PERP Program December 2000 Chem Systems' Process Evaluation/Research Planning program has published a new report, Epichlorohydrin

(99/00S11). Epichlorohydrin (epi) was first introduced in the mid-1930s by Shell using a process based on the high temperature chlorination of propylene to give allyl chloride and byproduct hydrogen chloride (HCl). At lower temperatures, the predominant reaction is the addition of chlorine to the double bond to give dichloropropane. Allyl chloride was then converted to glycerol chlorohydrin (dichloropropanol) by reaction with hypochlorous acid (HOCl). HOCl was obtained by reaction of chlorine and water, with byproduct HCl also formed. Dehydrohalogenation of the glycerol chlorohydrin with a base such as calcium hydroxide gave epichlorohydrin and byproduct calcium chloride. This classical chemistry, shown as Route 1 in the figure, is still in use today for the manufacture of epi. In the mid-1980s, Showa Denko commercialized a process based on the chlorination of allyl alcohol, as illustrated by Route 2 in the figure. Showa Denkos route to allyl alcohol is by oxidative acetoxylation of propylene to allyl acetate, followed by hydrolysis. Allyl alcohol is also obtainable from the isomerization of propylene oxide. Allyl alcohol is then chlorinated in aqueous HCl to give glycerol dichlorohydrin/dichloropropanol. This intermediate is subsequently dehydrochlorinated with base as previously described. Route 3 depicts a reaction sequence patented by Dow that goes through acrolein as an intermediate. Propylene is oxidized to acrolein in the first step, with some further oxidation to acrylic acid. In the second step, acrolein is chlorinated to 2,3-dichloropropanal. Subsequent hydrogenation of this aldehyde gives 2,3-dichloropropanol, which is then dehydrochlorinated with base as previously described. A patent to Solvay discloses the epoxidation of the double bond of allyl chloride using hydrogen peroxide at low temperature. Designated as Route 4, this path skirts the formation of dichloropropanol and goes directly from allyl chloride to epi. Acetone is the key intermediate in Route 5. According to an Asahi patent, acetone, produced from propylene via cumene hydroperoxidation and cleavage with phenol as coproduct, can be chlorinated to give dichloroacetone. Upon hydrogenation, as per a Mitsubishi patent, dichloropropanol is formed. Dehydrochlorination with base affords epi as discussed previously.

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Comparing the chlorine utilization of these routes, the disadvantage of Route 1 is seen in its theoretical consumption of 2 moles of chlorine for each mole of epichlorohydrin produced. Only 0.5 mole of chlorine is present in the final epi product. Routes 2 through 5 all have a theoretical consumption of 1 mole of chlorine per mole of epi, thus halving the chlorine consumption relative to Route 1 and reducing the amount of byproduct calcium chloride formed.

+O2 (via Cumene) ROUTE 1 O2

(via Acetate)

ROUTE 4
Cl2

H2O2
HOCl

[Solvay]
Ca(OH)2

C3H6

H2C CH CH2Cl Allyl Chloride (+ HCl)

Propylene O2

H2C CH CH2 HO Cl Cl

O H2C CH CH2Cl Epichlorohydrin (+ CaCl2 + H2O)

ROUTE 3 O O Cl2 H2 H2C CH CH H2C CH CH Acrolein Cl Cl [Dow] 2,3-Dichloropropanal ROUTE 2 H2C CHCH2OH [Showa Allyl Alcohol Denko] ROUTE 5 O H3C C CH3 + Cl2
Cl2 (in HCl)

Glycerol Dichlorohydrin (dichloropropanol)

Glycerol Dichlorohydrin (dichloropropanol)

Ca(OH)2

Epichlorohydrin (+ CaCl2 + H2O)

Glycerol Dichlorohydrin (dichloropropanol)

Ca(OH)2

Epichlorohydrin (+ CaCL2 + H2O)

H2O + Cl2

O H2 Glycerol Ca(OH)2 Epichlorohydrin H2C C CH2 [Asahi] [Mitsubishi] Dichlorohydrin (+ CaCL2 + H2O) Cl Cl Acetone Dichloroacetone Alt: Electrochemical (+ H2) Conversion [PPG] HOCl + HCl

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EPICHLOROHYDRIN PROCESS ROUTES

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