the subsequent works (material and energy balances, equipment and instrumentation designs, etc.) depends upon the evaluation of the alternative processes. After the initial feasibility and market evaluation, the evaluation of alternative processes must be also considered to determine the most economical for the chlorobenzene manufacture. There are several processes for the manufacture of MCB but the most common are the direct chlorination of benzene and the Raschig process. Direct chlorination of benzene can be done with or without a catalyst. The comparative analysis of the direct chlorination between with or without catalyst is summarized below together with the Raschig process. Process 1: Production of Chlorobenzene using Raschig Process In the Raschig process, benzene is chlorinated by chlorine that has been produced in situ in the reactor by the catalytic oxidation of hydrogen chloride. A pre-heated mixture of benzene vapor, air, steam and HCI at ordinary pressure is brought into contact at 220°C - 260°C with catalysts of copper oxide. 2% of the total benzene combusts, giving rise to about one quarter of the total heat output of the process. Due to this, carbon deposition may be possible especially with a rise in temperature. Chlorobenzene mixtures behave in distillation as ideal solutions. In a continuous train, heat may be conserved by using condensers from some units as the reboilers for others thereby, saving process energy. HCI is a constant by-product in the manufacture of chlorobenzenes. It is usually recovered by passing the gas stream through a scrubber tower over which a reactor mixture containing chlorination catalyst is circulated. This removes any unreacted chlorine that may have passed through the reactors. The HCI is then passed through one or more scrubbing towers in which high boiling chlorobenzenes are used as the solvent to remove the organic content. The absorbent in the final tower is refrigerated to the lowest possible temperature. PROCESS SELECTION...1 “This study source was downloaded by 100000780S03673 from CouseHero com on 04-07-2021 23:08:29 GMT 05-00, pstwwcoursehero com file28990220/P ROCESS.SELECTION-vIdoexCHLOROBENZENE PHIL. CORP. co Se Ge Of preven a, sane Fig. 1: Production of Chlorobenzene using Raschig Process Process 2: Production of Chlorobenzene via Direct Chlorination (without catalyst) The continuous process is most often used because it produces high yields from 90 to 95 percent MCB and small amounts of DCB isomers. It is not possible by selecting catalyst conditions or by modifying process parameters to prevent the formation of DCBs. Basic operations that may be used in the continuous production of MCB are shown in Figure 1-2. The process begins with an externally cooled cast iron or steel vessels. Chlorine is supplied into the vessel through suitably positioned inlets to maintain a large benzene-to-chorine reaction at all points along the reaction stream. The temperature is held between 20°C to 40°C (68°F to 104°F) to minimize the production of DCBs which form at higher temperatures. Dry benzene and dried recycled benzene are introduced into the reactor, which produces an overhead gas. The gas stream (containing HCI, unreacted chlorine, inert gases from the chlorine feed, benzene, and other VOCs) is sent to an organic absorber where benzene and other VOCs are removed. The bottoms from the organic absorber flow to the HCI stripper for recovery of HCI. The overhead gas is sent to HCI absorption. Byproduct hydrogen chloride is then removed in the HCI absorber where it is saturated by washing with a refrigerated solvent (e.g., o-dichlorobenzene) or low vapor pressure oil, and then recovered in wash towers as commercially usable hydrochloric acid Following chlorination, the crude chlorobenzene (mixture of MCB and DCB) is neutralized with dilute sodium hydroxide (10-25% NaOH) forming a PROCESS SELECTION...2 ‘This study source was downloaded by 100000780S03673 from CouseHerocom on 04-07-2021 23:08:29 GMT 05-00, tpslnn: course. comie'28990220/P ROCESS-SELECTION-¥ doeCHLOROBENZENE PHIL. CORP. sludge which must be separated with the supernatant. The sludge contains dichlorobenzenes which are separated by distillation. Crude reaction liquid product enters the crude chlorobenzene distillation column which produces overheads containing most of the chlorobenzenes, unreacted benzene, and some HCI, and a bottom stream from which catalyst and other byproducts are separated and processed for reuse. The overheads pass through an HCI stripper and into a benzene recovery column. Part of the subsequent benzene-free stream is returned to the organic absorber while the remainder enters the MCB distillation column. The overhead MCB distillation product is then stored while the bottom stream containing DCB and TCB isomers is processed. Although in most cases, isomer separation processing is conducted simultaneously with MCB production. Fig. 2: Production of Chlorobenzene via Direct Chlorination without catalyst Process 3: Production of Chlorobenzene via Direct Chlorination (with catalyst) Liquid benzene (which must contain less than 30 ppm by weight of water) is fed into a reactor system consisting of two continuous stirred tanks operating in series at 2.4 bar. Gaseous chlorine is fed in parallel to both tanks. Ferric chloride acts as a catalyst, and is produced in situ by the action PROCESS SELECTION...3 ‘This study source was downloaded by 100000780S03673 from CouseHerocom on 04-07-2021 23:08:29 GMT 05-00, hpslnn:coursher.comie'28990220/P ROCESS-SELECTION-¥ doeCHLOROBENZENE PHIL. CORP. of hydrogen chloride on mild steel. Cooling is required to maintain the operating temperature at 328 K. The hydrogen chloride gas leaving the reactors is first cooled to condense most of the organic impurities. It then passes to an activated carbon adsorber where the final traces of impurity are removed before it leaves the plant for use elsewhere. ay mn Tee ts @ came en Fig. 3: Process Flow Diagram of Production of Chlorobenzene via Direct Chlorination with Catalysts The crude chlorobenzene stream leaving the reactor is washed with NaOH solution (20 wt%; maintained slightly alkaline to protect downstream equipment from corrosion) in a pre-neutralizer. The product stream is free of HCl. The product is fed to a Benzene Recovery Column, which is a distillation column. Here the bottoms are almost 100% pure chlorobenzene. The tops contain 99% by weight of benzene and 1% chlorobenzene and all of the benzene is recycled to the benzene storage via a purifier. From the purifier the monochlorobenzene is sent to the refrigeration system. The bottoms from the Benzene column contain monochlorobenzene and dichlorobenzene. This is fed to the chlorobenzene column, which is again a distillation column. This may be operated at a pressure ranging from 3 -7 Ib/in? abs. The temperature in the chlorobenzene column may be between 100-120°C. Monochlorobenzene is the overhead distillate product of a purity of 99%. Dichlorobenzene is the bottom residue product of a purity of 97%. PROCESS SELECTION...4 ‘This study source was downloaded by 100000780S03673 from CouseHero com on 04-07-2021 23:08:29 GMT-05-00, hpslnw:coursher.comie!28990220/P ROCESS-SELECTION-¥ doeCHLOROBENZENE PHIL. CORP. The reactions involved in the process are as follows: 1.G,Hg+Cl, + CH.CI+HCl 2.C,H,CI+Cl, > CH,Cl,+HCl Dichlorobenzene is assumed to be a para-isomer. Formation of trichloro- isomers is neglected. EVALUATION OF THE PROCESS Shown below is a tabulated summary of the characteristics of each of the three processes in the manufacturing of chlorobenzene. Process #1: Process #2: Process #3: could not sustain demand Chlorobenzene | Chlorobenzen | Chlorobenzene Production using | e Production | Production via Raschig Process Direct Chlorination (without (without catalyst) catalyst) Availability of Raw * Benzene * Benzene * Benzene Materials (liquid) (liquid) (liquid) Used * Hydrochloric * Chlorine * Chlorine acid gas gas Refineries in the Philippines sell benzene as Refineries in the petroleum by- Refineries in | Philippines sell product, the Philippines benzene as Hydrochloric acid is _| Sel! benzene as petroleum by- available inthe | Petroleum by- bees Philippines mostly Product. Chlorine gas can were being imported | Chlorine gas can | be imported due to few be imported from adjacent hydrochloric plant | from adjacent _| countries, operating which —_| countries ‘This study source was downloaded by 100000780S03673 from CouseHrocom on 04-07-2021 23:08:29 GMT 05-00, PROCESS SELECTION... hpslnn:coursher.comie'28990220/P ROCESS-SELECTION-¥ doeCHLOROBENZENE PHIL. CORP. + Benzene * Benzene 1 * So (99%) (99%) Materials 6 + Chlorine + Chlorine used in + Hydrochloric 5 0% used in aye toa) gas (99%) gas (99%) . dato uc CyHytCl, CoH CoHetHCl*30,- CH) 6 wach, =Cytty Reactions C.H,CeCh =, Involved | C,H,Cl+Cl,~C,H,Cl|_ C,H,Cl+Ch, = C, C,H,Cl#3Cl, + 6C+6F Novo 24 22 v7 Equipment The raw materials are} The raw The raw less costly compared | materials are | materials are Raw to other processes, high cost high cost Materials because of the | | because of its | because of its Cost availability of purity and purity and hydrochloric acid in| purchase will | purchase will be the Philippines be costly. costly. Equipment Cost - - Moderate cost | Moderate cost High cost equipment for the for the due to the vapour equipment equipment Phase chlorination | since most of since most of process. the operations | the operations The addition of are at low are at low catalytic reactor for pressure. pressure oxidation of HCI Additional increases the equipment are equipment cost due ‘added for ‘This study source was downloaded by 100000780S03673 from CouseHero com on 04-07-2021 23:08:29 GMT-05-00, PROCESS SELECTION...6 tpsln: course. comie'28990220/P ROCESS-SELECTION-¥ doeCHLOROBENZENE PHIL. CORP. Product Percentage Yield waste to the monitoring of treatment catalysts. which increases costing. 80% 90% 95% Produces lower yield because the high temperature greatly favours high combustion rates of benzene and the reaction may become uncontrollable. Produces lower yield compared to the one with catalysts but recycled streams maximize the production. Produces higher yield because of the purity of raw materials and recycled stream in the process in order to maximize the consumption of raw materials. By-product Impurities are produced by the reaction compared to other processes (Yield = 20%). Yield of the by- product varies ‘on the ratio of the raw materials Yield of the by- product varies on the ratio of the raw materials Advantages The process is very efficient due to the recycle streams and material recovery. Yield for the by- product is small. Direct chlorination without catalyst is commonly used for the production of phenol. Since the chlorination of benzene is carried out in liquid phase | is small making and in the moderate concentration of temperature _| the impurities Beside from the operation at moderate conditions, direct chlorination with catalyst gives the highest yield of MCB. Due to this, yield of HCI ‘This study source was downloaded by 100000780S03673 from CouseHero com on 04-07-2021 23:08:29 GMT 05-00, PROCESS SELECTION...7 hupsln: course. comie'28990220/P ROCESS-SELECTION-¥ doeCHLOROBENZENE PHIL. CORP. and pressure, the control and monitoring of the operation is easy. Maintenance for the equipment is low cost because of the absence of catalyst. Direct chlorination without catalyst produces more DCB compared to chlorination with catalyst. Raschig process is less recommended because of the vapour chlorination. High temperature causes favours the | Yield for HCl is Disadvanta_Sombustion ofthe | TENting ges mene tne ee impurities for the crude deposition in the reactor. Due to this, heat output on the process increases which may be uncontrollable. chlorobenzene higher. Sludge formation is present due to the treatment of dissolved HCI with caustic solution. lesser. Less waste is produced and recycles and material recovery maximizes the production making the plant efficient. Maintenance for the equipment increases the equipment costing especially in the reactor. Storage for HCI adds handling and monitoring but modification of the process can make it feasible. ‘This study source was downloaded by 100000780S03673 from CouseHero com on 04-07-2021 23:08:29 GMT-05-00, PROCESS SELECTION...8 hupsln: course. comie'28990220/P ROCESS-SELECTION-¥ doe