Hydrogen peroxide is well-established as an environmentally-friendly deodorising and bleaching agent. Its uses include organic and inorganic chemical processing, textile and pulp bleaching, metal treating, cosmetic applications, catalysis of polymerisation reactions, municipal odour control, industrial waste treatment (detoxification), and control of bulking in wastewater. These uses are continually expanding, making it a necessity not only to understand the mode of hydrogen peroxide application but the safe handling of the chemical as well.
Hydrogen Peroxide is a strong oxidising agent and a weak acid in water solution. The formula is similar to that of water, with an extra atom of oxygen attached, H2O2. It is completely soluble in water. Pure anhydrous hydrogen peroxide is a colourless to pale blue syrupy liquid that decomposes violently into water and oxygen if heated above 80 C. it also decomposes in light and in the presence of metal ions or oxidizable organic materials. A small amount of stabiliser such as acetanilide is added to the solutions to retard the decomposition. One volume of hydrogen peroxide releases ten volumes of oxygen when it decomposes.
Hydrogen peroxides are marketed in concentration of 3-90% by wt as a solution in water. The most valuable property of hydrogen peroxide is that it breaks down into water and oxygen and therefore does not form any persistent, toxic residual compounds. It is used in the processes of epoxidation, oxidation, hydroxylation and reduction. Its oxidising properties are used in the bleaching and deodorising for textile, hair and in paper manufacture. It is also used medicinally as an antiseptic. Its application involves the production of chemicals, e.g. organic peroxides, perhydrates. It is also used in water and sewage treatment, mining, electronics, food and cosmetic industry
Previously, hydrogen peroxide was prepared industrially by hydrolysis of the ammonium peroxydisulfate, which was itself obtained by the electrolysis of a solution of ammonium bisulfate.
Today, hydrogen peroxide is manufactured almost exclusively by the anthraquinone process, which was formalized in 1936 and patented in 1939. It begins with the reduction of an anthraquinone (such as 2-ethylanthraquinone or the 2-amyl derivative) to the corresponding anthrahydroquinone, typically by hydrogenation on a palladium catalyst; the anthrahydroquinone then undergoes autoxidation to regenerate the starting anthraquinone, with hydrogen peroxide as a by-product. Most commercial processes achieve oxidation by bubbling compressed air through a solution of the derivatized anthracene, whereby the oxygen present in the air reacts with the labile hydrogen atoms (of the hydroxy groups), giving hydrogen peroxide and regenerating the anthraquinone. Hydrogen peroxide is then extracted, and the anthraquinone derivative is reduced back to the dihydroxy (anthracene) compound using hydrogen gas in the presence of a metal catalyst. The cycle then repeats itself.
The economics of the process depend heavily on effective recycling of the quinone (which is expensive) and extraction solvents, and of the hydrogenation catalyst.
A process to produce hydrogen peroxide directly from the elements has been of interest for many years. Direct synthesis is difficult to achieve, as the reaction of hydrogen with oxygen thermodynamically favours production of water. Systems for direct synthesis have been developed, most of which are based around finely dispersed metal catalysts. None of these has yet reached a point where they can be used for industrial-scale synthesis.
Properties of Hydrogen Peroxide
A basic understanding of the properties of hydrogen peroxide is essential to the safe handling of this chemical. Hydrogen peroxide is clear, colorless, waterlike in appearance, and has a characteristic pungent odor. Nonflammable, it is miscible with water in all proportions and is sold as a water solution.
The amount of hydrogen peroxide in commercial solutions is expressed as a percentage of the solution's weight. Thus, a 35% solution contains 35% hydrogen peroxide and 65% water by weight. Most municipal and industrial applications call for 35% or 50% concentrations.
Hydrogen Peroxide is a highly useful substance with many industrial applications, including use as a bleaching agent in the manufacturing of paper, pulp textiles and dyes. It is also a powerful oxidizing agent used in the electronics manufacturing industry where it is used for etching PCB plates and manufacturing semiconductors and is widely used in the food industry as well. It is also used in wastewater treatment processing. The applications of hydrogen peroxide fall into the following broad categories:
- Pulp and paper bleaching
- Water/waste and effluent treatment
- Chemical Synthesis
- Textile bleaching
- Mining & metallurgy
- Food and other markets
Indian Industry Status
In India there are 4 units engaged in making Hydrogen Peroxide with combined capacity of 109-kilo tons. GACL has two plants one at Baroda with capacity of 12,540-tons and another 26,540-tpa plant at Dahej. The Company is also expanding Hydrogen Peroxide capacity by putting another new 14,000 TPA plant at Dahej. The project is planned to go on stream in May, 2018.
National Peroxide Limited, established in 1954 is a pioneer in India for Peroxygen chemicals and is the largest producer of Hydrogen Peroxide with capacity of 95,000 MTPA (Metric Tonnes Per Annum) on 50% w/w basis. Its fully integrated manufacturing site is located at Kalyan in Maharashtra. Company has plans to expand the capacity to 1,50,000-tons in the next few years.
Asian Peroxide was incorporated in 1986 by NRI promoter S.K. Dewanas 100% EOU unit with initial capacity of 5,000-tons and later expanded to 18,000-tons. Company’s plant is located at Sullurpet, in Andhra Pradesh. Company debonded its EOU status in two stages in 1995 and then in 2005 and currently caters to domestic demand. Company is also looking to expand its capacity by another20,000-tons on 100% w/w basis by putting up a new plant in Gwalior.
Hindustan Organic Chemicals Ltd. (HOC) was the last entrant into this field. HOC makes hydrogen peroxide at its Kochi plant in Kerala and has installed capacity of 5,225-tpa. HOC.s plant, commissioned in 1997, is based on UHDE.s ethyl anthraquinone process.
Besides above units Meghmani Organics and Chemplast Sanmar have evinced interest in setting up Hydrogen Peroxide plants in India.
Table 1: Hydrogen Peroxide capacity in India on (100% w/w basis)
Table 2 provides the trend in production of hydrogen peroxide in India. Production has registered CARG of 7.65% during last 7 years.
Table 2: Production of Hydrogen Peroxide in India (50% w/w Basis)
Source: Ministry of Chemicals Annual Reports
Table 3: Imports of Hydrogen Peroxide into India (Quantity in Tons, Value in Rs. Lakhs and unit CIF in Rs/Kg.)
As can be seen from table 3 imports of hydrogen peroxide have almost doubled in last 8 years. Imports are mainly coming in from countries like Bangladesh, Korea, Indonesia and Thailand.
Anti-dumping duties on hydrogen peroxide imports
National Peroxide Limited and Hindustan Organic Chemicals Ltd had jointly filed an application before Directorate General of Anti-Dumping & Allied Duties for initiation of anti-dumping investigation and imposition of Anti-dumping duty concerning imports of Hydrogen Peroxide, originating in or exported from Bangladesh, Taiwan, Korea, Indonesia, Pakistan and Thailand. The India’s revenue department of ministry of finance issued a gazette notification slapping the duty on the same on these six countries that are Bangladesh, Taiwan, South Korea, Indonesia, Pakistan and Thailand.
As per the recommendations made by Directorate General of Anti- Dumping and Allied Duties in April India’s government has approved imposition of anti-dumping duty in June 2017 of up to $118 per tonne on import of hydrogen peroxide from Bangladesh and five other countries. The duty — in the range of $16.91-117.94 per tonne of the chemical — will remain in place for five years. The petition was supported by Gujarat Alkalies & Chemicals Ltd. The definitive anti-dumping duty, which will be valid for a period of five years, ranges from $16.91 per tonne to $117.94 per tonne, depending on the producer and exporter. This duty will protect the margins of domestic manufacturers including National Peroxide.
Exports of hydrogen peroxide from India are not very significant.
The total consumption of hydrogen peroxide during 2016-17 is estimated at around 1.05 lakh tons on 100% w/w basis. Overall demand for hydrogen peroxide in volume terms is expected to grow at 9 percent per annum. At this rate the demand is expected to rise to 1.62 lakh tons by 2021-22 on 100%w/w basis.
Drivers of growth
Industrial Hydrogen Peroxide market is expected to witness an escalating demand among the consumers because of its broad use and increasing presence paper and pulp industry throughout the world. Industrial Hydrogen Peroxide market is driven by the growing adaptation in paper and pulp industry. Companies all around the world are getting attracted towards Industrial Hydrogen Peroxide because of easy to use features and great usage which is driving the market. Use in making detergent bleaches, textile bleaching and purification of water are giving a push to Industrial Hydrogen Peroxide market.
Higher demand from Paper & Pulp industry will raise the demand for hydrogen peroxide
Paper and pulp industry is the key user of Hydrogen peroxide in India. The Indian Paper Industry is now a vast industry comprising more than 750 pulp and paper mills. However, only 50 of these mills have a capacity of 50,000 metric tonnes per annum or more. While demand for newsprint paper is being lost as readers move online, the ever-increasing migration by consumers to make purchases online is generating demand growth for transport packaging. The domestic Paper & pulp industry has been doing well over the past few quarters. Hydrogen Peroxide is initially used to ease the preparation of paper which is nowadays the biggest reason for Industrial Hydrogen Peroxide market growth. Almost all the paper and pulp manufacturers use hydrogen peroxide as an ingredient in the manufacturing process. It is useful in a variety of oxidation possibilities and pH ranges in which it can be utilized as an oxidizer.
India is a large under-penetrated country, as despite the sustained growth witnessed by the industry, the per capita paper consumption in India stands at a little over 13 kg, behind the global average of 57 kg. The domestic demand in India grew from 9.3 million tonnes in FY08 to 17 million tonnes in FY17 at a CAGR of 6.9%.
For the Indian paper industry, strong economic growth has been accompanied by equally robust demand for paper. The demand drivers and growth triggers have come from a combination of factors such as rising income levels, growing per capita expenditure, rapid urbanization and a larger proportion of earning population which is expected to lead consumption and there is enormous potential for the paper industry in the country. CARE Ratings expects that the overall paper demand growing at a CAGR of 6.7% to touch 20.7 million tonnes in FY20.
Figure one below provides consumption pattern of hydrogen peroxide in India. 50% of the consumption goes into making papers, followed by 35% in textiles and 8% in Chemical intermediates and chemical synthesis and balance in other miscellaneous uses.
Figure 1: It shows the graph of consumption patter of Hydrogen Peroxide in India
The global Hydrogen Peroxide Market was valued at US$ 2.44 Bn in 2016 and is likely to reach US$ 3.68 Bn by 2025, expanding at a CAGR of 4.7% between 2017 and 2025. Paper and Pulp Industry to Remain Highly Promising for Hydrogen Peroxide Market.
Asia Pacific Market to Provide Promising Growth Avenues
In terms of application, the global market for hydrogen peroxide presently earns the majority of its revenue from the paper and pulp industry, trailed by the chemical segment. The paper and pulp industry is likely to remain lucrative for the global hydrogen peroxide market in the next few years as well.
Regionally, the market in Asia Pacific presently accounts for the dominant share in the global market. High demand from the steadily expanding paper and pulp industry in the region led to increased demand for hydrogen peroxide. While the region is likely to remain lucrative in the next few years, thanks to the highly attractive market in China, the rising demand for consumable water, and increased awareness about the need for wastewater treatment, the markets in North America and Europe are also expected to remain promising.
Global Consumption Pattern of hydrogen peroxide
The hydrogen peroxide market is dominated by the pulp and paper industry, with the main uses being in pulp bleaching and deinking of recycled paper. Growth of the pulp industry has been particularly strong in Southeast Asia and Central and South America. Both regions have the competitive advantage of fast-growing eucalyptus as pulp raw material, and accordingly, investment in new pulp mills is made primarily in these regions. Southeast Asian producers have an additional advantage-their proximity to growing markets.
Global hydrogen peroxide market for wastewater treatment
Hydrogen peroxide is used for treating industrial wastewater and municipal wastewater, controlling parasites in aquaculture, and removing undesirable compounds such as cyanides, hydrogen sulfide, hypochlorite, phenols, and various oxygen-demanding organic compounds. The wastewater treatment segment is expected to grow at a moderate rate because of the increasing demand for safe drinking water, owing to the rise in global population.
Global hydrogen peroxide market for others
The others segment includes the food and beverages, healthcare, electronics, oil and gas, and agriculture sectors. Food grade hydrogen peroxide is used in the food processing industry. The etching of circuit boards in electronic applications in the manufacture of semiconductors is expected to boost the demand for hydrogen peroxide. In the consumer goods and healthcare segment, hydrogen peroxide is used for the development of hair color and acne control products.
Companies, such as Solvay and Evonik, have commercialized the electronics grade variants, along with several others which are under R&D. The growth of the electronic sector, especially in developing countries such as India and China, is expected to bring new opportunities for the global hydrogen peroxide market.
Apart from this, the global market for hydrogen peroxide is also experiencing a surge in the overall demand across other core end-use industries, including mining, chemical production, and wastewater management. The increasing applications of hydrogen peroxide in the wastewater management sector are also expected to drive the market towards a positive growth path in the near future. A vast surge in wastewater management projects across countries with a surging industrial sector is expected to allow for increased consumption of hydrogen peroxide in the near future. Looking at current trends, it can be safely assumed that wastewater treatment and paper and pulp industries will remain the most lucrative end-use application sectors for the market in the near future.
Figure 2: It provides global consumption pattern of hydrogen peroxide
The global hydrogen peroxide market is expected to undergo significant change. Pulp and paper is not expected to continue to be the growth engine for hydrogen peroxide consumption. The change from print to digital media has been occurring for some years, and it had been expected that this trend would result in decreasing paper consumption. Yet, since 2009, increasing paper consumption in the developing parts of the world and increasing demand for hygiene paper, tissues and packaging have outbalanced the shrinking use in newsprint in the developed world. In the current forecast period, the continued switch to digital media and shrinking paper consumption is expected to result in stagnation of this hydrogen peroxide market segment.
Hydrogen peroxide propylene oxide (HPPO) technology could be a game changer for PO
In the years to come downstream chemical uses are expected to make up the largest part of hydrogen peroxide consumption globally. The single most important use of hydrogen peroxide in this segment is the production of propylene oxide via the HPPO process. The first HPPO plant was started in 2008 by SKC/Evonik in the Republic of Korea. In the meantime, other plants using the same technology were started in Europe and other Asian countries, and are running with high capacity utilization rates as they provide a competitive production route to propylene oxide
Propylene Oxide (PO) plants based on the HPPO process are said to be more economical as they require 25% less capital to build. The process produces only water and PO, without the other products associated with the traditional processes. Raw materials required for the process are simpler – propylene and hydrogen peroxide. The process also avoids by-products generation such as propylene dichloride and styrene monomer. In addition, the process is said to be more environmentally friendly.
Hydrogen peroxide propylene oxide (HPPO) is a relatively simple process with few by-products. As such, it is seen as the most modern, cost efficient process.
It was simultaneously developed by BASF/Dow and by Degussa-Uhde. Degussa-Uhde claim the first plant – built in 2008 by SK Chemicals in Korea. This was very shortly followed by a BASF/Dow plant in Antwerp also in 2008. More plants came from BASF/Dow – a plant in Thailand in 2011, and a Dow joint venture Sadara Chemicals opening in Saudi Arabia in 2017.
Degussa-Uhde (now owned by Evonik) sold the technology under license, to Jishen Chemical industries in Jilin, China (from 2014). However, a couple of Chinese players are working on their own HPPO technologies and this could be a game changer for the PO market.
Sinopec has also developed an HPPO process. It opened the first HPPO plant in 2015 – in Yueyang (Sinopec Changling) with a capacity of 100,000 tonnes/year.
Additional HPPO plants are either under construction or are scheduled for construction in Asia, the Middle East and the CIS. No plant has been announced yet for North America; however, cheap energy costs would allow highly competitive production of hydrogen peroxide, which coupled with availability of propylene feedstock, makes it likely that an HPPO plant could also be built in the coming years.
Sodium percarbonate was a promising new product a few years ago, and was expected to be a growing outlet for hydrogen peroxide. The product mainly replaces perborate as a bleaching agent in detergents. Growth in the last five years has not met expectations. The massive replacement by more convenient liquid detergent formulations has led to a shrinking powder detergent market, and it is not expected that this trend can be reversed in the coming years.
Ministry of Chemicals-Annual Reports
Company Websites – NPL,GACL, APL
DGCIS-Ministry of Commerce
Transparency Market Research