Vinyl acetate Celanese process

A. Hagemeyer, H. Werner, U. Dingerdissen, K. Kuhlein, G. Dambeck, G. Geiss, A. Rutsch, and S. Weidlich, Catalysts for the gas-phase oxidation of ethylene and acetic acid to vinyl acetate, a process for producing them and their use, US Patent 6 849 243, assigned to Celanese Chemicals Europe GmbH (DE), February 1, 2005. 

In the United States, Celanese has obtained a license from Bayer to expand their vinyl acetate production. In addition, National Distillers has developed an alternative vapor-phase process and will use it in a new plant nearing completion. The adoption by Celanese of the Bayer vapor-phase process has led to patent infringement litigation among National Distillers, Celanese, and Bayer (6). 

The industrial process for the vapor-phase manufacture of vinyl acetate monomer is quite common (Daniels, 1989) and utilizes widely available raw materials. Vinyl acetate is used chiefly as a monomer to make polyvinyl acetate and other copolymers. Hoechst-Celanese, Union Carbide, and Quantum Chemical are reported U.S. manufacturers. DuPont also currently operates a vinyl acetate process at its plant in LaPorte, Texas. To protect any proprietary DuPont information, all of the physical property and kinetic data, process flowsheet information, and modeling formulation in the published paper come from sources... 

The liquid phase processes resembled Wacker-Hoechst s acetaldehyde process, i.e., acetic acid solutions of PdCl2 and CuCl2 are used as catalysts. The water produced from the oxidation of Cu(I) to Cu(II) (Figure 27) forms acetaldehyde in a secondary reaction with ethylene. The ratio of acetaldehyde to vinyl acetate can be regulated by changing the operating conditions. The reaction takes place at 110-130°C and 30-40 bar. The vinyl acetate selectivity reaches 93% (based on acetic acid). The net selectivity to acetaldehyde and vinyl acetate is about 83% (based on ethylene), the by-products being CO2, formic acid, oxalic acid, butene and chlorinated compounds. The reaction solution is very corrosive, so that titanium must be used for many plant components. After a few years of operation, in 1969-1970 both ICI and Celanese shut down their plants due to corrosion and economic problems. 

A recent study indicates that if the Wacker process proves to be substantially cheaper than the acetylene route, no more vinyl acetate plants will be built in the United States, based on the latter process (38). Table XV gives estimated production costs for manufacturing vinyl acetate. Several companies are building or have already built plants to manufacture vinyl acetate from ethylene. These include Distillers Co., Ltd., British Celanese, Imperial Chemical Industries, and Celanese Corp., to name only a few. 

The first new process was introduced by Celanese in the late 1950 s. The Celanese vinyl acetate process took advantage of the equilibria ... 

In 1960, quickly after the introduction of the Celanese process, Wacker-Chemie commercialized a liquid phase vinyl acetate process which represented and extension of its earlier acetaldehyde process wherein acetic acid was simply substituted for water. (See equation [19]. This chemical transformation is also referred to as oxidative acetoxylation.) As shown in Figure 2, wherein R=Ac, the liquid phase oxidative acetoxylation of ethylene utilized the same catalytic cycle as the Wacker-Chemie acetaldehyde process. 

We will begin with the carbonylation of Mel which in situ is generated from MeOH for acetic acid production because of its industrial importance. Acetic acid is an important chemical commodity with a wide range of appUcations in organic chemistry. In organic synthesis, acetic acid is mainly used as a raw material for vinyl acetate monomers and acetic anhydride synthesis, as well as a solvent for producing terephthalic acid from xylene via the oxidation process. In 1998 the world s capacity of acetic acid production was approximately 7.8 milUon tons, of which more than 50 % were produced by BP-Amoco and Celanese. 

Johnston, V., Chen, L., Zink, J., et al. (2009). Worldwide Patent 2010056299Al, Integrated Process for the Production of Vinyl Acetate from Acetic Acid via Ethylene (Celanese International Corporation, USA.). 

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