Acetic production capacities

Acetals are produced by Asahi Chemical (homopolymer Tenac, copolymer Tenac-C, and conductive copolymer Lynex-T ), BASF (copolymer Ultraform ), DuPont (homopolymer Delrin ), Mitsubishi Gas Chemical (copolymer lupital ). Polyplastics (copolymer Duracon in Asia) and a joint venture between Ticona and Daicel Chemical Industries, Ticona/Celanese AG (copolymer Celcon and Hostaform in Europe). Mitsubishi Gas Chemical, Polyplastics, and Ticona are (jointly, directly, or through affiliates) increasing acetal production capacity in the Asia/Pacific area, with a new 60,(XX) metric ton/year plant to be completed in 2004 in Nantong, Jiangsu province, north of Shanghai. ... 

Acetic anhydtide [108-24-7] (CH2C0)20, is a mobile, colorless liquid that has an acrid odor and is a more pierciag lacrimator than acetic acid [64-19-7]. It is the largest commercially produced carboxyUc acid anhydride U.S. production capacity is over 900,000 t yearly. Its chief iadustrial appHcation is for acetylation reactions it is also used ia many other appHcations ia organic synthesis, and it has some utility as a solvent ia chemical analysis. 

Fig. 1. U.S. production, capacity, and price of vinyl acetate, where A shows total capacity B, total production and C, hst price.

This process may be competitive with butane oxidation (see Hydrocarbon oxidation) which produces a spectmm of products (138), but neither process is competitive with the process from synthesis gas practiced by Monsanto (139) and BASF (140) which have been used in 90% of the new acetic acid capacity added since 1975. 

Acetic acid is an important bulk commodity chemical, with world annual production capacity of ca. 7 million tonnes. The principal use (ca. 40%) of acetic acid is in the manufacture of vinyl acetate, a monomer of great importance in the polymer industry. A variety of other acetate esters are also... 

In 1970, the first rhodium-based acetic acid production unit went on stream in Texas City, with an annual capacity of 150 000 tons. Since that time, the Monsanto process has formed the basis for most new capacities such that, in 1991, it was responsible for about 55% of the total acetic acid capacity worldwide. In 1986, B.P. Chemicals acquired the exclusive licensing rights to the Monsanto process, and 10 years later announced its own carbonylation iridium/ruthenium/iodide system [7, 8] (Cativa ). Details of this process, from the viewpoint of its reactivity and mechanism, are provided later in this chapter. A comparison will also be made between the iridium- and rhodium-based processes. Notably, as the iridium system is more stable than its rhodium counterpart, a lower water content can be adopted which, in turn, leads to higher reaction rates, a reduced formation of byproducts, and a better yield on CO. 

Coburn " synthesized 2,4,6-tris(picrylamino)-l,3,5-triazine (TPM) (190) from the reaction of aniline with cyanuric chloride followed by nitration of the product with mixed acid. Treatment of TPM (190) with acetic anhydride-nitric acid leads to Al-nitration and the isolation of the corresponding tris-nitramine. The high thermal stability of TPM (m.p. 316 °C) coupled with its facile synthesis and low sensitivity to impact has led to its large scale manufacture in the US by Hercules Inc. China has reported a low-cost synthetic route to TPM but this has a limited production capacity. 

Table 8.1 shows the stochastic model solution for the petrochemical system. The solution indicated the selection of 22 processes with a slightly different configuration and production capacities from the deterministic case, Table 4.2 in Chapter 4. For example, acetic acid was produced by direct oxidation of n-butylenes instead of the air oxidation of acetaldehyde. Furthermore, ethylene was produced by pyrolysis of ethane instead of steam cracking of ethane-propane (50-50 wt%). These changes, as well as the different production capacities obtained, illustrate the effect of the uncertainty in process yield, raw material and product prices, and lower product... 

This is one of the most important industrial oxidation processes. Terephthalic acid (TPA) is mostly used for the manufacture of polyester fibers, films and plastics, and its world production capacity reaches 8 Mt/year. Two major processes have been developed. The Amoco-Mid Century process produces terephthalic acid by the one-step oxidation of p-xylene in acetic acid, whereas the Dynamit Nobel process yields dimethyl terephthalate in several steps and in the absence of solvent.83,84,86... 

As seen from the above, conventional uses of methanol cover a wide range of products which in turn find application in a very broad cross-section of industrial and consumer goods. New end uses have continued to develop and spur the growth of methanol production. One such development is the Monsanto low pressure process that carbonylates methanol to acetic acid (6). Essentially all new acetic acid capacity now being installed is based on Monsanto technology. By 1981, eleven plants converting methanol to acetic acid are scheduled to be on stream. At capacity they will consume over 300 million gallons of methanol. 

Acetic Acid. The worldwide production of acetic acid was reported to be 15.7 billion lb in 1998. Acetic acid is a global product with about one third of production capacity now outside the United States, Western Europe, and Japan. The majority buildup is in Asia. In the future, the capacity in Asia will continue to increase substantially. 

Biopolymer Technologies (Biop) offers a starch-based material containing an additive consisting of a vinyl alcohol/vinyl acetate copolymer. In 2005, the company transferred production of its bioplastics from The Netherlands to Schwarzheide in Germany and invested 7m in a new plant there, increasing its production capacity to 10,000 tonnes per annum. The announcement followed the decision earlier in 2005 by BASF to produce its Ecoflex biodegradable plastic, one of the components of Biop s Biopar resins, at the Schwarzheide site. 

The Wacker process reached a maximum production capacity of 2.6 Mt/a worldwide in the mid 1970 s. The cause of the decline in the following years (1.8 Mt/a in 2003) was the increase in the manufacture of acetic acid (the most important product made from acetaldehyde) by the carbonylation of methanol. In future new processes for chemicals, such as acetic anhydride and alkylamines (which were also made from acetaldehyde) will probably further decrease its importance. With the growing use of syngas as feedstock, the one-step... 

In both processes the aqueous crude aldehyde is concentrated and byproducts are removed in a two-step distillation. Both processes give 94% yields of aldehyde, along with small amounts of 2-chloroethanol, ethyl chloride, acetic acid, chloroacetaldehydes and acetaldehyde condensation products. The Wack-er-Hoechst process currently accounts for 85% of the worldwide production capacity for acetaldehyde. 

Most vinyl acetate is converted into polyvinyl acetate (PVA) which is used in the manufacture of dispersions for paints and binders and as a raw material for paints. It is also copolymerized with vinyl chloride and ethylene and to a lesser extent with acrylic esters. A substantial proportion of vinyl acetate is converted into polyvinyl alcohol by saponification or transesterification of polyvinyl acetate. The main applications for polyvinyl alcohol are either as raw material for adhesives or for fibres. It is also employed in textile finishing and paper glueing, and as a dispersion agent (protective colloid). The world production capacity of PVA was 4.35 Mt/a in 2005, of which 2.1 Mt were converted into polyvinyl alcohol. 

Acetic acid is one of the major commodity chemicals, with a current world production capacity of ca. 9 Mt/a. It has long been a mainstay of the organic chemicals industry, its manufacture increasing in sophistication and selectivity over the years. From being a simple agrochemical made in small quantitites as a foodstulf additive it has become a major bulk chemical with many important downstream applications (Box 2). 

Table 4 Production Capacities and Trade Names for Acetal Copolymers...

Acetic acid is a key commodity building block [1], Its most important derivative, vinyl acetate monomer, is the largest and fastest growing outlet for acetic acid. It accounts for an estimated 40 % of the total global acetic acid consumption. The majority of the remaining worldwide acetic acid production is used to manufacture other acetate esters (i.e., cellulose acetates from acetic anhydride and ethyl, propyl, and butyl esters) and monoehloroacetic acid. Acetic acid is also used as a solvent in the manufacture of terephthalic acid [2] (cf. Section 2.8.1.2). Since Monsanto commercially introduced the rhodium- catalyzed carbonylation process Monsanto process ) in 1970, over 90 % of all new acetic acid capacity worldwide is produced by this process [2], Currently, more than 50 % of the annual world acetic acid capacity of 7 million metric tons is derived from the methanol carbonylation process [2]. The low-pressure reaction conditions, the high catalyst activity, and exceptional product selectivity are key factors for the success of this process in the acetic acid industry [13]. 

The future of the commercial acetaldehyde processes mainly depends on the availability of cheap ethylene. Acetaldehyde has been replaced as a precursor for 2-ethylhexanol ( aldol route ) or acetic acid (via oxidation cf. Sections 2.1.2.1 and 2.4.4). New processes for the manufacture of acetic acid are the Monsanto process (carbonylation of methanol, cf. Section 2.1.2.1), the Showa Denko one-step gas-phase oxidation of ethylene with a Pd-heteropolyacid catalyst [75, 76], and Wacker butene oxidation [77]. Other outlets for acetaldehyde such as pentaerythritol and pyridines cannot fill the large world production capacities. Only the present low price of ethylene keeps the Wacker process still attractive. 

See osmosis. The pressure forces the water component of the solution through the membrane, thus effectively separating the components of the solution. Membranes used are cellulose acetate or graphitic oxide. This method is planned for use in a desalination plant proposed for the brackish waters of the lower Colorado River that is said to be the world s largest. It is also used in a Potomac River installation. (4) Flash distillation appears to be the most effective method so far developed for seawater desalination, accounting for about 90% of world production capacity. 

With the permission of the author [3], we borrow here data (Table 1) which indicates the production capacity of the major industrial processes using oxygen for functionalizing hydrocarbons. The production of acetic acid should be added to the list, although 60% of its 6.1 million t/year total world capacity (to reach 67% in the next future) is due to the Monsanto process (methanol carbonylation) [4]. Only the rest (2.4 million t/year) is produced by oxidation of butane or other alkanes or acetaldehyde or, for a small proportion, hy the Showa Denko process (oxidation of ethylene). 

The catalytic oxidation of acetaldehyde in the liquid phase to acetic add by air or oxygen is still widely applied, and accounts for about 40 per cent of installed worldwide production capacity. 

Table 8.5 gives the average commercial specifications of acetic add. Table 8.6 lists the main uses in per cent in 1984 for Western Europe, the United States and Japan, as well as the production, capacities and consumption for these three geographic areas. 

Until 1992, about 10% of the total acetic acid capacity in the United States was still based on oxidation of acetaldehyde. However, Eastman Chemical, the only domestic producer making acetic acid from acetaldehyde, shut down their unit and put it on standby at that time. As a result, all U.S. production is now by carbonylation of methanol. Some large European producers, such as BP Chemicals, are still using naphtha oxidation for acetic acid, but the amount made by acetaldehyde oxidation is nominal. 

Acetic Acid Demand. The production capacity for acetic acid by each major process is illustrated in Table 4 [10]. Table 4 shows that methanol carbonylation has nearly replaced oxidation processes for acetic acid production in the United States. Carbonylation accounted for less than 20% of total capacity in 1978 and more than 75% in 1994. The same trend has occurred outside of the United States. In 1978, carbonylation was less than 10% of worldwide capacity and today amounts to about 50%. 

Pd-catalyzed acetoxylation of ethylene with acetic acid and Oj accounts for approximately 80% of todays vinyl acetate production [1]. Vinyl acetate has a worldwide production capacity of about 6 million tons/year (2007) and is used to prepare a number of important polymers (e.g., PVA, EVA, PVCA). 

---