Feedstock Deficit Curbing China's Ethanolamine Production

By Yan Qingning, Gao Fugeng, CNCIC

Ethanolamines, including monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA), are now mainly produced by the process with ethylene oxide and ammonia as raw materials.

1. Production capacity increasing rapidly

World total capacity of producing ethanolamine was 1.27 million t/a in 2001 and reached 2.2 million t/a in 2011, with a net increase of 0.93 million t/a. The annually average growth rate was 5.7% between 2001 and 2011, leading in the chemical industry.  
Before 2006 China's production capacity of ethanolamine had been around 40 000 t/a for many years, accordingly the annual output hovered between 30 000 tons and 40 000 tons. As of 2008 China's ethanolamine capacity reached 120 000 t/a. In 2009 the capacity increased to 170 000 t/a and the output approached to 100 000 tons. The total capacity rocketed to 410 000 t/a in 2010, representing a growth of 240% year on year. In 2012 China had 560 000 t/a capacity of ethanolamines, and produced 240 000 tons of ethanolamines in total. Due to the rapid expansion of capacity, this industry operated well below the full capacity. After 2008 the capacity utilization rate stayed at 40% - 50%. China's major ethanolamine producers and their capacities are listed in Table 1.   

2. Feedstock supply constraining the production.

By investigation and analysis, it was found that the supply deficit of raw material ethylene oxide caused the low capacity utilization rate in the ethanolamine production in China. Ethylene oxide is an important raw material for producing ethanolamine. Currently 65% of China's ethylene oxide consumption was contributed by the production of ethylene glycol, and the remaindering 35% of commercial ethylene oxide is consumed in the production of non-ionic surfactants, ethanolamines, ether of ethylene glycol, polyether polyols, medicines etc.   
Given to its low boiling point of 10.7 degree Centigrade at atmosphere, and characters of flammable and explosive, ethylene oxide is not suitable for long distance delivery, which resulting in few imports of commercial ethylene oxide. In China the production of ethylene oxide is monopolized by several companies who control the pricing decision in the market. With the rapid development of China's ethylene oxide downstream production in recent years, the domestic ethylene oxide users suffered supply deficit, particularly in the ethanolamine sector. Due to its physical and chemical characters causing difficulties in storage and transportation, ethylene oxide must be sold as soon as it is produced, leaving a little amount for commercial sale. The market price was hence pushed to create new record one by one.
By comparing the market price trends of China-made ethanolamines, the imported ethanolamines and ethylene oxide in the period of 2009 to 2012, it can be seen that the price of imported ethanolamines has always been below the price of domestically made ethylene oxide, causing that the import of ethanolamines remained strong even if it faced against the antidumping measures of China's government. China-made ethanolamine producers have to remain a low operation rate because of high price of raw material ethylene oxide.

Table 1   China's Major Ethanolamine Manufacturers as of 2012  (kt/a)

Company                                     Capacity    Products
Fushun Beifang Chemical Co., Ltd.                30        MEA, DEA, TEA
Liaoning North Chemical Industries Co., Ltd.     50        MEA, DEA, TEA
Fushun Jiahua Chemical Co., Ltd.                 20        TEA
Shanghai Fujia Fine Chemical Co., Ltd.             40        TEA
Jilin Zhongxin Chemical Group Co., Ltd.         60        TEA
Jilin Beifang Huifeng Chemical Co., Ltd.         20        TEA
Honam Petrochemical (Jiaxing) Co., Ltd.         50        MEA, DEA, TEA
AkzoNobel Ethylene Amines (Ningbo) Co., Ltd.     100        MEA, DEA, TEA
Jiaxing Jinyan Chemical Co., Ltd.                100        MEA, DEA, TEA
Oriental Petrochemical (Yangzhou) Corporation     40        MEA, DEA, TEA
Shijiazhuang Haisen Chemicals Co., Ltd.         6        TEA
Xingtai Lanxing Auxiliary Factory                 5        TEA
Hubei Xianlin Chemical Co., Ltd.                 40        MEA, DEA, TEA
Maoming Petrochemical Shihua Co., Ltd.             6        MEA, DEA, TEA
BASF-YPC Co., Ltd.                                 76        MEA


3. Active downstream industries

Ethanolamines are mainly used to produce surfactants, medicines, pesticides, polyurethane products, auxiliaries for textiles, gas purifiers, rubber processing auxiliaries etc. Of which, MEA is mainly used to manufacture medicine products, textile auxiliaries, papermaking auxiliaries. DEA is consumed in the production of surfactants, pesticides, medicine products, cooling agent, cleaning agent, desulfurization agent for petroleum. TEA is used to make cement grinding agent, cosmetics, processing auxiliaries for rubber and metals, chemical weapons.
A.  Surfactants
In the production of surfactants, ethanolamines are main raw materials. TEA and DEA can be directly used as surfactants. Ethanolamines can also be reacted with many kinds of acids to synthesis important common surfactants, for example, DEA can be reacted with fatty acids (such as lauric acid and cocoatic aicd) to produce alkanolamide, TEA can react with sodium dodecylbenzenesulfonate to make triethanolamine dodecylbenzenesulfonyl.
B.  Pesticides
In the pesticide industry, DEA is mainly used to produce herbicide glyphosate. There are two processes for the production of glyphosate, the TEA process and the glycine process. The previous one has technical advantages than the latter. But the glyphosate made by DEA, which has a higher cost because of high DEA price, can not compete with that made by glycine and has to be sold abroad.   
C.  Medicines
Medicines made by ethanolamine contain anti-infective drugs such as furazolidone, moroxydine and ketoconazole, nutrition enhancers like taurine, anti-parasitic drugs like tetramisole, and cardiovascular drugs like dipyridamole.
D.  Polyurethane products
Ethanolamines (TEA accounting for majority share) can be used as catalyst and crosslinker in the manufacture of polyurethane articles. The production of casting rigid polyurethane foaming articles commonly uses TEA as catalyst because TEA has a low activity. In the production of semi-rigid and high resilience polyurethane articles, TEA or DEA can be selected as crosslinker. In addition, TEA can be used as crosslinker in processing thermal polyurethane elastomers articles.
E.  Gas purification
Ethanolamines can be used as desulfurization agent in gas purification. It is a common high efficient desulfurization agent in the world. Now many petroleum refining facilities and medium and large scale synthetic ammonia facilities in China employ the ethanolamine desulfurization process.   
F.  Rubber processing auxiliaries
TEA is one of the important rubber processing auxiliaries. It is often used as vulcanization activator for non-carbon black reinforced rubber materials, and can also play the roles of dispersing agent and waterproofing agent. When silica white or other delay vulcanization fillings are used as reinforced agents, TEA is an indispensable auxiliary.
G.  Textiles
At present China has already been the worldwide largest synthetic fiber producing country, needing large amount of textile auxiliaries each year. In the textile industry, ethanolamines are mainly used as finishing agent, fabric softener and emulsifier.    
H.  Fluorescence brighteners
Ethanolamines are used to make fluorescence brighteners VBL for textiles. VBL is an old variety in the fluorescence brightener family. China manufactures plenty of VBL each year and exports much of them. Ethanolamines involve in the production of liquid fluorescence brightener BBU for papermaking. China's demand for BBU has grown continuously.    
I.  Cleaning and processing of metals
Relying on its excellent emulsification and weak corrosion ability, ethanolamines acquire wide applications in metal cleaning and are also a good choice in the formulation of metal processing liquid.  
J.  Polyvinyl pyrrolidone
The consumption of MEA in the production of polyvinyl pyrrolidone (PVP) is worth to concern. PVP is an important fine chemical serving the production of drugs, foodstuffs and beer. China now has a dozen of PVP production plants.
K. Grinding agent for cement and concrete admixtures
TEA is the main raw material for the cement grinding agent, accounting for 75% in the grinding agent formulation. Addition of grinding agent can help to increase the production of cement by 10%-20%.
TEA can be directly added in cement clinker with a concentration of 0.01 percent, which can help to lift cement production and make the cement finer and reduce energy consumption. This method is widely employed by many cement manufacturers
TEA is also the main raw material of concrete water reducer and early strength agent.
L. Ethylene amines
Ethylene amines refer to acyclic polymerizing products of ethylenediamine, such as ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine and pentaethylenehexamine, and cyclic amines such as piperazine, aminoethylpiperazine and hydroxyethyl piperazine.  
Ethylene amines, the important fine chemical intermediates, are widely used in the sectors of organic synthesis, medicines, dyestuffs, pesticides, chemical auxiliaries, rubber and plastic auxiliaries, organic solvent, epoxy solidifier etc. Currently more than 90% of China's ethylene amines consumption relies on imports. Ethylene amines are one of the fine chemical intermediates for China to develop urgently.
By raw material routine, the production process of ethylene amines can be divided into two kinds. One is the ethylene dichloride process and another is the ethanolamine process, with a capacity split of 50:50.  
M. Others
Ethanolamines can also be used to produce automobile anti-freezing agent in which the typical content of ethanolamines is 0.4 percent. Coatings production needs MEA and DEA while leather auxiliaries production needs DEA and TEA. In the cosmetics sector, TEA is needed in the production of emulsified cosmetics such as lotions, emulsified foundation cream and hair cream. Some veterinaries, for example, olaquindox and furazolidone are also important consumers of ethanolamines.  
From 2004 to 2012 China's consumption distribution of ethanolamines has changed a lot, of which the largest growths came from the consuming sectors of polyurethane products, grinding agent for cement and concrete admixtures.
With the changes in the consumption distribution of ethanolamines, the relative consuming shares of MEA, DEA and TEA followed to change, which are shown in Table 2.  

Table 2   China's Ethanolamines Consumption Share in 2004-2012

Year    MEA    DEA    TEA
2004    24%    59%    17%
2009    22%    53%    25%
2012    26%    29%    45%


4. Domination of imported ethanolamine will remain unchanged

In supply, China's ethanolamines production capacity has exceeded 500 000 t/a, which should have met the demand from all downstream industries if the capacity is fully utilized. However, the country's average capacity utilization rate has been very low, constrained by high price and supply shortage of raw material ethylene oxide. The imported ethanolamines occupy a domination position by lower cost comparing with China-made products. It is predicted that the imported ethanolamines will continue to hold a big share in Chinese market in a long term, which will place a huge pressure on China's domestic producers.
Presently China is still eager to develop coal chemical industry and has got big progress in the industrialization of coal to olefin and coal to ethylene glycol. New production routine of ethylene glycol can help to ease the pressure of domestic supply deficit, in turn, it will help to increase the supply of commercial ethylene oxide or drive the ethylene oxide price to go down and therefore benefit the domestic ethanolamines production. Ethanolamines players should moderately pay attention to this opportunity but shall not wish more on its assistance to solve the difficult situation of ethylene oxide supply in a short term.  
What is urgent for China's ethanolamines producers is to improve their own production technology and management level, to reduce raw materials consumption to the world advanced level, therefore to cut the cost and enhance competitive edge. They shall do better in the cooperation with domestic ethylene oxide producers to gain the best price and sufficient supply in order to improve the capacity utilization rate of ethanolaimines plants.