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ETHANOLAMINES AND SECONDARY PRODUCTS

Ethanolamines are industrially valuable products whose main use is for the manufacture of detergents by reaction with fatty acids. The principal secondary products of ethanolamines are morpholine, ethylenimine and ethylenediamine.

15.1. ETHANOLAMINE PROCESS Commercial production of ethanolamines (EOA) is by reaction of ethylene oxide with aqueous ammonia. The ethylene oxide reacts exothermically with 20% to 30% aqueous ammonia at 60 to 150C and 30 to 150 bar in a tubular reactor to form the three possible ethanolamines (mono-ethanolamine - MEA, di-ethanolamine - DEA and tri-ethanolamine - TEA) with high selectivity. The product stream is then cooled before entering the first distillation column where any excess ammonia is removed overhead and recycled. In the second column, ammonia and water are removed and the EOAs are separated in a series of vacuum distillation columns.

The composition of the reaction product stream can be influenced by temperature and pressure, but it is especially sensitive to the ratio of ammonia to ethylene oxide. Higher ratios of excess ammonia lead to a higher monoethanolamine content as shown in Table 15.1. The high triethanolamine

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content that results from an equimolar mixture of reactants indicates that the primary reaction with ammonia is slower than the secondary reactions46.
Table 15.1. Effect of Excess Ammonia on Ethanolamine Selectivity

Molar Ratio to EO) 10:1 1:1

Mono75 12

Selectivity Ratios Di21 23

Tri-ethanolamine 4 65

A typical ethanolamine flowsheet is shown in Figure 15.1. Nippon Shokubai has developed technology that uses a new zeolite catalyst. This new catalyst suppresses the formation of TEA and produces more MEA and DEA120. A process that was proposed by some students at Rice University is shown in Figure 15.2. They claim that a single column with multiple product streams (instead of the typical series of three columns) can achieve high purity separation while reducing material and energy costs. Their separation unit makes 99.7% MEA, 97.5% DEA and 99.6% TEA. They also claim that the design has the ability to handle varying production levels as well as different feed compositions121. Himtek Engineering in St. Petersburg, Russia offers ethanolamine (EOA) technology that operates at 40 to 70C and 15 to 35 atmospheres. The ammonia and part of the MEA are recycled. Three vacuum stills are used to separate the three products. This technology is protected by Russian patents No. 2,141,475 and No. 2,063,955122. EOAs are corrosive and will attack some plastics and rubbers. They are a moderate fire hazard. MEA and TEA are clear, viscous liquids with a mild ammonia-like odor. EOAs absorb water and carbon dioxide from air. DEA is crystalline or a viscous liquid. All are soluble in water and ethanol. Vapor is irritating to the eyes, skin and respiratory tract and depression of the central nervous system can occur. It can also be absorbed by the skin in toxic amounts120. Physically, EOAs are clear, viscous liquids at room temperature and white crystalline solids when frozen. Diethanolamine has the highest freezing point of the group, 28.0C, and monoethanolamine the lowest, 10.5C. They all have comparatively high boiling points, although at elevated temperatures they are subject to decomposition, particularly diethanolamine. Their odors are ammoniacal to varying degrees, with monoethanolamine being the most marked. The ethanolamines are hygroscopic and miscible with water, most alcohols, and polyols. They and their aqueous solutions are alkaline. Being bifunctional, ethanolamines react with acids to form esters or salts, and most of their industrial applications are dependent to some degree on these features.

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15.2. PRODUCTION
All EOA plants make a mixture of products. The most important is MEA, which accounts for about half of total production. It is followed by DEA with 30% to 35% of production. As of April, 2001 INEOS plc is the largest global producer followed by BASF and Huntsman. EOA demand is growing between 4% and 6% annually with MEA and DEA growth rates substantially exceeding that for TEA. In 2001 EOA supply exceeds demand, and the oversupply situation will continue through 2002 with startups of more new plants. In 2000 European operating rates were at 86% of capacity. The European operating rates were expected to fall to 75% in 2003, but then recover to 85% by 2005. About 50% of EOA capacity is in the Americas, more than 30% is in Europe and the balance is in the Pacific Rim and the Middle East. Table 15.2 summarizes world consumption and growth rates for EOA38, 120. Table 15.2. World Consumption of Ethanolamines and Growth Rates120 Region Americas Western Europe Asia Middle East / Africa Totals Americas Western Europe Asia Other Totals
1995

Consumption (thousands of tonnes) 2002 2000 2005

279 260 99 27 665 . .

358 329 157 60 904

388 377 196 30 988 -

424 417 297 36

5.1 4.8 9.7 17.3 6.3

3.1 3.2 4.6 8.4 3.8

The historical prices (1995 to 2000) for different ethanolamines are listed below249: MEA: DEA: TEA: High = $0.59/lb, Low = $0.56/lb High = $0.61/lb, Low = $0.57/lb High = $0.67/lb, Low = $0.67/lb

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15.3. USES EOA production is consumed in the following areas: Detergents (32%), Ethyleneamines (20%), Gas Purification (17%), Metal Cleaning (10%), Herbicide Intermediates (10%), Textiles (5%) and Miscellaneous (6%) . At 140 to 160C, the fatty acid can react 1) with the amino group on the EOA to form a fatty acid ethanolamide, 2) with the hydroxyl group on the EOA to give a fatty acid aminoethyl ester or 3) with both groups to form a di-fatty acid ethanolamide ester46. MEA is used as an intermediate for cosmetics, surface-active agents, emulsifiers and plasticizing agents; as a gas-scrubbing agent for absorption and removal of and from refinery and natural gas streams; and in and ammonia manufacturing123. DEA is used as an intermediate for cosmetics; as surface-active agents in household detergents and textile specialties; in insecticides and herbicides; in petroleum demulsifiers; as a gas scrubber in refinery and natural gas operations; in waxes, polishes and coatings emulsifiers; in soluble oils; and as corrosion inhibitors123. TEA is used as an intermediate for surface-active agents used in textile specialties, waxes and polishes, herbicides, petroleum demulsifiers, toilet goods, cement additives, cutting oils, and photograph-film developers; as corrosion inhibitors; as a dispersant for dyes, casein, shellac, and rubber latex; as sequestering agents; and as a rubber chemicals intermediate123. 15.4. SECONDARY PRODUCTS OF ETHANOLAMINE 15.4.1. Morpholine Morpholine is a solvent and intermediate for optical brighteners and rubber chemicals. It is also a corrosion inhibitor, especially in steam boiler systems. Some other uses include: An emulsifier for cosmetics, rubless waxes, and polishes, A separating agent for volatile amines, An intermediate for textile lubricants, softening agents, adjuvants in medical applications, whitening agents, sizing emulsifiers, rubber vulcanization accelerators, antioxidants, surface-active agents, plasticizers, viscosity improvers, insecticides, fumigants, herbicides, dyes, and catalysts.

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In one process morpholine is obtained from DEA by dehydration with 70% to close the ring:

In the USA a newer production route has eclipsed the cyclization of diethanolamine. In this method, diethylene glycol, ammonia and a little hydrogen react at 150C to 400C and 30 to 400 bar over a catalyst containing Ni, Cu, Cr or Co to give morpholine. The process is operated by Huntsman Chemical Company in Port Neches, Texas, but more details are not known46. Morpholine is a colorless, oily, hygroscopic, volatile liquid with a characteristic amine odor. It is heavier than air and, as a result, the vapor can travel a significant distance to a source of ignition and flash back. Morpholine can undergo a diversity of chemical reactions. It is an amino ether. The ether function of the molecule is typically inert and most of the reactions involve the secondary amine group. Morpholine is distributed as an anhydrous liquid and as 40% and 88% solutions with water. It is marketed as a product with approximately 99% purity. 248 The physical properties of morpholine are shown in Table 15.3 . Table 15.3. Physical Properties of Morpholine Chemical Formula: Molecular Weight: Boiling point at 101.3 kPa Melting point Relative density (water=l) Solubility in water Vapor pressure, kPa at 20C Relative vapor density (air=l) Relative density of the vapor / air mixture at 20C (air=l) Flash point (open cup) Autoignition temperature Explosive limits, vol% in air Octanol/water partition coefficient as

87.1 129C -5C

1.0
miscible 1.06 3.00 1.01 38-43C 310C 1.8-15.2 -0.86 (at pH 5)

Morpholine is a colorless hygroscopic liquid, with a characteristic odor; It decomposes on heating and produces nitrous oxides. It is a base that reacts violently with acids, and it is corrosive to aluminum, zinc and copper. Morpholine reacts with oxidants and nitrites. In addition, the carcinogenic Nnitrosomorpholine can be formed from nitrosation of morpholine248.

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15.4.2. Ethylenimine Ethylenimine can be made from MEA. BASF and Hoechst developed an industrial process that has two steps.

If the imine formation is conducted in a flow tube, residence times of 4 to 10 seconds can be used to suppress secondary reactions such as the polymerization of ethylenimine. The imine selectivity then increases to 80% to 85% (based on MEA)46. Dow makes ethylenimine by reacting 1,2-dichloroethane with ammonia in the presence of CaO at about 100C:

Most ethylenimine is converted into polyethylenimine, a processing aid in the paper industry. It also serves as a reaction intermediate when ureas are formed with isocyanates46.