China's Rubber Auxiliary Sector Focuses on Green Production


Production

In 2011, China had around 150 rubber auxiliary producers with a combined capacity of 1.007 million t/a, of which around 20 enterprises had a capacity of over 10 thousand t/a and around 20 producers had a production value of more than RMB200 million. After years of development, domestic rubber auxiliary sector has changed significantly.
   At present, some influential production enterprises have gradually emerged in China, of which major rubber antioxidant producers include p-phenylenediamine and quinoline rubber auxiliary enterprise Sinopec Nanjing Chemical Industry Co Ltd, p-phenylenediamine rubber antioxidant enterprise Shandong Sinorgchem Co Ltd and quinoline rubber antioxidant enterprise Tianjin Labo Auxiliary Plant, etc. The main rubber accelerator enterprises in China include Shandong Shanxian Chemical Co Ltd, Northeast Auxiliary Chemical Co Ltd, Tianjin No.1 Organic Chemical Plant, Puyang Weilin Danei Chemical Co Ltd and Henan Hebi Jinshi Chemical Co Ltd, etc. The scale of the antiscorching agent unit in Shandong Yanggu Huatai Chemical Co Ltd and silane coupling agent unit in Nanjing Shuguang Chemical Group Co Ltd is the largest in Asia.

Demand is growing and production is expanded

During 2009-2011, China’s rubber auxiliary sector once again conducted the capacity expansion upsurge. After the expansion, the strength of the enterprises became stronger and the selected locations for the expansion are more suitable for the development of rubber auxiliary sector. According to the statistics made by China Rubber Industry Association, the sales revenue in the domestic rubber auxiliary sector was expected to reach around RMB14.0 billion in 2011, up around 7.7% year-on-year.
   With the bright prospect of the domestic demand, enterprises actively expand their production and improve their competitiveness.
   The new expansion projects in Table 3 are mostly under construction or the preparation stage. If all the projects are completed and put into operation, the newly added capacity of rubber auxiliaries will reach 210 thousand t/a (excluding the capacity of the old factories planned to be closed in Tianjin No.1 Organic Chemical Plant and Zhenjiang Sopo Chemical Co Ltd). In addition, there are still many companies that are constructing or plan to construct rubber auxiliary projects in China.

Table 1 China’s Major Rubber Auxiliary Producers in 2010 (thousand t/a)

Producer    Capacity     Product variety
Shandong Sinorgchem Co Ltd    95    Antioxidant 4010NA and 4020
Shandong Shanxian Chemical Co Ltd    85    Accelerator M, CBS, NS, NOBS and TMTD, and antioxidant RD
Sinopec Nanjing Chemical Industry Co Ltd    75    Antioxidant RD, 4020 and 4010NA, and accelerator M and CBS
Tianjin Labo Auxiliary Plant    70    Antioxidant RD, and accelerator M, CBS and DZ
Tianjin No.1 Organic Chemical Plant    50    Accelerator M, DM, CBS, DZ, D and TMTD, and Antioxidant MB
Northeast Auxiliary Chemical Co Ltd    30    Accelerator M, DM, CBS, DZ, NS and TMTD, and Antioxidant 4020
Shandong Yanggu Huatai Chemical Co Ltd    30    Accelerator NS, antiscorching agent CTP and peptizer
Zhenjiang Sopo Chemical Co Ltd    25    Accelerator M, DM, CBS, DZ, NOBS and NS
Puyang Weilin Danei Chemical Co Ltd    25    Accelerator M, CBS, NS and DM
Zhejiang Zhedong Auxiliary Co Ltd    25    Accelerator M, CBS and NS, and processing auxiliaries
Wuhan Jinghe Chemical Co Ltd    25    Super accelerator and peptizer A
Jiangsu Ate Polymer Materials Co Ltd    20    Accelerator CBS and NS, and antioxidant 4020 and RD
Nanjing Shuguang Chemical Group Co Ltd    20    Silane coupling agent Si-69
Shandong Rongcheng Chemical Complex    20    Accelerator M, DM, CBS and NOBS, and antioxidant RD
Henan Kaicang Chemical Co Ltd     20     Accelerator M and DM, and antioxidant RD
Henan Hebi Jinshi Chemical Co Ltd    12    Accelerator D, M, DM and TMTD, and antioxidant RD
Zhejiang Ultrafine Powders & Chemicals Co Ltd     10    Accelerator NS, CBS, TETD and TBZTD
Others    370    -
Total    1 007    
Source: CNCIC


Stable market price

Aniline is the key raw material for the production of rubber auxiliaries. In early 2011, due to the startup of the aniline unit in Yantai Wanhua Polyurethanes Co Ltd, the aniline unit is matched with diphenylmethane diisocyanate (MDI) project. The supply of aniline in China has been sufficient with the price remaining at a low level in the Chinese market, and the prices of rubber auxiliaries were therefore basically stable in the country. With the environmental protection issues, rubber accelerator units in Kemai (Inner Mongolia) Chemical Co Ltd and Zhenjiang Sopo Chemical Co Ltd suspended production. As a result, the prices of accelerator CBS and NS climbed constantly beginning from March 2011, and the profit of the enterprises was higher. In the second half of 2011, because of slump of market demand, the prices of rubber auxiliaries dropped slightly in China. Due to the low price of aniline and the startup of the first phase expansion project of Shandong Sinorgchem Co Ltd in Cao county, Shandong province, the prices of rubber antioxidants continued to fluctuate slightly in the country. In the fourth quarter of 2011, the price of antioxidant 4020 began to decline constantly because of the inventory in major production enterprises.

Table 2 China’s Output of Rubber Auxiliaries during 2009-2010   thousand tons
Variety     2009    2010
Rubber antioxidants         
  Antioxidant 4020    76.9    115.0
  Antioxidant 4010NA    24.2    35.0
  Antioxidant RD    74.0    98.0
Diphenylamine antioxidant    20.3    17.7
Naphthylamine antioxidant    2.0    2.2
Phenolic antioxidant and others    7.8    12.5
Subtotal    205.2    280.4
Rubber accelerators        
  Accelerator M    45.6    553.0
Accelerator DM    32.8    37.0
  Accelerator CZ    45.0    46.0
  Accelerator NS    43.0    43.0
  Accelerator NOBS    6.7    6.0
  Accelerator DZ    9.1    7.3
  Accelerator D    8.8    11.2
  Accelerator TMTD    18.5    19.1
  Other accelerators    22.6    24.6
Subtotal    232.1    247.2
Insoluble sulfur    36.6    38.7
Processing auxiliaries    67.3    69.7
Special functional auxiliaries    44.4    50.5
Other auxiliaries    10.0    14.5
Total    595.3    701.0
Source: CNCIC



In the fourth quarter of 2011, the prices of major rubber auxiliary varieties began to decrease, mainly due to downturn of the tire sector and the slack export market of rubber auxiliaries. In Q4 2011, Jilin Connell Chemical Industry Co Ltd conducted wet commissioning on its 180 thousand t/a new aniline unit, and Shandong Jinling Chemical Co Ltd started wet commissioning on its 240 thousand t/a aniline unit. The overcapacity of aniline is more serious now and the prices will continue to maintain at a low level. Due to the uncertainty of the global economic situation, the low prices of the rubber auxiliary raw materials and the gradual release of the new capacity of rubber auxiliaries, the prices of major rubber auxiliary varieties will continue to remain at a low level in 2012 in China.

Demand for rubber auxiliaries keeps growing

Considering the domestic output, import and export, and combining as well as domestic consumption of rubbers, the demand for p-phenylenediamine rubber antioxidants, quinoline rubber antioxidant, thiazole accelerators, sulfenamide accelerators and insoluble sulfur reached around 112 thousand tons, 75 thousand tons, 80 thousand tons, 85 thousand tons and 110 thousand tons, respectively in 2010.
   The sustained growth of the automobile and tire sectors has driven the rapid development of rubber auxiliary sector. After five-year boom, the output of automobiles began to grow at a slowing pace. However due to the immense base number of the automobiles, the absolute amount of the automobile output is still significant. According to the information released by the Ministry of Industry and Information Technology of China in April 2011, in the next few years, the automobile markets in second-tier and third-tier cities, and rural areas will increase stably and the growth of automobiles in first-tier cities will slow down. It is expected that in 2015, China’s output of automobiles will reach 23.0 -25.0 million and the vehicle population will be more than 150 million. The stable growth of the automobile output and the vehicle population will effectively promote the demand growth of rubber tire and its supporting auxiliaries and materials.
   With the drastic growth of the domestic automobile sector and the global tire production moving eastward, China’s output and export amount of tires has presented a high growth trend in recent years. The output of the tires and radial tires experienced an annual growth of 26.78% and 30.5%, respectively in the 2001 - 2010 period. It is expected that the domestic tire sector will growth  around 8% yearly in the next five years.
   The rapid development of automobile and tire sectors has laid a good foundation for the development of rubber auxiliary sector. It is expected that the demand for rubber auxiliaries in China will rise 7% annually during the 12th Five-Year Plan period (2011-2015), and the demand for p-phenylenediamine rubber antioxidants,  quinoline rubber antioxidant, thiazole accelerators, sulfenamide accelerators and insoluble sulfur will reach 160 thousand tons, 105 thousand tons, 115 thousand tons, 130 thousand tons and 160 thousand tons, respectively by 2015. With the stronger competitiveness in rubber auxiliary sector, the export of rubber auxiliaries in China will still maintain rapid growth in the next few years. Therefore, the market potential and development prospects of rubber auxiliary sector are worth expecting.

Cleaner process

The p-aminodiphenylamine production process in China has gradually tended to nitrobenzene method to reach international leading level in the production technology of p-aminodiphenylamine and antioxidant 4020. The production technologies independently developed by China such as silane coupling agent production technology, full closed process route, the synthesis of cobalt salt adhesion promoter and the synthesis of high quality antioxidant RD using solid acid have reached the advanced level in the world, and China is implementing the industrialization of these technologies.
   China is conducting the research and development of the cleaner production process of accelerator M. On the basis of the nation's 11th Five Year Scientific Technology Support Program “the clean production process of rubber auxiliaries and the development of special functional products”, the industry association has continued to declare the nation's 12th Five Year Scientific Technology Support Program about the clean production process of accelerator M from the state. It is expected that in the next 2-3 years, China will realize the clean production of accelerator M, complete the construction of 50 thousand t/a demonstration production line and conduct the popularization in the whole sector.
   China has made a progress in one-step gasification production process of insoluble sulfur and has built a 1 000 t/a production unit. The successful promotion of the process technology will end the situation that China’s insoluble sulfur with high thermal stability for the production of radial tires is heavily dependent on imports.
   The development for the clean production process of the pre-disperse rubber auxiliaries has been accelerated. The large quantity of powdered rubber auxiliaries is pre-dispersed in small amounts of polymer supports to make pre-disperse parent rubber particles- final products of rubber auxiliaries. This process technology is a major transformation of rubber auxiliary formulation. In China, a 10 000 t/a pre-disperse rubber auxiliary unit has been built.

Table 3 China’s Newly-built and Expanded Rubber Auxiliary Units
Producer    Remarks
Shandong Sinorgchem Co Ltd    Startup of the 50 thousand t/a p-aminodiphenylamine and 40 thousand t/a antioxidant 4020 project is
            expected to be postponed to the end of 2012 due to the general sales condition
Sinopec Nanjing Chemical Industry Co Ltd    30 thousand t/a new antioxidant RD project is expected to go on stream in the second half of 2012
Shandong Shanxian Chemical Co Ltd    30 thousand t/a accelerator M project went on stream in the second half of 2011 and the 15 thousand t/a
            new p-aminodiphenylamine project was put into operation by the end of 2011
Tianjin No.1 Organic Chemical Plant    The whole plant are relocated, and its total capacity of rubber auxiliaries is expected to reach around 70
            thousand t/a in 2012
Northeast Auxiliary Chemical Co Ltd    10 thousand t/a insoluble sulfur unit came on stream in mid 2011
Shandong Yanggu Huatai Chemical Co Ltd    15 thousand t/a accelerator M and 10 thousand t/a antiscorching agent project was expected to be put into
            operation in early 2012
Kemai (Inner Mongolia) Chemical Co Ltd    10 thousand t/a accelerator M unit went on stream in June 2011
Zhenjiang Sopo Chemical Co Ltd    30 thousand t/a rubber accelerator project is expected to go on steam in mid 2012
Shanxi Xiangyu Chemical Co Ltd    40 thousand t/a antioxidant 4020 unit is planned to start up in the second half of 2012
Shandong Ekesen Chemical Co Ltd    The first phase of 45 thousand t/a antioxidant 4020 project is expected to go on stream in 2012
Wuhan Jinghe Chemical (Qianjiang) Co Ltd    2.5 thousand t/a rubber accelerator and peptizer project is expected to start up in mid 2012
Source: CNCIC



China’s rubber auxiliary sector has further implemented the research and application of substitute products along with accelerating the technical progress of the clean process. In recent years, sulfenamide accelerator NOBS (N-oxydiethylene-2-benzothiazole sulfenamide) has been successfully replaced by the products like NS (N-tert-butyl-2-benzothiazole sulfenamide). Because of nitrosamine issues, the products like super accelerator TMTD (tetramethyl thiuram disulfide), TMTM (teramethyl thiuram monosulfide) and carbamate rubber auxiliary ZDC (zinc diethyldithiocarbamate) are also gradually replaced. The application of pentachloro-thiophenol chemical peptizers has been stopped in Europe and the United States, and their major alternative product- DBD (2,2'-dibenzamido-diphenyldisulfide) has been successfully developed in China. Due to the restriction on the use of the polycyclic aromatic hydrocarbons (PAHs) in European Union (EU) 2005/69/EC regulations, domestic enterprises have paid great attention to the research and development of environmental friendly aromatic oil. Suntec Yang (Ningbo) Co Ltd, a joint venture between Sunoco of the United States and Hansen & Rosenthal of Germany, has become a major supplier of environmentally friendly aromatic oil to China’s tire enterprises. The rubber auxiliary enterprises like PetroChina, Sinopec, CNOOC, Qingdao Haijia Chemical Co ltd, Changchun Dacheng Group and Shandong Tianyuan Chemical Co Ltd are also developing the similar products. Vulcanization activator with little pollution to the environment and high activity is also the important research subject in China. China has successfully developed nanometer zinc oxide, nanometer inorganic filler zinc and organic zinc compounds, etc. In addition, with the promotion of the low carbon and environmental protection concepts, the output of carbon black with low rolling resistance and silica white with high dispersion has increased gradually.

Domestic rubber auxiliary sector focuses on "greener "

The low-carbon economy, environmental protection, energy saving and emission reduction become highlights today, and the development of rubber auxiliary sector should focus on "greener " chemical and clean production. In the aspect of the process, focus should be on the promotion of the production technologies such as synthesis of p-aminodiphenylamine using nitrobenzene method, synthesis of accelerator M using solvent method, synthesis of accelerator DM using hydrogen peroxide oxidation method, synthesis of antioxidant RD using solid acid method, synthesis of sulfenamide accelerator using oxygen oxidation method, precious metal catalytic synthesis of p-phenylenediamine rubber antioxidants and the production of insoluble sulfur with high thermal stability, etc. In the product varieties, the application of accelerator CBS、NS、TBSI、CBBS、OTTOS and TBZTD without generating nitrosamines should continue to be conducted. Sulfur donor mainly selects no morpholinyl donor, DTDC、Duralink HTS and Perkalink900, etc. Renacit 11 (2,2'-dibenzamido-diphenyldisulfide) replaces pentachloro-thiophenol to produce peptizers, and antioxidant FR gradually replaces antioxidant RD. The application of phenolic and phosphite antioxidants should be paid great attention. The development of other rubber auxiliaries such as rubber homogenizing agent 40MS, antiscorching agent HTM and super tackifying resin KORESIN should be accelerated.