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Ethyl Acetate: A Techno-Commercial Profile PANKAJ DUTIA E-mail:
[email protected]
manufacture, but the larger ones use continuous thyl acetate is a colourless liquid with a fruity columns with a reboiler for the reaction. The water odour, having a molecular weight of 88.10. It formed in the reaction (and also from the 95% alcohol is slightly soluble in water and soluble in most used as raw material) is removed continuously. Condiorganic solvents, such as alcohol, acetone, ether and tions are such as to ensure maximum conversion of chloroform. It finds use as a solvent in a wide range of acetic acid, which is costlier than ethyl alcohol. applications, across many industries, including:
INTRODUCTION
E
Surface coating and thinners : Ethyl acetate is one
of the most popular solvents and finds wide use in the manufacture of nitrocellulose lacquers, varnishes and thinners. It exhibits high dilution ratios with both aromatic and aliphatic diluents and is the least toxic of industrial organic solvents. Pharmaceuticals: Ethyl acetate is an important com-
ponent in extractants for the concentration and purification of antibiotics. It is also used as an intermediate in the manufacture of various drugs. Flavours and essences: Ethyl acetate finds exten-
sive use in the preparation of o f synthetic fruit essences, flavours and perfumes. Flexible packaging : Substantial quantities of ethyl
TABLE 1 SPECIFICATIONS OF ETHYL ACETATE USED IN INDIA Property
Value
Clarity Ester contents (% by mass, Min) Acidity as acetic acid (% by mass, Max) Water content (% by mass, Max) Residue on evaporation (% by mass, Max) Rela Relati tive ve dens densit ity y at 2/27 2/27°C °C Distillation range (at (at 760 760 mm Hg), Hg), not less less than 95 % by volume
Clear, colourless liquid 9 9 .0 0 .0 1 0.1 0.01 0.89 0.894 4 -0.8 -0.898 98 Shall distil within the rang rangee of of 7676-78 78°C °C
acetate are used in the manufacture of flexible packaging and in the manufacture of polyester films and BOPP Developments in process Most commercial production is by esterification of films. It is also used in the treatment of aluminium foils. acetic acid with ethanol or liquid-phase oxidation of Miscellaneous : Ethyl acetate is used in the manu- n-butane with ethyl acetate as a by product, but some facture of adhesives, cleaning fluids, inks, nail-polish material is also made by condensation of acetaldehyde. removers and silk, coated papers, explosives, artificial Several new technologies have been commercialised. leather, leather, photographic films & plates. BP’s new Avada process, employed in a new plant at Hull, UK, uses ethylene and acetic acid with solid acid Manufacture Ethyl acetate is produced by the esterification reac- catalyst. Davy Process Technology (formerly Kvaerner) tion of ethyl alcohol and acetic acid using catalysts such has licensed its ethanol-based process to Sasol; in this as sulphuric acid, para toluene sulphonic acid or ion process ethanol is dehydrogenated to acetaldehyde, exchange resins. Most of the production in India is based which further reacts to form ethyl acetate. on sulphuric acid catalysis; very little acid is required, though corrosion is a problem if material of construcChinese National Petroleum has developed a onetion is not appropriate. step ethanol process where ethanol is partially oxidised to acetic acid and then esterified with excess ethanol to There are small producers using batch process for give ethyl acetate. CHEMICAL WEEKLY
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during the period 1996-97 to 2003-04. The capacity utilisation during 2003-04 was 75%.
PRESENT STATUS IN INDIA
Until few years ago there were more than two dozen units – both in the organised and small-scale sector – making ethyl acetate. However, after globalisation, consolidation and restructuring has resulted into unviable units moving out of the business. Today, there are only nine units in operation, with a total capacity of 121,500-tpa (see Table 2). Years Jubilant Organosys Ltd. (formerly VAM Organics), Laxmi Organics, Industrial Organics (formerly Trident Alco-chem) and Somaiya Organics are the four major producers constituting 90% of the total capacity and 90% of the total production.
TABLE 3 PRODUCTION TRENDS IN ETHYL ACETATE [Tons] Production
1990-91 1996-97 2001-02 2002-03 2003-04
18,700 48,000 65,000 75,000 90,000
Source: Industry
Production of ethyl acetate is estimated to have grown from 18,700-tons in 1990-91 to 48,000-tons in 199697 and further to 90,000-tons in 2003-04. Production has registered a growth rate of 17% per annum during the period 1990-91 to 1996-97 and 11% per annum
Foreign trade
Small quantities of ethyl acetate are imported into the country, while good quantities are exported. Table 4 and Table 5 provide import end export statistics dur-
TABLE 2 CAPACITY AND PRODUCTION OF ETHYL ACETATE IN INDIA [2003-04] (Tons) Location
Installed capacity
Estimated production
30,000
24,000
49,500 15,000 16,500 9,000 2,400 9,000 1,800 1,800 3,600 7,000 600 1,268 1,800 5,000 1,200 1,800 1,500
30,000 15,000 n.a n.a n.a 0 n.a n.a 0 0 0 0 0 n.a 0 0 0
Total
158,768
90,000
Total capacity in operation
121,500
90,000
Laxmi Organic Industries Ltd. Jubilant Organosys Ltd. Somaiya Organics Ltd. Industrial Organics Ltd. Dhampur Alco-Chem Ltd. Sanjivani SSK Indian Organics Ashok Organics Trichy Distilleries King Chemicals Ester Industries Ltd. Mysore Acetate Andhra Sugars Vamotivala Pentokey Organics Krishna Orgochem Ichalkaranji EID Parry
Mahad, Mah. Nira, Mah. Gajraula, U.P. U.P. Ludhiana, Pun. Delhi Ahmednagar, Mah. Khopoli, Mah. Nandasari, Guj. Trichy, T.N. T.N. Delhi Mandia, Kar. Tanuku, A.P. Mumbai, Mah. Mumbai, Mah. Ichalkaranji, Mah. Thyagavalli, T.N.
Status
Partially operating Closed
Closed Closed Closed Closed Closed Partially operating Closed Closed Closed
Source: Industry 180
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ing the last few years. As can be seen, imports have been fluctuating between 100 to 600-tons, although there are market indications that they have increased substantially in the last couple of months. The unit CIF value paid on imports has also been fluctuating.
TABLE 7 PRICE TREND IN ETHYL ACETATE [Rs. Per kg] Period
May 2003 As can be observed from Table 5, exports have been June 2003 witnessing an increasing trend and have grown from Aug. 2003 1,474-tons in 1998-99 to 28,948-tons in 2002-03 and Sep. 2003 to estimated figure of 32,000-tons in 2003-04. The to- Oct. 2003 tal value of exports during 2002-03 was Rs. 94.70- Nov. 2003 crore. Dec. 2003 Jan. 2004 The unit FOB value realised from exports is in the Feb. 2004 range of Rs. 29-33 per kg. The major destination of March 2004 exports are UAE, Taiwan, Netherlands, Malaysia, Iran, April 2004 Egypt, Sri Lanka and Thailand. May 2004 June 2004 TABLE 4 July 2004 IMPORTS OF ETHYL ACETATE
Year
Quantity Value Unit value [Tons] [Rs. Lakhs] [Rs/Kg]
1998-1999 1999-2000 2000-2001 2001-2002 2002-2003
165.77 604.12 129.06 91.63 362.55
15.97 20.39 11.51 9.19 22.46
96.33 33.74 89.19 100.27 61.95
Basic bulk
Market rate
28.00 28.00 27.50 28.00 27.50 27.50 29.00 28.50 29.00 31.00 34.00 35.00 38.00 40.00
39.00 38.50 37.50 38.00 37.50 37.00 39.00 38.50 39.00 41.00 45.00 47.00 52.00 54.00
Note: Market rate is for packed material and includes Excise Duty
Consumption pattern and demand
The present total demand for ethyl acetate is estimated to be in the region of 90,000-tons. This constitutes domestic demand of 55,000-tons and export demand of 35,000-tons. Table 8 provides the pattern of consumption during 2003-04.
Source: DGCIS
TABLE 5 EXPORTS OF ETHYL ACETATE Year
Quantity Value Unit value [Tons] [Rs. million] [Rs/Kg]
1998-1999 1999-2000 2000-2001 2001-2002 2002-2003 2003-2004
1,474.12 5,832.65 7,027.47 9,630.20 28,948.83 35,000.00
Source: DGCIS
Price trend
42.75 1,46.25 2,32.12 2,98.99 9,47.13 —
29.00 25.07 33.03 31.04 32.72 —
TABLE 8 CONSUMPTION PATTERN OF ETHYL ACETATE [2003-04] Sector
Paints & Inks Adhesives Flexible packaging Pharma Al. Foils Electronics Misc. uses
Consumption [Tons]
Share [%]
13,750 5,500 13,750 11,000 5,500 1,650 3,850
25.0 10.0 25.0 20.0 10.0 3.0 7.0
55,000 100.0 The current basic price of ethyl acetate for bulk sales Total is Rs. 40 per kg exclusive of excise and sales tax. The price of the packed material in carbouys is ruling around Paints Rs. 54 per kg, excluding sales tax. The trend in the prices The paints and printing ink industry are the biggest over the period of last two years is given in Table 7. consumers of ethyl acetate in India. It is used as a solCHEMICAL WEEKLY
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Product Focus TABLE 6 DESTINATION-WISE EXPORTS OF ETHYL ACETATE [Quantity in Tons; Value in Rs. Million] 2000-01 Australia Bangladesh Barbados Belgium Brazil China Colombia Cyprus Egypt Germany Greece Hong Kong Iran Israel Italy Jamaica Japan Jordan Kenya Korea North Lebanon Malaysia Maldives Mauritius Nepal Netherlands Netherlands Antilles New Zealand Nigeria Oman Pakistan Philippines Russia Saudi Arabia Singapore Slovenia South Africa Spain Sri Lanka Syria Taiwan Tanzania Thailand Tunisia Turkey Turks C Islands UAE USA Vietnam Yemen Total 182
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2001-02
2002-03
Qty
Val
Qty
Val
Qty
Val
115.20 14.40 28.80
3.81 0.38 0.93
216.00 65.80
6.66 2.52
337.60 280.00
11.37 9.55
236.15
9.39
0.25
0.06 662.30
17.23
1,822.20 220.22 387.80 135.12 2,607.60 445.60 616.49
60.24 11.43 14.17 5.32 79.51 15.05 22.59
286.38 156.80
8.89 5.19
547.20 2,720.48 0.20
17.97 81.27 0.01
24.60 2,803.07 569.23 43.20 57.20 100.40
0.68 120.89 17.91 1.57 1.59 3.34
14.40 21.00 451.60 315.04 40.79 92.00 261.56 1,014.60 86.40 2,536.61
0.44 0.63 15.71 10.62 1.95 2.99 9.30 35.18 2.78 66.99
1,176.87 14.40 229.20 379.80 6,995.83
33.91 0.35 7.73 13.56 221.60
129.60 128.80
4.16 4.07
28,948.33
947.14
260.00
8.81
115.20
3.13
144.40
4.59
72.00 20.80
2.39 0.79
130.05
4.27
561.67
19.43
0.85 168.80 1,141.00
0.02 5.19 34.52
14.40 28.80 0.01 404.51
0.43 0.68 13.35
28.80 54.00 273.65 204.75 72.00 1,297.20
0.70 2.29 8.42 5.18 2.19 42.73
0.50 0.40
14.25 193.80 11.00
14.40 49.30
0.08
0.46 5.64 0.85
0.47 1.52
0.37
0.05
1,460.15
45.95
172.80
5.24
3,627.15 6.19
113.44 9.33
59.00
2.11
208.45
7.56
489.60 402.40
15.09 11.52
42.80
1.36
28.40 43.20 1,086.64 14.40 129.80
0.89 1.18 27.76 0.44 4.00
89.61 9.94 0.46 2.20 298.99
14.40
0.48
3,062.72 6.23 14.40 71.60
7,027.47
232.12
9,630.21
CHEMICAL WEEKLY
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vent in the manufacture of nitrocellulose based paints, prices of ethyl acetate. It is used as a solvent and reacthinners & varnishes. In fact, ethyl acetate was the most tant in the manufacture of drugs such as sulphapreferred solvent by the paints and printing inks indus- methoxazole, rifampicin etc. The total consumption by try around five-years back, accounting for around 50% this sector is presently estimated at 11,000-tons. of total consumption. However, its share in this industry has come down sharply to 25% due to greater use Aluminium foils of cheaper solvents such as acetone, MIBK, etc. Higher Ethyl acetate finds usage in the treatment of aluprices of ethyl acetate have prompted many paint and minium foils & sheets. It is also used during the screen ink consumers to switchover to cheaper solvents. printing stage. India Foils Ltd., Kolkata; Indian Aluminium Co. Ltd., Thane; and P.G. Foils, Rajasthan are The consumption of ethyl acetate in paints and inks the three manufacturers of aluminium foils. The consegment is estimated to be in the region of 13,750-tons, sumption of ethyl acetate by this sector is 5,500-tons. constituting 25% of total demand in 2003-04. Adhesives This end-use accounts for around 10% of total consumption. Converters & Adhesives Chemicals Ltd., Navi Mumbai is the biggest user in this segment. Total consumption by the adhesives industry is estimated at 5,500-tons annually. Flexible packaging & lamination Ethyl acetate due to its fast evaporating properties is used in flexible packaging industry at the screen printing stage. This industry has emerged as one of the bulk consumers of ethyl acetate. The packaging industry was hardly recognised as an industry about three decades back, but recognition came, and that too at a galloping pace. Today, it has attained the status of a large scale industry, which boasts not only of technological advancement, but also of meeting export needs. Out of the various packing products, flexible laminates are enjoying a healthy growth rate. The industry is enjoying growth of around 15% per annum.
Some of the major manufacturers of flexible packaging are: Flex Industry Ltd., Delhi; Garware Plastics & Polyesters Ltd.; Essel Packing Ltd., Mumbai; Ester Industries Ltd.; Sharp Industries Ltd., Mumbai; Bakelite Hylam Ltd.; Flexo Films Ltd.; and Cosmo Films Ltd. The total consumption of ethyl acetate in this sector is estimated at 13,750-tons, constituting 25% of total consumption. Pharmaceuticals Like the paints industry, the pharmaceuticals was also one of the major users of ethyl acetate five-years ago, accounting for 35% of total consumption. This share has also come down to 20% again due to rising CHEMICAL WEEKLY
Electronics Small quantities of ethyl acetate are also used in the manufacture of video/audio tapes. Magnetic media of tapes are purified with ethyl acetate. It is also used for head cleaning, etc. In fact, ethyl acetate of 99.7% quality is the best solvent for cleaning, etc. However, production is concentrated in the small scale sector. The consumption by this sector is estimated in the region of 1,650-tons Miscellaneous uses The other minor applications of ethyl acetate include its applications in the textiles, dyestuffs, explosives, photographic films & plates, artificial leather, etc. Around 300-tons of ethyl acetate are being consumed by ordinance factories for use in explosives. These miscellaneous uses account for a total consumption of 3,850-tons, constituting 7% of total consumption. Future demand for ethyl acetate
Among the different end-use segments of ethyl acetate, the packaging, adhesives and pharmaceutical industries is enjoying a healthy growth rate in the range of 12 to 15% per annum. The growth rates in other segments, such as paints, foils, electronics etc. is expected to be in the region of around 5-7% per annum. Sources within the industry are expecting an average growth rate of around 8% per annum. Based on this growth rate, the domestic demand for ethyl acetate is estimated to be around 75,000-tons by 2007-08. As far as export demand is concerned, according to industry sources the demand has already peaked and may not increase, in future, but may decline due to alcohol shortage within the country and high prices of raw materials. AUGUST 10, 2004
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Product Focus GLOBAL SCENARIO
The total global capacity for ethyl acetate is estimated to be in the region of 1.5-mt and the production at around 1.3-mt. BP Chemicals, UK; Showa Denka, Japan; Rhodia Brasil, Brazil; and Celanese, US are the major producers (see Table 9). Consumption pattern
Ethyl acetate is an active solvent that is available in three grades: 85-88%, 99% and 99.5% (urethane grade). The most popular grade, 99% is mainly used in indus-
trial lacquers and surface coating resins. It is also used as an extraction solvent in the production of pharmaceuticals and food and as a carrier solvent for herbicides. About 60% of demand is in coatings. Process solvents, including pharmaceuticals and organic synthesis, account for 15% of demand, as does printing inks. Miscellaneous uses, including adhesives and cosmetics, account for 10% of consumption. Europe
The European markets are suffering from weak de-
TABLE 9 MAJOR GLOBAL ETHYL ACETATE PRODUCERS [’000 TPA] Company
Location
Aliachem Atanor BP Chemicals Celanese
Pardubice, Czech Republic Buenos Aires, Argentina Hull, UK La Cangrejera, Mexico Pampa, Texas, US Pulau Sakra, Singapore Ichihara, Japan Kingsport, Tennessee, US Longview, Texas, US Tarragona, Spain Ulsan, South Korea Gajraula and Nira, India Ulsan, South Korea Yokkaichi, Japan Mahad, India Paulinia, Brazil Secunda, South Africa Shandong, China Wujing, China Nanyo, Japan Merak, Indonesia Antwerp, Belgium, Springfield Massachusetts, US Treton, Michigan, US Domsjo, Sweden Stockholm, Sweden Chongging, China
Chiba Ethyl Acetate Eastman Ercros International Ester Jubilant Organosys Korea Alcohol Industrial Kyowa Hakko Kogyo Laxmi Organic Industries Rhodia Brasil Sasol Shandong Jinyimeng Chemical Shanghai Jinyimeng Chemical Showa Denko Showa Esterindo Indonesia Solutia
Svensk Etanolkemi Union Carbide Yangtze River Acetyls
Capacity
12 10 220 92 60 60 50 27 32 60 75 32 25 40 35 100 50 80 30 150 60 12 14 11 35 30 30 1432
Others Total
83 1515
Source: ECN 184
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mand and excess availability. The economic slowdown Japan has impacted consumption this year, particularly in the In Japan, Showa Denko set up a 55:45 joint venture printing inks and coatings. Supply has also lengthened with Kyowa Hakko Kogyo, called Japan Ethyl Acetate, following the restart of BP’s Hull, UK plant in late and the partners are converting an idled acetic acid fa2002 after a six-month long outage and this, together cility at Oita to produce 100,000-tpa of ethyl acetate. with players fighting for market share, has added to Production was expected to start in April this year. pressure on prices. Import volumes have declined, par- Kyowa Hakko will then close its existing unit in ticularly in the second half of this year. Less material is Yokkaichi. now available from Russia, where output has been reduced and plants focus instead on the production and The US Scenario export of acetic acid feedstock. Future demand growth In the US, Celanese, Eastman, and Solutia are the in Europe is put at 2-3% per year. No new capacity is major producers with a total combined capacity of planned, or likely, in Europe. Most capital investment is 0.132-mt. targeted for Asia, and China in particular, where demand TABLE 10 is growing rapidly. The Southeast Asian paints and coatETHYL ACETATE CAPACITY IN U.S. ings market is expected to grow at 5-6% per year. Asia-Pacific China
Between 1990 and 2000, China increased capacity for ethyl acetate by over 14% and output by around 15%. Imports remained at a high level. The acetic acid/ ethanol esterification process is used by most producers in China and the operating rate is relatively low. Larger acetate units completed since 2001 include a 30,000-tpa unit in May 2001 by Shandong Jinyimeng Group, which now has a capacity of 80,000-tpa. In all, China has over 30 producers with a total capacity of around 391,700-tpa and an output of around 200,000tons during 2002. Shandong Jinyimeng Group and Yangzijiang Acetyl Chemical Co Ltd. are the two leading producers among the top-ten producers, with a capacity of 80,000-tpa each.
Producer
Annual capacity [million lbs]
Annual capacity [tons]
Celanese, Pampa, Tex. Eastman, Kingsport, Tenn. Eastman, Longview, Tex. Solutia, Springfield, Ma. Solutia, Trenton, Mich.
130 59 51 30 24
59,091 26,818 23,182 13,636 10,909
Total
294
133,636
Source: Chemical Market Reporter
Capacities are extremely flexible, as ethyl acetate can be made in the same equipment used to produce other acetate esters, depending on demand. Most commercial production is by esterification of acetic acid with ethanol or liquid-phase oxidation of n-butane with ethyl acetate as a by product, but some material is made China imported 45,800-tons of ethyl acetate in 2002 by condensation of acetaldehyde. The demand for ethyl and exported 11,000-tons. The apparent consumption of acetate in US was 71,000-tons in 2001 and 68,000ethyl acetate in China is about 238,200-tons, which is tons in 2002. Demand for the year 2006 is projected at expected to rise to 260,000-tons in 2005. While ethyl ace- 81,000-tons. tate is used mostly in inks and coatings worldwide, in China the main applications are pharmaceuticals and adhesives. The historical growth during the period 1997-2002 Several new plants are slated in China for post-2004. was -5.3% per year. Ethyl acetate is used for a variety Showa Denko is considering building a new plant in China of solvent and vehicle applications: Coatings, 60%; or expanding its Indonesian subsidiary by 20,000-tpa in a Process solvent, including pharmaceuticals and organic span of two years. If the company decides to build in China, synthesis, 15%; Printing inks, 15%; Miscellaneous, init will be in either Shanghai-Nanjing or Hong Kong- cluding adhesives and cosmetics, 10%. Guangdong, as these are areas where ethyl acetate demand is strongest. The additional output will take the firm’s Ethyl acetate is used as a solvent in a variety of coatoverall capacity to 300,000-tpa, making it the world’s big- ing formulations including epoxies, urethanes, gest manufacturer of ethyl acetate, surpassing BP. cellulosics, acrylics and vinyls. These coatings are used CHEMICAL WEEKLY
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for wood furniture and fixtures, agricultural, construction and mining equipment, containers and closures, auto refinishing, and maintenance and marine applications. Over the past twenty years, ethyl acetate coatings have been losing share to waterborne and highsolids coatings, powder and two-component coatings systems, due to environmental constraints on volatile organic compound (VOC) emissions. This conversion has apparently run its course, and that market which still remains should begin growing again, but at less than GDP growth. Ethyl acetate is used as a solvent in inks for flexographic and rotogravure printing, where its main function is to dissolve the resin, control the viscosity and modify the drying rate. As with industrial coatings, the decline in the use of acetate because of environmental constraints has largely been completed and future growth is estimated to be a healthy 3% per annum. While demand has fallen during the past five years, averaging a decline of 5% per year, production has held relatively steady at 270-mn pounds. During this time,
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ethyl acetate exports were increasing at a rate even higher than the domestic demand decline, 6.5%. The market, however, was balanced by a decline in imported material, amounting to -6.8% annually. With signs of the economy turning around ethyl acetate demand is already up considerably in 2003. Total demand for the year is projected to be 175-mn pounds – a considerable turnaround from the past five years. Consistent with this, exported product is down considerably over last year (down 20%, annualised), while imported product is up 50% over 2002. For the forecast period through 2006, demand growth is estimated to be 3.4% per year; with most of the growth occurring this year, then 2.0% per year thereafter. South America
The Brazilian company Cloroetil will use Davy Process Technology’s single-stage ethyl acetate process in its 50,000-tpa ethyl acetate plant at Sao Paulo, Brazil. Investment in the plant is e21.5-mn ($25.5-mn). The construction contract for the plant has been awarded to Ferrostaal. Construction of the plant would have begun in March 2004 and completion is scheduled for end-2005.
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