Morpholine Will Be Oversupply

Morpholine is one of the important fine chemicals. It can be used
to produce rubber accelerators, antirust agents, anticorrosive
agents, cleaning agents, scale inhibitors, pain killers, local
anesthetics, surfactants, optical bleaching agents, fruit
antistaling agents and textile dyeing/printing agents and has
extensive applications in rubber, pharmaceutical, pesticide,
dyestuff and coatings sectors.
   Methods for the morpholine production include the
diethanolamine (DEA) process and the diethylene glycol (DEG)
process.
   The DEA process is a traditional production method. Raw
material diethanolamine has to be imported and has a high price.
The reaction yield is low, the production cost is high and
products already no longer have market competitive edge.
   The DEG process is a new morpholine production method
developed in recent years. Two thirds of domestic producers use
this process today. The utilization rate of diethylene glycol
is not high in China and a considerable amount of the product
is for export at low price. Using diethylene glycol to synthesize
morpholine is therefore an economically rational method with
development prospect.

Rapid production development

The rapid development of the rubber industry and especially the
tire industry in China in the early 1990s promoted and stimulated
the morpholine production. Not only the product output and the
quality of morpholine have improved greatly today, the synthesis
technology has also been shifted from the traditional DEA
process to the DEG process popular in foreign countries. The
product quality and the raw material consumption in some
domestic producers have reached the world advanced level. There
are however many medium and small producers with a great
difference in production technology and product quality.
   China has more than 20 morpholine producers. The total
capacity of major production units has reached 24.5 thousand t/a.
The output was around 12.3 thousand tons, the demand was around
15 thousand tons in 2005 and import had to be made to bridge the
deficit.
   The Research Institute of CNPC Jilin Petrochemical Co., Ltd.
conducted research on the synthesis of morpholine through the
DEG low-pressure ammoniation process and developed related
catalysts. A 500 t/a unit was constructed in Liaoyuan Fine
Chemical Plant of CNPC Jilin Petrochemical Co., Ltd. in 1990.
The capacity of the unit has been expanded to 3 thousand t/a today.
The plant has become a morpholine producer with the most complete
product varieties in China. The product quality has reached the
level of similar products made by Germany. Quite a few producers
in China have used the technology and constructed commercial
production units. The 8 thousand t/a unit in Anhui Haoyuan
Chemical Plant is the largest production unit in Asia. The 8
thousand t/a unit constructed by Yifang Industrial Corporation
of CNPC Liaoyang Petrochemical Fiber Engineering Co., Ltd.
started production in December 2005. (CCR2006, No. 7) The
completion of several morpholine units has satisfied the
increasing demand in the domestic market, changed the situation
of massive import and produced satisfactory economic benefits
and social benefits.
   In the synthesis of morpholine through the reaction between
diethylene glycol and ammonia, besides a considerable amount of
intermediate product diethylene glycol ammonia, the product
usually contains some ether impurities such as ethylene glycol
monomethyl ether. As the boiling point of ether impurities is
very close to the boiling point of morpholine, the separation
is difficult and the product application is affected. CNPC Jilin
Petrochemical Co., Ltd. has overcome the problems in the
synthesis of morpholine through the DEG ammoniation process and
developed a new catalyst for the production of morpholine
through the DEG ammoniation process. The new catalyst has a low
content of active ingredients but great strength and excellent
activity and selectivity. It has been used in most domestic
producers. A second-generation catalyst variety has already
been developed and its application evaluation is being conducted
in the morpholine unit of Liaoyuan Fine Chemical Plant of CNPC
Jilin Petrochemical Co., Ltd.

Market prospect is not optimistic

Morpholine can be used to synthesize several dozen
pharmaceuticals such as pain killers, local anesthetics,
sedatives and stimulants for respiratory systems and blood
vessels. Morpholine in China is mainly used to synthesize
moroxydine, ibuprofen, naproxen, dichloroaniline and sodium
phenylacetate. The consumption of morpholine in the
pharmaceutical sector is around 1 thousand tons a year today.
As these pharmaceuticals are all traditional varieties, the
market demand will have no great increase. It is expected that
the demand of morpholine in the pharmaceutical sector will be
around 1.5 thousand tons in 2007.
   Morpholine as metal corrosion inhibitor is mainly used in the
corrosion prevention of iron, copper, zinc and lead. The
application is just starting in China. The application of
morpholine in solvents, surfactants, fluorescent whitening
agents, textile assistants and catalysts also started rather
late in China.
   Morpholine in foreign countries is mainly used to synthesize
rubber accelerators (such as NOBS
(N-oxydiethylene-2-benzothiazole sulfenamide), DS and OTOS).
The major application is the synthesis of NOBS. The consumption
of morpholine in rubber accelerators accounted for more than 50%
of the total in advanced countries and regions such as the United
States, Western Europe and Japan before the 1990s. In China more
than 30% of the morpholine consumption is in the synthesis of
NOBS.
   The toxicity of accelerators that can easily generate
hazardous nitrosamine in rubber processing has aroused great
attention in the international community in recent years. Years
ago many countries already took sulfamide accelerators as the
research target for the possible generation of nitrosamine.
Analysis to their nitrosamine-generating mechanism and their
substitution has been conducted. Research proves that
accelerator NOBS with excellent property that holds a leading
position in the international market indeed generates
nitrosamine in its use. Many restrictive laws and regulations
have therefore been formulated. For example, Germany issued laws
and regulations on controlling the nitrosamine content in as
early as 1982. The United States, Japan, France and Britain have
actively developed new accelerators with no generation of
nitrosamine and stopped the use of accelerators with generation
of nitrosamine.
   The consumption of morpholine in foreign countries is
therefore going down with the prohibition in the use of
accelerator NOBS. China has not yet formulated laws and
regulations on the prohibition in the use of accelerator NOBS.
Even if there are no such laws and regulations in China,
foreign-funded tire producers request rubber accelerators in
China to be environmental friendly. The replacement of NOBS by
non-toxic accelerators has become an inevitable trend. The
demand of NOBS in China has reduced distinctly in recent years.
According to the development program for rubber auxiliaries,
China will basically not use secondary amine accelerators with
the decomposition of nitrosami