Propylene oxide chlorohydrin route

There have been a number of cell designs tested for this reaction. Undivided cells using sodium bromide electrolyte have been tried (see, for example. Ref. 29). These have had electrode shapes for in-ceU propylene absorption into the electrolyte. The chief advantages of the electrochemical route to propylene oxide are elimination of the need for chlorine and lime, as well as avoidance of calcium chloride disposal (see Calcium compounds, calcium CHLORIDE Lime and limestone). An indirect electrochemical approach meeting these same objectives employs the chlorine produced at the anode of a membrane cell for preparing the propylene chlorohydrin external to the electrolysis system. The caustic made at the cathode is used to convert the chlorohydrin to propylene oxide, reforming a NaCl solution which is recycled. Attractive economics are claimed for this combined chlor-alkali electrolysis and propylene oxide manufacture (135). 

Due to the presence of a terminal double bond in 1-butene, oxidation of this isomer via a chlorohydrination route is similar to that used for propylene. 

Isobutylene oxide is produced in a way similar to propylene oxide and butylene oxide by a chlorohydrination route followed by reaction with Ca(OH)2. Direct catalytic liquid-phase oxidation using stoichiometric amounts of thallium acetate catalyst in aqueous acetic acid solution has been reported. An isobutylene oxide yield of 82% could be obtained. 

The process was commercially so superior to the chlorohydrin route, that by the 1970s, the new chemistry had completely replaced the old. Adding some momentum to this transition was the fact that the obsolete and abandoned chlorohydrin plants could be readily converted to propylene oxide plants. The silver bullet for that process has yet to be found. 

You have to talk about propylene oxide and propylene glycol after ethylene oxide and glycol. Its not that the chemical configurations are so similar (they are), or that the process chemistry is about the same (it is). The Fact is that much of the propylene oxide is now made in plants originally designed and constructed to produce EO, not PO. As you read in the last chapter, the chlorohydrin route to EO was abandoned by the 1970s in favor of direct oxidation. At the same time, the EO producers found that the old EO plants were suitable for the production of PO and certainly the cheapest hardware available to satisfy growing PO demands. 

Z. Why is the chlorohydrin route losing favor as the preferred route to propylene oxide ... 

The epoxidation of propylene to propylene oxide is a high-volume process, using about 10% of the propylene produced in the world via one of two processes [127]. The oldest technology is called the chlorohydrin process and uses propylene, chlorine and water as its feedstocks. Due to the environmental costs of chlorine and the development of the more-efficient direct epoxidation over Ti02/Si02 catalysts, new plants all use the hydroperoxide route. The disadvantage here is the co-production of stoichiometric amounts of styrene or butyl alcohol, which means that the process economics are dependent on finding markets not only for the product of interest, but also for the co-product The hydroperoxide route has been practiced commercially since 1979 to co-produce propylene oxide and styrene [128], so when TS-1 was developed, epoxidation was looked at extensively [129]. 

Another example of a famous organic chemical reaction being replaced by a catalytic process is furnished by the manufacture of ethylene oxide. For many years it was made by chlorohydrin formation followed by dehydrochlorination to the epoxide. Although the chlorohydrin route is still used to convert propylene to propylene oxide, a more efficient air epoxidation of ethylene is used and the chlorohydrin process for ethylene oxide manufacture has not been used since 1972. 

The direct oxidation of ethylene to EO by O2 has now replaced the chlorohydrin process entirely because it is cheaper and involves less byproducts, but propylene oxide (a monomer in polyurethanes) is still made by the chlorohydrin route. 

Chlorine is principally used to produce organic compounds. But, in many cases chlorine is used as a route to a final product that contains no chlorine. For instance propylene oxide has traditionally been manufactured by the chlorohydrin process. Modern technology permits abandoning this route in favor of direct oxidation, thus eliminating a need for chlorine. 

The direct oxidation of propylene on silver catalysts has been intensively investigated, but has failed to provide results with commercial potential. Selectivities are generally too low and the isolation of propylene oxide is complicated by the presence of many by-products. The best reported selectivities are in the range 50-60% for less than 9% propylene conversion. The relatively low selectivity arises from the high temperature necessary for the silver catalysts, the radical nature of molecular oxygen, as well as the allylic hydrogens in propylene. Thus alternative routes have been studied based on the use of oxidants able to act heterolytically under mild conditions. Hypochlorous acid (chlorine+water) and organic hydroperoxides fulfill these requirements and their use has led to the introduction of the chlorohydrin (Box 2) and the hydroperoxide processes, both currently employed commercially. 

Two process routes to propylene oxide are commercially practiced hydroperoxide formation and then use of this to oxidize propylene, and formation of propylene chlorohydrin followed by treatment with a base to form propylene oxide [22, 23]. It has not been possible to produce adequate yields of propylene oxide via the direct oxidation of propylene with air in the manner in which ethylene oxide is now produced, although attempts to come close to this continue [24]. 

To minimize hydrolysis of the propylene oxide (b.p. 34.2°C) as it is formed, it is flashed (rapidly removed) from the reactive lime slurry. Yields of propylene oxide are 75% or better based on propylene. The advantage of the chlorohydrin route to propylene oxide over the two hydroperoxidation processes is that it yields essentially a single product to market. The disadvantage is the large quantities of coproduced aqueous calcium chloride that has to be discarded safely. The small amount of by-product 1,2-dichloropropane may be pyrolyzed to allyl chloride, useful for the preparation of allyl monomers, allyl alcohol, and allylamines. Or it may be blended with 1,3-dichloropropene to produce an effective soil fumigant. 

Propylene oxide (PO) is an important chemical intermediate, which is mainly used in the manufacture of polyols, propylene glycols, and propylene glycol ethers [1]. The world annual production capacity of PO is about 7 million metric tons [2]. PO is mainly produced commercially by either the chlorohydrin (about 43%) or organic hydroperoxide processes. The chlorohydrin route produces large amounts of salt by-product, and new plants have used the hydroperoxide processes [3]. 

New routes to hydrogen peroxide new methods for direct synthesis of hydrogen peroxide (from hydrogen and oxygen) in a controlled, safe manner could provide a lower cost oxidant that reduces the use of chlorine. For example, in situ generation of hydrogen peroxide can be used to produce propylene oxide in place of the chlorohydrin route and... 

The Chlorohydrin process involves the reaction of propylene with chlorine and water to produce propylene chlorohydrin. The propylene chlorohydrin is then dehydrochlorinated with lime or caustic to yield propylene oxide and a salt by-product. The chemistry is very similar to the chlorohydrin route from ethylene to ethylene oxide which was eventually replaced by the direct oxidation process. There are two major problems with the chlorohydrin route which provided the incentive for developing an improved process. There is a large water effluent stream containing about 5-6% calcium chloride or 5-10% sodium chloride (depending on whether lime or caustic is used for dehydrochlorination) and trace amounts of chlorinated hydrocarbon by-products that must be treated before disposal. Treatment of these by-products is expensive. The only practical way to handle it is to use caustic so that sodium chloride is produced and then integrate the effluent stream with a caustic-chlorine plant so that it can be recycled to the caustic plant. This, however, is also expensive because recovery of sodium chloride from this relatively dilute stream has a high energy cost. 

Two processes are currently used for the production of propylene oxide. About 50% is produced by the chlorohydrin process and the other 50% by the peroxidation process. The chlorohydrin process is the older technology and it is slowly being replaced by the more economical and environmentally acceptable peroxidation route. There are environmental issues associated with the large aqueous by-product stream of calcium chloride and chlorinated hydrocarbon by-products from the chlorohydrin process. The only producers that will continue to operate chlorohydrin plants are highly integrated caustic-chlorine producers who have chlorine production facilities which can handle the calcium chloride by-product and chlorinated hydrocarbons [9]. 

The majority of propylene oxide is produced in the chlorohydrin process (CHPO), or co-product routes Baer, H., Bergamo, M., Forlin, A., Pottenger, L.H., and Lindner, J. (2012) Propylene oxide, in UUmann s Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH Co. KGaA, Weinheim. 

Until about 1970, the chlorohydrin route to propylene oxide predominated worldwide. 

Modern propylene oxide plants in which the chlorohydrin route is followed have reached a close integration of the chlorine cycle with a conventional chlor-alkali plant. 

The most widely used industrial routes to propylene oxide (PO) are based on the chlorohydrin process or hydroperoxide methods. Much attention has also been directed to processes performed in the presence of hydrogen peroxide in the liquid phase with a TS-1 molecular sieve as the catalyst, iron complexes accommodated in amorphous SBA-15 and MCM-41 modified with alkaline metal salts, and SBA-3 mesoporous molecular sieves doped with transition metal ions (Fe, V, Nb, and Ta). 

There are two major processes used to produce propylene oxide the chlorohydrin process and peroxidation of propylene. More than half of world production is by the chlorohydrin route. In this process, the first step is reaction of propylene with hypochlorous acid to obtain propylene chlorohydrin. 

Although many efforts have been made to develop a direct oxidation route to propylene oxide, none has been successful. The low yields of propylene oxide obtained render the route uneconomical the methyl group is readily oxidized so that substantial amounts of acrolein are also formed. However, hydroperoxidation processes have been developed and are becoming of increasing importance. In fact, it seems likely that these processes eventually will displace the chlorohydrin method. Two variations of the hydroperoxidation method are operated ... 

Propylene oxide was manufactured by the chlorohydrin route first during World War I in Germany by BASF and others. This route (below) involves reaction of propylene with hypochlorous acid followed by treatment of the resulting propylene chlorohydrin with a base such as caustic or lime. The products of the second reaction are propylene oxide and sodium or calcium chloride. Figure 22.26 is a diagram of the chlorohydrin process. 

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