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Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid


Richard J. Sheehan, Amoco Research Center, Amoco Chemical Company, Naperville, Illinois, United States Introduction . . . . . . . . . . . . . . . . . Physical Properties . . . . . . . . . . . . Production . . . . . . . . . . . . . . . . . . Amoco Oxidation . . . . . . . . . . . . . Amoco Purication . . . . . . . . . . . . Multistage Oxidation . . . . . . . . . . . Dynamit-Nobel (Witten) Process . . . Esterication of Terephthalic Acid . . Hydrolysis of Dimethyl Terephthalate Alternative and Past Technologies . Environmental Protection . . . . . . . Quality Specications . . . . . . . . . . Storage and Transportation . . . . . Uses . . . . . . . . . . . . . . . . . . . . . Economic Aspects . . . . . . . . . . . . Toxicology and Occupational Health References . . . . . . . . . . . . . . . . . . . . . . . . .

1. 2. 3. 3.1. 3.2. 3.3. 3.4. 3.5. 3.6.

1 1 2 3 4 5 5 7 7

3.7. 4. 5. 6. 7. 8. 9. 10.

8 9 9 10 10 11 12 12

1. Introduction
Terephthalic acid [100-21-0], and isophthalic acid [121-91-5], both C8 H6 O4 , have the IUPAC names 1,4- and 1,3-benzenedicarboxylic acid. Dimethyl terephthalate [120-61-6 ], C10 H10 O4 , is also known as 1,4-benzenedicarboxylic acid dimethyl ester. The acids are produced by oxidation of the methyl groups on the corresponding p-xylene [106-42-3] or m-xylene [108-38-3]. After oxidation to a carboxylic acid, reaction with methanol [67-56-1] gives the methyl ester, dimethyl terephthalate. Terephthalic acid and dimethyl terephthalate are used to make saturated polyesters with aliphatic diols as the comonomer. Isophthalic acid is used as a feedstock for unsaturated polyesters as well as a comonomer in some saturated products. Structures are as follows:

were unsuitable to be spun into bers. Whineld and Dickson found that symmetrical aromatic diacids yield high-melting, crystalline, and ber-forming materials; poly(ethylene terephthalate) has since become the largest volume synthetic ber. Worldwide, terephthalic acid plus dimethyl terephthalate ranked about 25th in tonnage of all chemicals produced in 1992, and about tenth in terms of organic chemicals.

2. Physical Properties
Terephthalic acid, M r 166.13, is available acommercially as a free-owing powder composed of rounded crystals. It forms needles if recrystallized slowly. Vapor pressure is low: 0.097 kPa at 250 C, with sublimation at 402 C and atmospheric pressure. Melting has been reported at 427 C. Dimethyl terephthalate, M r 194.19, melts at 140.6 C and has sufcient vapor pressure for vacuum distillation. The molten form is preferred commercially, but akes and briquettes are available when long transport distances are required. Isophthalic acid, M r 166.13, melts at 348 C. Vapor pressure is 0.61 kPa at 250 C. Both terephthalic and isophthalic acid are stable, intractable compounds with low solubilities in most solvents; isophthalic acid is 2 5 times more soluble than terephthalic acid in the same solvent. Terephthalic acid solubilities > 10 g per 100 g solvent at room temperature occur with ammonium, potassium, or sodium hy-

Terephthalic acid came to prominence through the work of Whineld and Dickson in Britain around 1940 [4]. Earlier work by Carothers and coworkers in the United States established the feasibility of producing high molecular weight linear polyesters by reacting diacids with diols, but they used aliphatic diacids and diols. These made polyesters which
c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a26 193

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid


Table 2. Solubility of terephthalic acid and isophthalic acid (g/100 g solvent) 25 C 150 C 200 C 250 C 12.6 5.7

Table 1. Physical properties of terephthalic acid and isophthalic acid Terephthalic Isophthalic Crystal density, g/cm3 , 25 C Specic heat, J g1 K1 , to 100 C Heat of formation, kJ/mol Heat of combustion, kJ/mol, 25 C First dissociation constant Second dissociation constant Ignition temperature in air, C 1.58 1.20 816 3189 2.9104 3.5105 680 1.53 1.22 803 3203 2.4104 2.5105 700

Terephthalic acid solubility, g/100 g solvent Water 0.0017 0.24 1.7 Methanol 0.10 3.1 Acetic acid 0.013 0.38 1.5 Isophthalic acid solubility, g/100 g solvent Water 0.012 2.8 25.2 Methanol 1.06 8.1 Acetic acid 0.23 4.3 13.8

44.5

droxide, dimethylformamide, and dimethyl sulfoxide. Tetramethylurea and pyridine each dissolve ca. 7 g per 100 g. Dimethyl terephthalate is also stable, and more soluble in common organic solvents than the acids. Its main physical properties are a melting point below the point of degradation, and a vapor pressure which allows for purication by distillation. Other physical properties of terephthalic acid and isophthalic acid are listed in Tables 1 and 2. Some physical properties of dimethyl terephthalate are listed below:
Solubility, g/100 g solvent Methanol, 25 C Methanol, 60 C Ethyl acetate, 25 C Ethyl acetate, 60 C Trichloromethane, 25 C Trichloromethane, 60 C Benzene, 25 C Benzene, 60 C Toluene, 25 C Toluene, 60 C Dioxane, 25 C Dioxane, 60 C Vapor pressure, kPa 140 C 160 C 200 C 250 C Density at mp Viscosity, 180 C Viscosity, 200 C Specic heat, solid Specic heat, liquid Heat of fusion Heat of vaporization Heat of formation Heat of combustion, 25 C Flash point, DIN 51 758 1.0 5.7 3.5 16.0 10.0 23.0 2.0 14.0 4.3 10.4 7.5 26.5 1.58 2.62 10.88 42.60 1.07 g/cm3 0.0071 Pa s 0.0060 Pa s 1.55 J g1 K1 1.94 J g1 K1 159.1 kJ/Kg 355.5 kJ/Kg 740.2 kJ/mol 4660 kJ/mol 141 C

xylene is used for all isophthalic acid. Oxidation catalysts and conditions have been developed which give nearly quantitative oxidation of the methyl groups, leaving the benzene ring virtually untouched. These catalysts are combinations of cobalt, manganese, and bromine, or cobalt with a co-oxidant, e.g., acetaldehyde [75-07-0]. Oxygen is the oxidant in all processes. Acetic acid [64-19-7 ] is the reaction solvent in all but one process. Given these constant factors, there is only one industrial oxidation process, with different variations, two separate purication processes, and one process which intermixes oxidation and esterication steps.

3.1. Amoco Oxidation


About 70 % of the terephthalate feedstock used worldwide is produced with a catalyst system discovered by Scientic Design [5, 6]. Almost 100 % of new plants use this reaction. A separate company, Mid-Century Corporation, was established to market this technology, and subsequently purchased by Amoco Chemical. Amoco developed a commercial process, as did Mitsui Petrochemical, now Mitsui Sekka. Mitsui was an early licensee of Mid-Century. Both Amoco and Mitsui participate in joint-venture companies, and both have licensed the process. Licensees are distributed around the world, and some have relicensed the process to other companies. A soluble cobalt manganese bromine catalyst system is the heart of the process. This yields nearly quantitative oxidation of the pxylene methyl groups with small xylene losses [7]. Acetic acid is the solvent, and oxygen in compressed air is the oxidant. Various salts of cobalt and manganese can be used, and the bromine source can be HBr, NaBr, or

3. Production
p-Xylene is the feedstock for all terephthalic acid and dimethyl terephthalate production; m-

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid

Figure 1. Catalytic, liquid-phase oxidation of p-xylene to terephthalic acid by the Amoco process a) Oxidation reactor; b) Surge vessel; c) Filter; d) Dryer; e) Residue still; f) Dehydration column

tetrabromoethane [79-27-6 ] among others. The highly corrosive bromine acetic acid environment requires the use of titanium-lined equipment in some parts of the process. A feed mixture of p-xylene, acetic acid, and catalyst is continuously fed to the oxidation reactor (Fig. 1). The feed mixture also contains water, which is a byproduct of the reaction. The reactor is operated at 175 225 C and 1500 3000 kPa. Compressed air is added to the reactor in excess of stoichiometric requirements to provide measurable oxygen partial pressure and to achieve high p-xylene conversion. The reaction is highly exothermic, releasing 2108 J per kilogram p-xylene reacted. Water is also released. The reaction of 1 mol p-xylene with 3 mol dioxygen gives 1 mol terephthalic acid and 2 mol water. Only four hydrogen atoms, representing slightly over 2 wt % of the p-xylene molecule, are not incorporated in the terephthalic acid. Owing to the low solubility of terephthalic acid in the solvent, most of it precipitates as it forms. This yields a three-phase system: solid terephthalic acid crystals; solvent with some dissolved terephthalic acid; and vapor consisting of nitrogen, acetic acid, water, and a small amount of oxygen. The heat of reaction is removed by solvent evaporation. A residence time up to 2 h is used. Over 98 % of the p-xylene is reacted, and the yield to terephthalic acid is > 95 mol %. Small amounts of p-xylene and acetic acid are lost, owing to complete oxidation to carbon oxides, and impurities such as oxidation intermediates are present in reactor efuent. The excellent

yield and low solvent loss in a single reactor pass account for the near universal selection of this technology for new plants. The oxidation of the methyl groups occurs in steps, with two intermediates, p-toluic acid [99-94-5] and 4-formylbenzoic acid [619-66-9]. While 4-formylbenzoic acid is the IUPAC name of the intermediate, it is customarily referred to as 4-carboxybenzaldehyde (4-CBA).

4-Formylbenzoic acid is troublesome, owing to its structural similarity to terephthalic acid. It co-crystallizes with terephthalic acid and becomes trapped and inaccessible for completion of the oxidation. Up to 5000 ppm 4-formylbenzoic acid can be present, and this necessitates a purication step to make the terephthalic acid suitable as a feedstock for polyester production. The slurry is passed from the reactor to one or more surge vessels where the pressure is reduced. Solid terephthalic acid is then recovered by centrifugation or ltration, and the cake is dried and stored prior to purication. This is typically referred to as crude terephthalic acid, but is > 99 % pure. Vapor from the reactor is condensed in overhead heat exchangers, and the condensate is re-

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid

Figure 2. Purication of terephthalic acid by the Amoco process a) Slurry drum; b) Hydrogenation reactor; c) Crystallizers; d) Centrifuge; e) Dryer

uxed to the reactor. Steam is generated by the condensation and is used as a heating source in other parts of the process. Oxygen-depleted gas from the condensers is scrubbed to remove most uncondensed vapors. Similar to the reactor condensate, liquid from centrifuges or lters is sent to solvent recovery. Since the centrifugate or ltrate contains dissolved species, it is rst sent to a residue still. Vapor from the still and other vents from throughout the oxidation process are sent to a solvent dehydration tower. The tower removes the water formed in the reaction as the overhead stream, and the acetic acid from the tower bottom is combined with fresh acetic acid to make up for process losses, and returned to the process. Isophthalic acid is also produced by this process from m-xylene. Because isophthalic acid is several times more soluble than terephthalic acid, much less precipitates in the reactor. Consequently, isophthalic acid from this process contains much less 3-formylbenzoic acid, since it tends to stay in solution where complete oxidation can occur. Further purication was not carried out in the past, but a puried grade that is now being produced will become the standard.

3.2. Amoco Purication


The purication process developed by Amoco Chemical [8] and used on terephthalic acid from the Amoco oxidation process supplies over 60 % of the terephthalate feedstock for polyester production (Fig. 2). Crude terephthalic acid is unsuitable as a feedstock for polyester, primarily owing to the 4-formylbenzoic acid impurity concentration.

There are also yellow impurities and residual amounts of catalyst metals and bromine. The Amoco purication process removes 4formylbenzoic acid to < 25 ppm, and also gives a white powder from the slightly yellow feed. It is necessary to make all impurities accessible to reaction, so the crude terephthalic acid is slurried with water and heated until it dissolves entirely. A solution of at least 15 wt % is obtained, and this requires a temperature 260 C. The solution passes to a reactor where hydrogen is added and readily dissolves. The solution is contacted with a carbon-supported palladium catalyst. Reactor pressure is held above the vapor pressure of water to maintain a liquid phase. The 4-formylbenzoic acid is converted to ptoluic acid in the reactor, and some colored impurities are hydrogenated to colorless compounds. The reaction is highly selective; loss of terephthalic acid by carboxylic acid reduction or ring hydrogenation is < 1 %. After reaction, the solution passes to a series of crystallizers where the pressure is sequentially decreased [9]. This results in a stepped temperature reduction, and crystallization of the terephthalic acid. The more soluble p-toluic acid formed in the reactor, and other impurities, remain in the mother liquor. After leaving the nal crystallizer, the slurry undergoes centrifugation and/or ltration to yield a wet cake, and the cake is dried to give a free-owing terephthalic acid powder as the product. Over 98 wt % of the incoming terephthalic acid is recovered as puried product. As with the Amoco oxidation, this purication process is also used with isophthalic acid.

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid

3.3. Multistage Oxidation


Several companies, mostly in Japan [10, 11], have developed processes to reduce the 4formylbenzoic acid content to 200 300 ppm by more intensive oxidation. A separate purication step is eliminated; the concentration of 4formylbenzoic acid is low enough for the terephthalic acid to be suitable as a feedstock for some polyester products where high feedstock purity is not critical. The product is often called medium-purity terephthalic acid, and accounts for about 11 % of the terephthalic acid produced. Most of these processes also use the catalyst system discovered by Scientic Design. Most medium-purity terephthalic acid is produced by Mitsubishi Kasei and its licensees. They have named this product Q-PTA, and it has a typical 4-formylbenzoic acid level of ca. 290 ppm [10]. Mitsubishi has also developed a still more intensive oxidation process where the 4-formylbenzoic acid level is further reduced. The product is called S-QTA. The oxidation of p-xylene in acetic acid with a cobalt manganese bromine catalyst is carried out as in the Amoco oxidation. The slurry is heated to 235 290 C and oxidized further in another reactor. More catalyst can be added in addition to the temperature increase [12]. Heating gives increased terephthalic acid solubility, and as crystals dissolve, some 4formylbenzoic acid and colored impurities are released. Although the terephthalic acid is not completely soluble at the higher temperature, the crystals can digest. Digestion is a dynamic equilibrium process wherein crystals constantly dissolve and reform. This increases the release of 4-formylbenzoic acid into solution where oxidation can be completed. While the need for a separate purication process is eliminated, another reactor is needed in the oxidation process. Also, at higher temperature, acetic acid tends to be oxidized to a larger extent to carbon oxides and water [12]. The rest of the Mitsubishi process consists of solid liquid separation and drying to obtain the powdered product. Acetic acid must be dehydrated and recycled to the process. Eastman Chemical has also developed a medium-purity terephthalic acid product. The process does not employ manganese, only cobalt and bromine. Two oxidation stages are used,

both at 175 230 C [13]. Instead of heating between stages to obtain increased solubility, as performed by Mitsubishi, the contents of the rst reactor are sent to hydroclones where hot, fresh acetic acid displaces the mother liquor. Samarium may be added to the catalyst. A residence time up to 2 h with air addition provides sufcient digestion of the crystals to yield a 40 270 ppm level of 4-formylbenzoic acid [13]. Downstream recovery of the terephthalic acid crystals by solid liquid separation and drying must again be performed.

3.4. Dynamit-Nobel (Witten) Process


Most dimethyl terephthalate is made by a process rst developed by Chemische Werke Witten, with work also being done at a division of Standard Oil of California. Modications were made by Hercules and Dynamit-Nobel. H uls Troisdorf licensed the process with further modications [14]. Dimethyl terephthalate is formed in four steps. First, p-xylene is passed through an oxidation reactor, where p-toluic acid is formed. It then passes to an esterication reactor, the second step, where methanol is added to form methyl p-toluate [99-75-2]. The methyl ptoluate is isolated and returned to the oxidation reactor for oxidation to monomethyl terephthalate [1679-64-7 ], the third step, followed by the fourth step, esterication to dimethyl terephthalate. The sequence is as follows:

The process as licensed by H uls Troisdorf is illustrated in Figure 3. Fresh and recovered p-

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid

Figure 3. Production of dimethyl terephthalate by the Dynamit Nobel process a) Oxidation reactor; b) Esterier; c) Expansion vessel; d) Methanol recovery column; e, f) Methyl p-toluate and dimethyl terephthalate columns; g, j) Dissolvers; h, k) Crystallizers; i, l) Centrifuges

xylene, along with catalyst (mostly cobalt with some manganese) are combined with methyl ptoluate and fed to the liquid-phase oxidation reactor. Because bromine and acetic acid are not used, vessels lined with titanium or other expensive metals are not necessary. Oxygen supplied by compressed air is added at the bottom. Oxidation conditions are 140 180 C and 500 800 kPa. The heat generated by oxidation is removed by vapors of unreacted p-xylene and the water of reaction. Cooling coils in the reactor are used to generate steam. The steam and reactor vapors are condensed and combined to recover p-xylene for recycle. The oxidation efuent is then heated and sent to the esterication reactor, operated at 250 C and 2500 kPa. Excess vaporized methanol is sparged into the esterier, where the ptoluic acid and monomethyl terephthalate are converted noncatalytically to methyl p-toluate and dimethyl terephthalate, respectively. Overhead vapors from the esterication reactor are condensed and fed to a distillation system, where the water from the esterication is separated from methanol, which is recycled. The remainder of the process separates the dimethyl terephthalate from methanol and methyl p-toluate, which are recycled, and residue and wastewater, which go to waste treatment. The product from the esterier goes to an expansion vessel. Vapor from this vessel feeds a methanol recovery column, where the methanol overhead goes to methanol recovery, and the methyl p-toluate bottoms are recycled to the oxidation reactor. Liquid from the expansion ves-

sel feeds two vacuum distillation columns in series, which yield crude dimethyl terephthalate. The rst column recovers more methyl p-toluate overhead for recycle to oxidation, and the bottoms feeds the crude dimethyl terephthalate column, where the product is taken overhead. The bottoms from the dimethyl terephthalate column, containing heavy byproducts and catalyst metals, can be mixed with water from the oxidation, which dissolves the catalyst. The resulting slurry is centrifuged; the catalyst solution is recycled, and the cake is sent to disposal. The crude dimethyl terephthalate goes through two stages of crystallization. It is slurried with the methanol mother liquor from the second crystallization stage and dissolved by heating. Dimethyl terephthalate is crystallized from this solution on cooling, by ashing the methanol. The dimethyl terephthalate cake is separated by centrifugation, dissolved in fresh methanol, and crystallized in the same way. The wet dimethyl terephthalate cake can be melted and stored molten, or dried and aked. There is usually a distillation column after the second centrifuge for further purication. Mother liquor from the rst centrifugation is sent to the methanol recovery system. The centrifugation yields a cleaner mother liquor which is combined with methanol recovered from the melting operation for use in dissolving the crude dimethyl terephthalate entering the crystallization section. Side-streams from throughout the process are recycled to appropriate points to maximize yield and to minimize methanol and catalyst use.

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid

Figure 4. Esterication of terephthalic acid and separation of puried dimethyl terephthalate a) Esterier; b) o-Xylene scrubber; c) Methanol column; d) o-Xylene recovery column; e) 4-Formylbenzoic ester stripper; f) Purication column

3.5. Esterication of Terephthalic Acid


Terephthalic acid can be produced and, in a separate process, esteried with methanol to dimethyl terephthalate which is then puried by distillation (Fig. 4) [15, 16]. This process can be used on highly impure terephthalic acid, because of the purication achievable by distillation. Crude terephthalic acid and excess methanol are mixed and pumped to the esterication reactor. In this example, o-xylene [95-47-6 ] is used to enhance the subsequent separations. The terephthalic acid is rapidly esteried by the methanol at 250 300 C without catalysis, although a catalyst can be used. Methanol vapor carries dimethyl terephthalate and o-xylene from the reactor to a column where o-xylene is added to scrub out monomethyl terephthalate and return it to the reactor for completion of the esterication. The vapor contains the dimethyl terephthalate product as well as methanol, o-xylene, water from the esterication, and esteried impurities in the terephthalic acid feed. Several distillation steps are needed to separate out the dimethyl terephthalate and to process the separated streams for recovery of valuable components for recycle. The reactor overhead vapor rst goes to a methanol column where methanol is removed overhead, water and some methanol form a sidedraw, and the bottoms contain the dimethyl terephthalate, o-xylene, and impurities.

Next, in the o-xylene recovery column, dimethyl terephthalate purication is started; it operates at 10 20 kPa absolute so that a temperature of 200 230 C can be used. o-Xylene is removed overhead, the methyl esters of 4formylbenzoic acid and p-toluic acid are removed in the middle, and dimethyl terephthalate forms the bottoms. A 4-formylbenzoic acid stripping column follows, where the middle stream from the previous column is sent, so that 4-formylbenzoic ester can be removed overhead. Finally, the bottoms from both the o-xylene recovery column and the 4-formylbenzoic acid stripper are sent to a purication column, where the dimethyl terephthalate product is taken overhead. Methanol from the top of the methanol recovery column is sent to a purication column where the overhead contains low boilers, and the methanol from the bottoms is recycled. The methanol and water from the side-draw of the methanol recovery column are sent to a methanol dehydration column, where the water is removed and the dehydrated methanol recycled.

3.6. Hydrolysis of Dimethyl Terephthalate


High-purity terephthalic acid can be produced by hydrolysis of dimethyl terephthalate. Slightly over 2 % of terephthalate feedstock is produced by this route.

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid acetic acid solvent; the activator was 2-butanone [78-93-3]. After reaction, the crude terephthalic acid was leached by adding pure acetic acid and heating to achieve partial solubility; this removed gross impurities. Final purication was by sublimation and catalytic treatment of the vapor. Impure terephthalic acid was vaporized in a steam carrier, and catalyst and hydrogen were added to convert undesirable organic impurities. Subsequent cooling of the stream condensed the terephthalic acid, leaving impurities in the vapor. Product crystals were removed by cyclones. A process no longer practiced is based on Henkel technology. Starting with phthalic anhydride [85-44-9], the monopotassium and dipotassium o-phthalate salts were formed in sequence. The dipotassium salt was isolated from solution by spray drying, and isomerized to dipotassium terephthalate under carbon dioxide at 1000 5000 kPa and 350 450 C. This salt was dissolved in water and recycled to the start of the process, where terephthalic acid crystals formed during the production of the monopotassium salt. The crystals were recovered by ltration. Two proposed processes which were never commercialized were by Lummus, using a dinitrile route [19] and by Eastman, using the formation of 1,4-diiodobenzene [624-38-4] with carbonylation to aromatic acids [20]. Toluene [108-88-3] is a potential feedstock for manufacture of terephthalic acid and is cheaper than p-xylene. Mitsubishi Gas Chemical has researched a process where a complex between toluene and hydrogen uoride boron triuoride is formed, that can be carbonylated with carbon monoxide to form a p-tolualdehyde [104-87-0] complex [21]. After decomposition of the complex, p-tolualdehyde can be oxidized in water with a manganese bromine catalyst system to terephthalic acid. While cheaper toluene is the feedstock and acetic acid is not required, the complexities of handling hydrogen uoride boron triuoride and the need for carbon monoxide add other costs. This process has not been commercialized.

Dimethyl terephthalate and recovered monomethyl terephthalate are combined with water from the methanol recovery tower of the dimethyl terephthalate process and heated to 260 280 C at 4500 5500 kPa in a hydrolysis reactor, where the methyl esters are hydrolyzed. The overhead methanol plus water vapor is returned to the methanol recovery tower for separation. The hydrolysis reactor liquid is sent to a series of crystallizers and cyclones. After cooling to crystallize the terephthalic acid at ca. 200 C, washing cyclones are used to remove mother liquor which contains monomethyl terephthalate. The cyclone underow is further cooled to 100 C, and nal crystallization occurs. This slurry is centrifuged and dried to give the nal product. Monomethyl terephthalate from the cyclone overow is recovered, again by cooling to 100 C and centrifuging, and the cake is recycled to the hydrolysis reactor.

3.7. Alternative and Past Technologies


Oxidation of p- or m-xylene is also possible with acetic acid solvent and a cobalt catalyst with an acetaldehyde activator. Reaction temperature is 120 140 C, and as a result the oxidation requires a residence time 2 h. Titanium-lined vessels are not required because bromine is not used. The acetaldehyde is converted to acetic acid as it promotes the reaction. After reaction, the terephthalic or isophthalic acid is recovered by centrifugation or ltration and drying, much like the Amoco process, and acetic acid is recovered for recycle by distillation. With isophthalic acid, which has a lower concentration of 3-formylbenzoic acid, considerable purication is possible by slurrying in water to ca. 20 25 wt %, heating to 240 260 C to dissolve, and crystallizing by cooling in batch mode. Recovery of the crystals is again by centrifugation or ltration and drying. Eastman Chemical in the United States also used an acetaldehyde activator with a cobalt catalyst to produce terephthalic acid. Bromine is now being used in place of acetaldehyde [17]. Mobil Chemical in the United States had a commercial terephthalic acid operation which has since been abandoned [18]. As with the above processes, a cobalt catalyst was used with

4. Environmental Protection
The three chemicals discussed here consist only of carbon, hydrogen, and oxygen, so carbon

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid dioxide and water are the nal efuents of oxidative degradation. There are traces of the cobalt manganese bromine catalyst in waste streams, however. Efuents from the terephthalic acid process include water generated during oxidation and water used as the purication solvent. Gaseous emissions are mostly the oxygen-depleted air from the oxidation step. Volumes are large, but the chemicals in the streams can be effectively destroyed and removed. Water efuents are subjected to aerobic wastewater treatment, where the dissolved species, mostly terephthalic acid, acetic acid, and impurities such as p-toluic acid, are oxidized to carbon dioxide and water by the action of bacteria which are acclimated to these chemicals. The bacterial growth is a sludge which can be dried and burned or spread on land. An anaerobic process has been developed to treat the wastewater [22]. Advantages include much less waste sludge production, less utility consumption, and the generation of methane, which can be burned for energy recovery. Waste gas is scrubbed in process equipment to remove acetic acid vapors for recovery. Trace amounts of other compounds formed in the reactor can be removed by catalytic oxidation, followed by scrubbing to meet the most demanding regulations for process vents [23]. Waste streams from distillation in the dimethyl terephthalate process can be burned for energy recovery. Another aspect of environmental protection is the recyclability of polyesters. Post-consumer containers can be ground and cleaned, and then extruded and spun into ber to ll bedding, and quilted clothing. Textile bers can also be made. The polyester can also be reacted to regenerate the terephthalate feedstock. High-temperature hydrolysis yields terephthalic acid. Reaction with methanol yields dimethyl terephthalate.

sured, e.g., monofunctional compounds can cap the polyester chain and limit molecular mass buildup. Trifunctional carboxylic acids can cause chain branching which leads to undesirable rheological and spinning properties. Colored impurities can be incorporated into the polyester. In particular, 4-formylbenzoic acid limits polyester molecular mass and causes yellowness [24]. The particle size of terephthalic acid determines how the powder ows, and the viscosity of the slurry when mixed with 1,2ethanediol [107-21-1]. Owing to the consistent high purity of these products and the different effects of impurities, specications put limits on specic impurities or color, rather than overall purity (Table 3). Trends in quality specications are away from maximum or minimum values, toward a target value with an allowable range. This has been instituted to some extent by Amoco Chemical for the ptoluic acid content, for example.

Table 3. Specications and typical analyses of puried terephthalic acid Property Acid number, mg KOH/g Ash, ppm Metals, ppm Water, wt % 4-Formylbenzoic acid, ppm p-Toluic acid, ppm Specication 675 2 15 9 0.2 25 125 45 Typical value 673 675 <3 <2 0.1 15 125

Co + Mn + Fe + Cr + Ni + Mo + Ti. Medium-purity terephthalic acid typically has 250 ppm 4-formylbenzoic acid and <50 ppm p-toluic acid.

5. Quality Specications
Feedstocks for polyester production must be extremely pure; they are among the purest high-volume chemicals sold by industry. If certain impurities are present in high enough concentrations, harmful effects can be mea-

In Table 3, acid number, determined by titration, is an overall purity measurement. A perfectly pure sample will have an acid number of 675.5 mg KOH/g, but the low impurity levels make the acid number meaningless as a quantitative indication of purity, and it is being phased out. Impurities specied include p-toluic acid and 4-formylbenzoic acid, residual water, and trace metals, the ash being trace metal oxides. There are also color and particle size measurements. Polyester producers often have specic tests which they prefer for color or particle size. Medium-purity terephthalic acid specications address the same impurities, except that

10

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid

4-formylbenzoic acid concentrations are up to 300 ppm, and residual acetic acid is present. Typical dimethyl terephthalate specications are shown in Table 4. Freezing point is an extremely sensitive purity indicator. Since dimethyl terephthalate is often shipped and stored in molten form, color measurements are made on the melt. A color stability test can determine the samples resistance to degradation. This resistance is reduced by the presence of unesteried acid groups, so these residual groups are measured.
Table 4. Specications and typical analyses of dimethyl terephthalate Property Freezing point, C Acid number, mg KOH/g Molten color, APHA Color stability, APHA Water, wt % 4 h at 175 C Specication 140.62 0.03 25 25 0.02 Typical value 140.64 0.01 10 15 0.01

7. Uses
Terephthalic acid and dimethyl terephthalate are used almost exclusively to produce saturated polyesters. Poly(ethylene terephthalate), the alternating copolymer of terephthalic acid and 1,2ethanediol, accounts for > 90 % of this use, with a worldwide demand of 12.6106 t in 1992. Textile and industrial ber accounted for 75 % of this demand. Polyester is the largest volume synthetic ber. Food and beverage containers accounted for 13 %, and constituted the fastest growing segment. Film for audio, video, and photography took 7 %. Other uses are for poly(butylene terephthalate), a high-performance molding resin made by reaction with 1,4-butanediol [74829-49-5], and for special industrial coatings, solvent-free coatings, electrical insulating varnishes, aramid bers, and adhesives. A small amount of bis(2ethylhexyl) terephthalate [6422-86-2] is produced as a plasticizer, and some dimethyl terephthalate is ring-hydrogenated to produce the cyclohexane analog, 1,4-cyclohexanedicarboxylic acid [1076-97-7 ], for specialty polyesters and coatings. Isophthalic acid is used as a comonomer with terephthalic acid in bottle and specialty resins. It is also a feedstock for coatings and for high-performance unsaturated polyesters, being rst reacted with maleic anhydride [108-31-6 ] and then this resin is cross-linked with styrene [100-42-5].

Specications for isophthalic acid are similar to those of terephthalic acid, m-toluic acid and 3-formylbenzoic acid being the impurities.

6. Storage and Transportation


Terephthalic acid powder is stored in silos and transported in bulk by rail hopper car, hopper truck, or bulk container with a polyethylene liner. Hopper cars and trucks should be dedicated to this service, because of the extreme purity requirements. Shipment is also in 1 t bags, or paper bags containing ca. 25 kg. Isophthalic acid, being a much lower volume chemical, has a higher proportion shipped in bags. Dimethyl terephthalate is stored molten in insulated heated tanks, and is preferentially shipped molten in insulated rail tank cars or tank trucks. It is also solidied into briquettes or akes, and shipped in 1 t or 25 kg bags. The huge production volume of terephthalic acid and dimethyl terephthalate favors the use of bulk shipment with minimized packaging costs. Rail cars are preferred where possible, and they can accommodate up to 90 t. Containers with plastic liners hold 20 t terephthalic acid, and these are the preferred ocean shipping method.

8. Economic Aspects
Together, terephthalic acid and dimethyl terephthalate rank about 25th in tonnage of all chemicals, and about tenth for organic chemicals. The rapid growth of polyester use has led to an aboveaverage growth for these feedstocks, and this is projected to continue as deeper penetration into ber and container markets is made. The versatility of terephthalate and isophthalate polyesters is projected to drive growth in the foreseeable future. Capacity for the three types of terephthalate feedstocks since 1980 is given in Table 5. Puried terephthalic acid has grown rapidly, and is projected to supply virtually all the growth

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid for polyesters, about 7 % annually to the year 2000. Medium-purity terephthalic acid capacity has grown by construction of a few new plants, and by conversion of some dimethyl terephthalate capacity. Dimethyl terephthalate has shown little change in capacity since 1980, and essentially none is expected in the future.
Table 5. Capacity of terephthalate feedstocks (103 t/a) Feedstock PTA MTA DMT 1980 2800 420 3300 1986 4000 580 3600 1992 8100 1300 3300

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PTA puried terephthalic acid; MTA medium-purity terephthalic acid; DMT dimethyl terephthalate.

The Far East contains most of the worlds population and most of the garment manufacturing industry. As a result, it is experiencing most of the growth in manufacturing capacity for polyester bers, and most of the growth for terephthalic acid production (Table 6). Approximately 75 % of the growth in terephthalate feedstocks in 1986 1992 was due to puried terephthalic acid plants built in the Far East.
Table 6. Geographical distribution of terephthalate production (103 t/a) 1980 North America Europe Far East Rest of World 3300 1500 1500 220 1986 3400 2100 2300 380 1992 3600 2700 5800 600

producers are Mitsui Sekka in Japan and Imperial Chemical Industries in England and Taiwan. China is certain to become a major producer, and large plants are being planned in Southeast Asia. Larger producers of medium-purity terephthalic acid are Mitsubishi Kasei in Japan, and Eastman and DuPont in the United States. Some polyester producers have licensed technology to supply their own feedstock. All licensors are themselves producers of terephthalic acid, or have obtained the technology from a producer. Major dimethyl terephthalate producers are DuPont, Eastman Chemical, and Hoechst Celanese in the United States, Hoechst in Europe, and Teijin Petrochemical in Japan. There are several small, older plants, mostly in Europe and China. Isophthalic acid production capacity is 250103 t/a, ca. 2 % of the terephthalate total. Amoco Chemical is the major producer.

9. Toxicology and Occupational Health


Terephthalic acid, dimethyl terephthalate, and isophthalic acid all have low toxicity and cause only mild and reversible irritation to skin, eyes, and the respiratory system. For oral ingestion of terephthalic acid, LD50 values for rats have been reported as 18.8 g/kg [26], and for mice as 6.4 g/kg [27], or > 5 g/kg [28]. Dimethyl terephthalate LD50 values for rats are 6.5 g/kg [29] and 4.39 g/kg [26]. Some mortality was found at 5 g/kg oral ingestion [30], and with a 28-day oral uptake of 5 % in the feed, ca. 2.5 g/kg. For isophthalic acid, LD50 for rats was reported as 10.4 g/kg [26]. Interperitoneal administration of terephthalic acid in rats showed LD50 values > 1.43 g/kg [28] and 1.9 g/kg [31], with LD100 = 3.2 g/kg [31]. Mortality was found at 0.8 g/kg in mice and 1.6 g/kg in rats [27]. For dimethyl terephthalate, an LD50 of 3.9 g/kg has been reported [29], and for isophthalic acid, 4.3 g/kg [26]. Ingestion of terephthalic acid or dimethyl terephthalate results in rapid distribution and excretion in unchanged form [32]. In rats, at high ingestion rates of about 3 % terephthalic acid or dimethyl terephthalate in the feed, bladder calculi are formed which are mostly calcium terephthalate; these injure the bladder wall and lead

Pricing is often determined in conjunction with long-term contracts, and is most inuenced by the cost of p-xylene. In 1992, prices were about $ 0.60/kg for terephthalic acid and $ 0.57/kg for dimethyl terephthalate [25]. Because a given mass of terephthalic acid produces 17 % more polyester than the same mass of dimethyl terephthalate, the dimethyl terephthalate price must be adjusted downward, and allowance is made for the value of the methanol generated during transesterication. The major producer of puried terephthalic acid is Amoco Chemical, with over 17 % of the worlds production in 1992. Joint ventures of Amoco, the largest being China American Petrochemical in Taiwan and Samsung Petrochemical in Korea, also produce about 17 %. Other major

12

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid


2. P. Raghavendrachar, S. Ramachandran, Ind. Eng. Chem. Prod. Res. Dev. 31 (1992) 453 462. 3. J. E. McIntyre, Chem. Eng. Monogr. 15 (1982) 400 444. Specic References 4. Calico Printers Assoc, GB 578 079, 1941 (J. R. Whineld, J. T. Dickson). 5. Mid-Century Corp., US 2 833 816, 1955 (R. S. Barker, S. A. Soffer). 6. Mid-Century Corp., US 3 089 906, 1958 (R. S. Barker, S. A. Soffer). 7. W. Partenheimer in D. W. Blackburn (ed.): Catalysis of Organic Reactions, Marcel Dekker, New York 1990, pp. 321 346. 8. Standard Oil Company (Indiana), US 3 584 039, 1967 (D. H. Meyer). 9. Standard Oil Company (Indiana), US 3 931 305, 1973 (J. A. Fisher). 10. K. Matsuzawa, Chem. Econ. Eng. Rev. 8 (1976) no. 8, 25 30. 11. M. Hizikata, Chem. Econ. Eng. Rev. 9 (1977) no. 9, 32 38. 12. Mitsubishi Chem. Ind. Ltd., US 4 877 900, 1988 (A. Tamaru, Y. Izumisawa). 13. Eastman Kodak Company, US 4 447 646, 1983 (G. I. Johnson, J. E. Kiefer). 14. H. J. Korte, H. Schroeder, A. Schoengen: The PTA Process of H uls Troisdorf AG, AIChE Summer National Meeting, Denver, Co. 1988. 15. E. I. DuPont de Nemours, US 2 491 660, 1949 (W. F. Gresham). 16. Standard Oil Company (Indiana), US 2 976 030, 1957 (D. H. Meyer). 17. Eastman News 43 (1988) no. 14. 18. H. S. Bryant, C. A. Duval, L. E. McMakin, J. I. Savoca, Chem. Eng. Prog. 67 (1971) no. 9, 69 75. 19. A. P. Gelbein, M. C. Sze, R. T. Whitehead, CHEMTECH 3 (1973) 479 483. 20. Eastman Kodak Company, US 4 705 890, 1987 (G. R. Steinmetz, M. Rule). 21. Chem. Eng. (N.Y.) 83 (1976) no. 17, 27 28. 22. S. Shelley, Chem. Eng. (N.Y.) 98 (1991) no. 12, 90 93. 23. T. G. Otchy, K. J. Herbert: First Large Scale Catalytic Oxidation System for PTA Plant CO and VOC Abatement, Ann. Air Waste Managem. Assoc. Meet. 85th 1992. 24. W. Berger, D. Dornig, Faserforsch. Textiltech. 29 (1978) 256 262. 25. Chem. Markt. Rep. 242 (1992) no. 4, 42. 26. J. V. Marhold, Sb. Vys. Toxicologickeho Vysetrien Latid A Priravku 1972, 52.

to cancer. Calculi cannot form unless the calcium terephthalate solubility is exceeded (threshold effect) [33]. Neither compound has been found to be genotoxic (Ames test) [34]. Inhalation of terephthalic acid dust appears to pose no clear hazards. Inhalation by rats for 6 h/d, 5 d/week, for 4 weeks at 25 mg/m3 produced no fatalities [35]. Dimethyl terephthalate dust at 16.5 and 86.4 mg/m3 for 4 h/d caused no toxicological effects after 58 days [29]. The rats intermittently reacted to the nuisance dust levels at the higher concentration. Irritation of the skin, eyes, and mucous membranes by any of these chemicals is mild and reversible. In rabbits, the FHSA test for terephthalic acid for eyes gave scores of 14.0/110.0 and 3.5/110.0 at 1 and 24 h after exposure. The FHSA skin test score was 0.4/8.0 [35]. For isophthalic acid, eye and skin irritancy scores were 5.3/110.0 and 0.2/8.0 [36]. Irritation due to dimethyl terephthalate has also been reported to be mild [30]. Terephthalic acid, dimethyl terephthalate, and isophthalic acid can all form dust clouds. As with any ammable substance, an explosion can occur, given proper dust and oxygen concentrations. Reported limits on the explosive region for terephthalic acid dust clouds are minimum dust content of 40 g/m3 and minimum oxygen content 12.4 % at 20 C. At 150 C, minimum oxygen is 11.1 % [37]. The maximum concentration of an explosible dust cloud has been calculated as 1400 g/m3 [38]. Dimethyl terephthalate and isophthalic acid have a more stringent oxygen limit. In tests with carbon dioxide diluent, the minimum oxygen content was 12, 14, and 15 % for dimethyl terephthalate, isophthalic acid, and terephthalic acid [39]. The oxygen content is higher for carbon dioxide diluent than for nitrogen, owing to the higher heat capacity of carbon dioxide (the 12.4 % minimum oxygen content reported above for terephthalic acid was for nitrogen diluent). For molten dimethyl terephthalate, the ash and re points, determined by the Cleveland open-cup method, are 146 and 155 C [1].

10. References
General References 1. Kirk-Othmer, 18, 732 777.

Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid


27. A. E. Moftt et al., Am. Ind. Hyg. Assoc. J. 36 (1975) 633 641. 28. A. Hoshi, R. Yanal, K. Kuretani, Chem. Pharm. Bull. 16 (1968) 1655 1660. 29. W. J. Krasavage, Am. Ind. Hyg. Assoc. J. 34 (1973) 455 462. 30. Haskel Laboratories, unpublished data, Wilmington, Delaware, USA, 1979. 31. E. O. Grigas, R. Ruiz, D. M. Aviado, Toxicol. Appl. Pharmacol. 18 (1971) 469 486. 32. A. Hoshi, K. Kuretani, Chem. Pharm. Bull. 16 (1968) 131 135. 33. H. dA. Heck, Banbury Rep. 25 (1987) 233 244.

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34. E. Zeiger, S. Haworth, W. Speck, K. Mortelmans, EHP Environ. Health Perspect. 45 (1982) 99 104. 35. Amoco Chemical Company, Material Safety Data Sheet, Amoco TA-33, Chicago, Ill., 1993. 36. Amoco Chemical Company, Material Safety Data Sheet, Amoco PIA, Chicago, Ill., 1993. 37. A. D. Craven, M. G. Foster, Combust. Flame 11 (1967) 408 414. 38. S. Nomur, M. Torimoto, T. Tanake, Ind. Eng. Chem. Proc. Res. Dev. 23 (1984) 420 423. 39. M. Jacobson, J. Nagy, A. R. Cooper, Rep. Invest. U.S. Bur. Mines 5971 (1962) 25 26.

Terpene Resins

Resins, Synthetic