Industrial Chain is Key to Development of Cyclohexanone in China

By Song Chao, Technology Center of Sinopec Baling Petrochemical Co., Ltd

China’s cyclohexanone sector arose from the development of the caprolactam sector. When the preferred technology for producing caprolactam changed from the phenol route to the cyclohexane route, the cyclohexanone sector emerged in China. In the early days, cyclohexanone was only an intermediate product of caprolactam. Shanxi Taiyuan Chemical Plant, Jinxi Chemical Plant, Phosphate Fertilizer Plant of Sinopec Nanjing Chemical Industry Co., Ltd and the former Nylon Plant of Hunan Yueyang Petrochemical Co., Ltd all had cyclohexanone capacity that was matched to their caprolactam units, and no cyclohexanone was supplied to the market as a commodity. With the adjustment of the caprolactam product portfolio as well as the constant expansion of cyclohexanone applications, especially in the paint, ink, coatings and adhesive sectors as a high-grade organic solvent, the manufacture of cyclohexanone has truly become a sector unto itself. China has made constant breakthroughs in the technology for making cyclohexanone, and the capacity of most domestic cyclohexanone units has been expanded. However, the caprolactam sector has not developed in tandem due to technical constraints. The amount of cyclohexanone sold as a commodity has therefore increased to a considerable scale.

1.Both capacity and output increase constantly in China.

Since 2006, with the increasing application of cyclohexanone in sectors such as caprolactam, coatings/paint/ink solvents, dyestuff assistants, pharmaceutical assistants, polishing agents and adhesives, China’s output of cyclohexanone has increased steadily. The domestic output of cyclohexanone reached 880 000 tons in 2012, 1.92 times its 2006 level. China’s output of cyclohexanone during 2006-2012 is listed in Table 1.

Table 1   China’s Output of Cyclohexanone, 2006-2012

Year        2006    2007    2008    2009    2010    2011    2012
Output (kt)    459        490        423        580        679        783        880
Growth (%)    6.68    6.68   -13.65    37.08    17.14    15.30    12.30


With the development of downstream sectors, both the capacity and output of cyclohexanone in China have increased constantly. In 2007, China had ten cyclohexanone producers with a total capacity of 481 000 t/a. In 2012, China’s capacity to make cyclohexanone reached 1.75 million t/a. China’s major cyclohexanone producers in 2012 are shown in Table 2.

Table 2   China’s Major Cyclohexanone Producers, 2012 (kt/a)

Producer Capacity to make cyclohexanone    Capacity to make adipic acid Capacity
to make caprolactam
Shandong Haili Chemical Co., Ltd            380        225      200
Sinopec Baling Petrochemical Co., Ltd        260         -      300
Baling Hengyi Caprolactam Co., Ltd            200         -      200
Shandong Hongye Chemical Group Co., Ltd        160        250      100
Zhejiang Juhua Group Corporation            150         -      50
Shandong Hualu Hengsheng Chemical Co., Ltd    120        160      -
Sinopec Nanjing Chemical Industry Co., Ltd    120         -      -
Shijiazhuang Coking Chemical Group            100         -      -
PetroChina Liaoyang Petrochemical Co., Ltd    70        140      -
Shanxi Fengxi Chemical Group????            60        70      -
Fujian Dongxin Petrochemical Co., Ltd        60         -      -
Nanjing DSM Dongfang Chemical Co., Ltd        50         -      200
Neijiang Tianke Chemical Industry Co., Ltd    20         -      -
Total                                        1 750    845     1 050

Most of China’s cyclohexanone producers have matching downstream caprolactam and adipic acid units. Shandong Haili Chemical Co., Ltd is the largest cyclohexanone producer in China. Its capacity to make cyclohexanone reached 380 000 t/a in 2012.
In the next two years, with the growth of downstream demand, combined with the gradual startup of cyclohexanone projects that are now being built or planned for construction, China’s production and consumption of cyclohexanone will grow dramatically. China’s cyclohexanone projects being built in 2013 are listed in Table 3. All are matching units of caprolactam or adipic acid units, except the one being built by Jining Zhonglian Chemical Co., Ltd.

2. Sixty percent of cyclohexanone is consumed in the production of caprolactam.

With the growth of capacity to make caprolactam and adipic acid, the world’s capacity to make cyclohexanone has expanded. Cyclohexanone is also finding extensive use as a high-grade organic solvent in sectors such as coatings, ink, pharmaceutical, pesticide, adhesives and photosensitive materials, and it has a growing commodity market. China's consumption mix of cyclohexanone is 60% for caprolactam, 15% for coatings sector, 7% for rubber auxiliaries and around 18% for others.

3. Exports become an important growth opportunity for the market.

Over the years, China’s import volume of cyclohexanone has been more than its export volume. However, with the domestic capacity expansion, the gap between the import volume and export volume has constantly narrowed. Furthermore, due to the drastic growth of demand for cyclohexanone in Japan and Korea, China’s export volume of cyclohexanone greatly climbed to 40 000 tons in 2011, exceeding the import volume for the first time. In 2012, with the increased demand for cyclohexanone in China caused by the startup of new caprolactam units, China’s export volume of cyclohexanone was reduced considerably, but was still more than its import volume. The exports of cyclohexanone have become an important point of growth for the market. China’s import and export of cyclohexanone during 2006-2012 are shown in Table 4.
At present, many domestic enterprises have planned to construct or expand cyclohexanone and caprolactam units. Because of the huge investment and complex technology of caprolactam projects, most of the enterprises have chosen to first construct cyclohexanone units. Some enterprises only construct cyclohexanone units without building matching caprolactam units. This situation has resulted in more newly constructed and expanded cyclohexanone units in China in the last two years. Considering the expansion of the domestic cyclohexanone capacity as well as the price difference between the domestic market and overseas markets, it is expected that China’s total import volume of cyclohexanone will decline gradually in the next few years. With the output growth of cyclohexanone and improvement of product quality in China, it is expected that China’s export volume of cyclohexanone will increase continually in the next few years.

4. Strengthen the development of environmental protection technology and reduce the production cost.

China’s capacity to make cyclohexanone will continue to grow in the future. Because the demand does not grow synchronously, China should control the pace of domestic cyclohexanone development, strengthen the development of related environmental protection technology, reduce production costs, enhance the competitiveness of products, speed up the development and application of downstream products, strive to take an increasing share of the international market, and promote the healthy development of the cyclohexanone sector as well as related industries.

5. Promote technological progress and curtail pollution.

The cyclohexane oxidation process is the mainstream production process, both at home and abroad. Except for some cyclohexanone units of Shijiazhuang Coking Chemical Group and Shandong Haili Chemical Co., Ltd, all domestic cyclohexanone units use this process. However, the process has some drawbacks such as low yield (being only 75%-80%), excessive by-products, large discharge volumes of “the three wastes” (waste gas, waste water and industrial residue), and higher requirements to ensure safe operation. Therefore, China should develop new cyclohexane oxidation processes and catalytic systems, improve the atomic economy of reaction, reduce the cost of raw materials, reduce energy consumption and reduce environmental pollution. The partial hydrogenation of benzene to cyclohexene and cyclohexene hydration dehydrogenation to cyclohexanone is a cyclohexanone production method with low environmental impact and advanced technology. China should strengthen research and applications of this technology.

Table 3   China’s Cyclohexanone Projects Being Built in 2013

Producers                            Location         Capacity (kt/a)    Remarks
Jining Zhonglian Chemical Co., Ltd    Jining of Shandong province    60     Commercial cyclohexanone
Shandong Haili Chemical Co., Ltd    Yancheng of Jiangsu province    200    Matched with 200 kt/a caprolactam unit
Sinopec Nanjing Chemical Industry Co., Ltd    Nanjing of Jiangsu province    100     Matched with 200 kt/a new caprolactam unit of DSM
Liaoning Huafeng Chemical Co., Ltd    Liaoyang of Liaoning province    100    A subsidiary of Zhejiang Huafeng Spandex Corporation
Hubei Sanning Chemical Industry Co., Ltd????    Zhijiang of Hubei province    100    Matched with 100 kt/a caprolactam unit
Luxi Chemical Co., Ltd    Liaocheng of Shandong province    200    Matched with 200 kt/a caprolactam unit
Fujian Tianchen Yaolong New Material Co., Ltd    Fuzhou of Fujian province    200    Matched with 200 kt/a caprolactam unit
Zhejiang Shuyang Chemical Co., Ltd    Quzhou of Zhejiang province    60    Matched with 80 kt/a adipic acid unit
Total        1 020    


Table 4   China’s Import and Export of Cyclohexanone, 2006-2012

Year  Import volume (tons)    Import value (US$ million) Export volume (tons)    Export value (US$ million)
2006    45 200     59.2225    3 000    5.5954
2007    19 500     28.4791    2 700    5.3095
2008    4 200     6.4709        700        1.4999
2009    11 200     12.1670    1 000    1.7868
2010    15 100     25.3564    8 600    16.3983
2011    13 300     23.7214    40 400    80.7995
2012    9 300     16.6359    29 500    55.9394


6. Promote the application of coking benzene and reduce petroleum consumption.

In the mainstream production process, petroleum benzene is used as raw material, both at home and abroad. China's wealth of coal resources and comparative scarcity of oil brings with it unique options in the raw material sourcing and production costs of cyclohexanone. With the high price of petroleum in the world market, the operation of the domestic cyclohexanone sector faces difficulties. Therefore, the development and utilization of China’s advantageous resources through using low-cost coking benzene as raw material to produce cyclohexanone is one of the effective methods for broadening the sources of raw materials and reducing the cost.

7. Develop new markets.

Because cyclohexanone is an important chemical raw material used mainly as an intermediate of caprolactam and adipic acid, the development of the cyclohexanone sector is tied to the development of the other two sectors. Improving and promoting the development of downstream sectors can straighten out the upstream sector. In the past, the slow expansion of the capacity for both adipic acid and caprolactam restricted the development of downstream sectors. However, in the last two years, excessive expansion of that capacity has led to oversupply in the domestic market. Therefore, only by coordinating the development pace of upstream and downstream sectors can the whole industrial chain develop smoothly.
Cyclohexanone is also an important industrial solvent. China should continue to expand the fields of cyclohexanone applications, extend the industrial chain and improve the added value of products.
In addition, strengthening the application and development of cyclohexane and cyclohexanol – the intermediate products of cyclohexanone – is also an effective strategy for promoting the development of the cyclohexanone sector. Cyclohexane, an organic solvent with low toxicity and good solubility, is extensively used for the production of SBS (styrene-butadiene-styrene block copolymer), highly water-absorbent resin, pesticides and shoes. In recent years, China’s import volume of cyclohexane has climbed rapidly. Cyclohexanol is also extensively used in sectors such as pesticides, pharmaceuticals and resins, and its use indirectly expands the application fields of cyclohexanone.