Chemical reaction distillation

Gas-liquid processes that involve several components in each phase include many chemical reactions, distillation, and transfer of one or more species from a gas to a liquid (absorption or scrubbing) or vice versa (stripping). 

It is frequently convenient to carry out the steam distillation from the flask in which the chemical reaction has taken place losses due to... 

Boron trifluoride catalyst may be recovered by distillation, chemical reactions, or a combination of these methods. Ammonia or amines are frequently added to the spent catalyst to form stable coordination compounds that can be separated from the reaction products. Subsequent treatment with sulfuric acid releases boron trifluoride. An organic compound may be added that forms an adduct more stable than that formed by the desired product and boron trifluoride. In another procedure, a fluoride is added to the reaction products to precipitate the boron trifluoride which is then released by heating. Selective solvents may also be employed in recovery procedures (see Catalysts,regeneration). 

Petroleum refining, also called petroleum processing, is the recovery and/or generation of usable or salable fractions and products from cmde oil, either by distillation or by chemical reaction of the cmde oil constituents under the effects of heat and pressure. Synthetic cmde oil, produced from tar sand (oil sand) bitumen, and heavier oils are also used as feedstocks in some refineries. Heavy oil conversion (1), as practiced in many refineries, does not fall into the category of synthetic fuels (syncmde) production. In terms of Hquid fuels from coal and other carbonaceous feedstocks, such as oil shale (qv), the concept of a synthetic fuels industry has diminished over the past several years as being uneconomical in light of current petroleum prices. 

The three chemical reactions in the toluene—benzoic acid process are oxidation of toluene to form benzoic acid, oxidation of benzoic acid to form phenyl benzoate, and hydrolysis of phenyl benzoate to form phenol. A typical process consists of two continuous steps (13,14). In the first step, the oxidation of toluene to benzoic acid is achieved with air and cobalt salt catalyst at a temperature between 121 and 177°C. The reactor is operated at 206 kPa gauge (2.1 kg/cm g uge) and the catalyst concentration is between 0.1 and 0.3%. The reactor effluent is distilled and the purified benzoic acid is collected. The overall yield of this process is beheved to be about 68 mol % of toluene. 

These values, which match experience, suggest that distillation should be the preferred separation method for feed concentrations of 10—90%, but is probably a poor choice for feed concentrations of less than 1%. Techniques such as adsorption (qv), chemical reaction, and ion exchange (qv) ate chiefly used to remove impurity concentrations of <1%. 

Simultaneous heat and mass transfer also occurs in drying processes, chemical reaction steps, evaporation, crystallisation, and distillation. In all of these operations transfer rates are usually fixed empirically. The process can be evaluated using either the heat- or mass-transfer equations. However, if the process mechanism is to be fully understood, both the heat and mass transfer must be described. Where that has been done, improvements in the engineering of the process usually result (see Process energy conservation). 

Such a reaction is controlled by the rate of addition of the acid. The two-phase system is stirred throughout the reaction the heavy product layer is separated and washed thoroughly with water and alkaU before distillation (Fig. 3). The alkaU treatment is particularly important and serves not just to remove residual acidity but, more importantiy, to remove chemically any addition compounds that may have formed. The washwater must be maintained alkaline during this procedure. With the introduction of more than one bromine atom, this alkaU wash becomes more critical as there is a greater tendency for addition by-products to form in such reactions. Distillation of material containing residual addition compounds is ha2ardous, because traces of acid become self-catalytic, causing decomposition of the stiU contents and much acid gas evolution. Bromination of alkylthiophenes follows a similar pattern. 

Introduction Reactive distillation is a unit operation in which chemical reaction and distiUative separation are carried out simultaneously within a fractional distillation apparatus. Reactive distillation may be advantageous for liqiiid-phase reaction systems when the reaction must be carried out with a large excess of one or more of the reactants, when a reaction can be driven to completion by removal of one or more of the products as they are formed, or when the product recoveiy or by-product recycle scheme is complicated or macfe infeasible by azeotrope formation. 

The HETP of a packed-tower section, valid for either distillation or dilute-gas absorption and stripping svstems in which constant molal overflow can be assumed and in which no chemical reactions occur, is related to the height of one overall gas-phase mass-transfer unit Hqc by the equation... 

While the carbon dioxide/caiistic test method has become accepted, one should use the results with caution. The chemical reaction masks the effect of physical absorption, and the relative values in the table may not hold for other cases, especially distillation applications where much of the resistance to mass transfer is in the gas phase. Background on this combination of physical and chemical absorption may Be found earher in the present section, under Absorption with Chemical Reaction. ... 

All refining operations may be classed as either conversion processes or separation processes. In the former, the feed undergoes a chemical reaction such as cracking, polymerization, or desulfurization. Separation processes take advantage of differences in physical properties to split the feed into two or more different products. Distillation, the most common of all refinery separation processes, uses differences in boiling points to separate hydrocarbon mixtures. 

The SIMULAR, developed by Hazard Evaluation Laboratory Ltd., is a chemical reactor control and data acquisition system. It can also perform calorimetry measurements and be employed to investigate chemical reaction and unit operations such as mixing, blending, crystallization, and distillation. Ligure 12-24 shows a schematic detail of the SIMULAR, and Ligure 12-25 illustrates the SIMULAR reaction calorimeter with computer controlled solids addition. 

The natural world is one of eomplex mixtures petroleum may eontain 10 -10 eomponents, while it has been estimated that there are at least 150 000 different proteins in the human body. The separation methods necessary to cope with complexity of this kind are based on chromatography and electrophoresis, and it could be said that separation has been the science of the 20th century (1, 2). Indeed, separation science spans the century almost exactly. In the early 1900s, organic and natural product chemistry was dominated by synthesis and by structure determination by degradation, chemical reactions and elemental analysis distillation, liquid extraction, and especially crystallization were the separation methods available to organic chemists. 

Multicomponent distillations are more complicated than binary systems due primarily to the actual or potential involvement or interaction of one or more components of the multicomponent system on other components of the mixture. These interactions may be in the form of vapor-liquid equilibriums such as azeotrope formation, or chemical reaction, etc., any of which may affect the activity relations, and hence deviations from ideal relationships. For example, some systems are known to have two azeotrope combinations in the distillation column. Sometimes these, one or all, can be broken or changed in the vapor pressure relationships by addition of a third chemical or hydrocarbon. 

Commercial triethylamine (obtained from Eastman Organic Chemicals), was distilled from phosphorus pentoxide, and the pure amine (b.p. 86-90°) was stored under a nitrogen atmosphere. Since the presence of even a small excess of triethylamine is deleterious in these reactions, the quantities of this amine used should be measured by weight rather than volume. 

In processing, it is frequently necessary to separate a mixture into its components and, in a physical process, differences in a particular property are exploited as the basis for the separation process. Thus, fractional distillation depends on differences in volatility. gas absorption on differences in solubility of the gases in a selective absorbent and, similarly, liquid-liquid extraction is based on on the selectivity of an immiscible liquid solvent for one of the constituents. The rate at which the process takes place is dependent both on the driving force (concentration difference) and on the mass transfer resistance. In most of these applications, mass transfer takes place across a phase boundary where the concentrations on either side of the interface are related by the phase equilibrium relationship. Where a chemical reaction takes place during the course of the mass transfer process, the overall transfer rate depends on both the chemical kinetics of the reaction and on the mass transfer resistance, and it is important to understand the relative significance of these two factors in any practical application. 

Smart chemical reaction engineering can also solve the separation problem. Multifunctional reactors based on distillation or membrane separation wil gain importance in the future (see also Chapter 6). 

Balance with no chemical reaction. Estimate the steam and the cooling water required for the distillation column shown in the figure. 

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