Good scope for manufacturing plant waste based Furfural and its derivatives
Furfural, also known as furfuraldehyde is an organic compound with the formula C4H3OCHO. It is a colorless liquid, although commercial samples are often brown. It consists of a formyl group attached to the 2-position of furan. It is a product of the dehydration of sugars, as occur in a variety of agricultural byproducts, including corncobs, oat, wheat bran, and sawdust. The name furfural comes from the Latin word furfur, meaning bran, referring to its usual source. Aside from ethanol, acetic acid and sugar it is one of the oldest renewable chemicals. It is also found in many processed foods and beverages.
Furfural was first isolated in 1821 (published in 1832) by the German chemist Johann Wolfgang Döbereiner, who produced a small sample as a by-product of formic acid synthesis. At the time, formic acid was formed by the distillation of dead ants, and Döbereiner's ant bodies probably contained some plant matter. In 1840, the Scottish chemist John Stenhouse found that the same chemical could be produced by distilling a wide variety of crop materials, including corn, oats, bran, and sawdust, with aqueous sulfuric acid; he also determined an empirical formula of (C5H4O2). George Fownes named this oil furfurol in 1845 (from furfur - bran, and oleum). This name persisted prominently in the literature until 1901 when the German chemist Carl Harries deduced furfural's structure.
Furfural remained relatively obscure until 1922, when the Quaker Oats Company began mass-producing it from oat hulls. Today, furfural is still produced from agricultural by-products like sugarcane bagasse and corn cobs. The main countries producing furfural today are the Dominican Republic, South Africa and China.
Furfural dissolves readily in most polar organic solvents, but it is only slightly soluble in either water or alkanes. Furfural participates in the same kinds of reactions as other aldehydes and other aromatic compounds. It exhibits less aromatic character than benzene, as can be seen from the fact that furfural is readily hydrogenated to the corresponding tetrahydrofuran derivatives. When heated in the presence of acids, furfural irreversibly polymerizes, acting as a thermosetting polymer.
Furfuraldehyde is an organic compound derived from a variety of agricultural products such as corn cobs, oat, wheat bran and sawdust. The process of furfural includes hydrolysis of pentosan, which is present in the above mentioned agricultural products.
Corn cobs are cut into 3 to 6 mm size and subjected to vapor phase hydrolysis using sulphur trioxide gas and steam at elevated temperature and pressures in cylindrical vessel. The process generates formation of Furfural along with other chemicals. The Furfural thus generated is then taken out of the cylindrical vessel by using dry steam under pressure and these vapors are cooled and fractionated to obtain Furfural along with other by-products namely Acetic Acid, Acetone and Methanol. By employing specific conditions of temperature, pressure and relative concentrations of sulphur trioxide, 9 to 12% furfural yield is extracted.
Furfural is used as a solvent in the refining of lubricating oils; extraction of mineral oils; and as a solvent or wetting agent in the manufacture of abrasive wheels, brake linings and refractory products. Furfural is also used in a range of applications which include pharmaceutical intermediates, as a nemacide in agriculture or horticulture, as a flavor/fragrance ingredient in food & beverages, and as a chemical intermediate in the production of furfural derivatives such as furan and tetrahydrofuran.
Hydrogenation of furfural provides furfuryl alcohol (FA), which is a used to produce furan resin, which is exploited in thermoset polymer matrix composites, cements, adhesives, casting resins and coatings. Further hydrogenation of furfuryl alcohol leads to tetrahydrofurfuryl alcohol (THFA), which is used as a solvent in agricultural formulations and as an adjuvant to help herbicides penetrate the leaf structure.
Another important solvent made from furfural is methyltetrahydrofuran. Furfural is used to make other furan derivatives, such as furoic acid, via oxidation, and furan itself via palladium catalysed vapor phase decarbonylation.
Furfural is also a specialized chemical solvent. There is a good market for value added chemicals that can be obtained from furfural such as furfuralamine and 2-furoic acid.
Global Furfuryl market has grown from US $ 450 mn in 2014 to US$ 730 mn in 2018. In terms of volume the market has grown from 300 kilo tons in 2013 to 510 kilo tons in 2018.
China has emerged as the leading regional market for furfural and accounting forbetween 50 to 55%% of total market volume. China along with being the largest consumer is also the largest producer of furfural which has been a major factor for the growth of domestic market. Low production cost of furfural in China is expected to remain a key driving factor for the domestic market. However, the furfural industry has been facing an issue of availability of corn cob, basic raw material to manufacture furfural. The prices of corn cob have been witnessing an upward trend in the recent past which has prompted the government agencies to stockpile corn cob.
Asia-Pacific is the largest furfural consuming region in the world with an estimated 2018 share of 77%. The region is projected to witness the fastest CAGR during the analysis period 2018-2024 with 4.8% and 6.2% for volume and value respectively.
Increasing furfural demand in markets such as Thailand, Indonesia, Malaysia and India is expected to augment the global market growth. Growth of major end-use industries such as chemicals, pharmaceuticals and foundry industries particularly in emerging markets of Asia Pacific is expected to be a major factor contributing to the market growth.
Global furfural market is fragmented with a presence of large number of small scale manufacturers in China. Major companies are integrated along the value chain and are involved in the production of furfural derivatives such as furfuryl alcohol.
Some of the major companies operating in the global market include Teiling, Central Romana Corp.(Dominican Republic),Aurus Speciality Company Limited (Thailand), International Furan Chemicals, TransFurans Chemicals (Belgium), Penn A Kem LLC (USA), Henan Huilong Chemical Co., Ltd. (China), Hongye Holding Group Corporation Limited (China), Shanxi Province Gaoping Chemical Co., Ltd. (China), Hebei XingtaiChunleiFurfuryl Alcohol Co., Ltd. (China) and Sugar Illovo Ltd.
Furfuryl alcohol is an organic compound containing a furan substituted with a hydroxymethyl group. It is a colorless liquid, but aged samples appear amber. It possesses a faint odor of burning and a bitter taste. It is miscible with but unstable in water. It is soluble in common organic solvents
Furfuryl alcohol is the most important application of Furfural. At present, approximately 88 percent of all furfural produced is converted to furfuryl alcohol attributed to demand for this product in the production of foundry resins. Furfural as a solvent is the second largest application for furfural globally.
Furfural (Furfuraldehyde) is reacted with Hydrogen Gas in liquid phase using Raney Nickel Catalyst to form Furfuryl Alcohol. By employing specific conditions of temperature, pressure and relative concentrations of these three components, a high selectivity is achieved at relatively low pressures of Hydrogen leading to over 95% yield.
The majority of furfuryl alcohol is used in the production of furan resins for foundry sand binders in the metal casting industry. Currently, furfuryl alcohol is used mainly in binders for the traditional furan no-bake system and in smaller quantities in furan hot-box, warm-box, and gas-hardened processes. In its main application, the foundry business, furfuryl alcohol competes primarily with phenol, the feedstock for phenolic resins.
Global furfuyrl alcohol market is estimated to have grown from 270 kilo tons in 2013 to 460 kilo tons in 2018. On the basis of application, the furfuryl alcohol market has been segmented into furan resins, bio-fuel, tetrahydrofurfuryl alcohol (THFA), flavor and fragrance chemicals, solvents, pharmaceuticals, and pesticides.
On the basis of both value and volume, furan foundry binders held the largest share in the market in 2018(approx.. 80 to 85%). Generally, 2-(Hydroxymethyl)furan is used in the furan foundry binders for WARM BOX, HOT-BOX, and Furan NO-BAKE processes.
The remaining applications include tetrahydrofurfuryl alcohol (THFA), and use in solvents, flavor and fragrance chemicals, pesticides, and pharmaceuticals. THFA is used mainly as a specialty solvent or chemical intermediate, with its primary end markets being agricultural chemicals, coatings, and cleaning solutions. The production and use of furfuryl alcohol is centered in China. Low-cost production in China forced most of the industry in North America, Western Europe, and Japan to shut their operations in the 1990s. China has also captured most of the foundry business. Little change is expected in the near future. Any growth in the global industry will depend on activity in China.
China continues to be the world’s largest producer and consumer of furfuryl alcohol, accounting for 80–85% of worldwide capacity and production and about 55% of global consumption in 2018. Since 2000, a number of foundries have relocated to China, which has led to increased domestic demand for furan resins, especially from the automotive, windmill, and machinery industries. However, it is expected that Chinese demand for furan resins in the heavy casting industry will grow at a slower rate in the near future, at about 3% annually on average.
Global cement industry is going to experience steady growth in coming years owing to increase in customers investing in residential and non- residential infrastructure projects. Furfuryl alcohol is water miscible and has usage as wetting agent in cement industry. Wetting agent are used in paints & coatings to prevent agglomerate formation. The chemical compound gets absorbed on the pigment surface as spacer. With help of wetting agents, the agglomerate formed are easily separated in individual particle and permanently settles in uniform distribution.
Pesticides are used to protect crops from diseases and weed. Global pesticide market is expected to grow over 6% in coming years owing to rise in population supported by increasing food & beverages demand. Tetrahydrofurfuryl alcohol (THFA) is used as inert ingredient in pesticide. An inert material is not active but intentionally introduced in pesticide product. Inert material serves as solvent and permitting active ingredient in plant outer surface. It protects pesticides from degradation owing to exposure to sun thus extending pesticide shelf life. The growth in pesticide industry should drive the product demand.
Global anti- corrosion coating market was valued at over USD 23 billion in 2016 and expected to further grow as corrosion is predicated to contribute heavy financial losses by gradually weakening construction materials. Coating is effective solution to protect material and extend its life. furfuryl mono polymers have exceptional corrosion-resistant property but the coating formed is brittle in nature. To overcome this problem epoxy resins are added to furfuryl alcohol making it tougher, increasing adhesiveness, imparting higher resistance to abrasion and heating properties. It is also applied to pitted and corroded steel to extend its existing life. Expanding coating industry owing rising demand from end use industry such as healthcare, residential, commercial and automotive may fuel product demand.
TransFurans Chemicals a leading manufacturer for biomass based chemicals have recently developed furfuryl alcohol from sugarcane for building & construction and wood modification applications. This bio based alcohol is further polymerized to polyfurfuryl alcohol in polymer industry application.
Till recently most of the furfuryl alcohol demand was met through imports as there was no local production of either furfural or furfuryl alcohol.
KRBL Ltd, which owns India Gate basmati rice, has set up a furfuryl alcohol plant at Dhuri (Sangrur district in Punjab) as part of its forward integration strategy. The plant, set up with an investment of Rs 7 crores, commenced commercial production of furfuryl in December 2017 and that of furfuryl alcohol few months later. KRBL is an exporter of basmati rice and a significant player in the branded food industry. It manufactures products like rice bran oil, furfural and de-oiled cakes. KRBL makes furfuryl alcohol from furfuryl oil, which is produced from rice husk that arises as a by-product during the processing of rice.
Besides KRBL, Galaxy Laboratories, Aurangabad also put up a small plant to make furfural, furfurylalohol, furfuralamine and 2-Furoic acid. Galaxy Laboratories is an API manufacturer and a leading furfuyl amine supplier. It commenced production of furfyrl amine in 1995. Galaxy Laboratories has capacity to make 600MT of furfural, 3601 MT of furfuryl alcohol, 480 Mt of furfurlamine and 60 MT of 2-Furroic acid. Most of the fufural and furfuryl alcohol produced are used captively by the company for making API intermediates. Besides, Galaxy, furfurylamine is also manufactured by Alkyl Amines & Chemicals Ltd.
Local demand for furfuryl alcohol in India is estimated to be around 14,000 to 15,000 tons and that of furfural at 15,500 to 16,500 tons.
Table below provides data on imports of furfurl alcohol & tetra hydro furfurl alcohol imported under HIS code: 29321300.
Imports of furfurl alcohol & tetra hydro furfurl alcohol
Table-2: sourcewise imports of furfuryl alcohol
Derived from plant-based waste such as sugarcane bagasse, corn cobs, wheat bran, rice bran etc, there is good scope for making furfuryl and its derivatives in India. Demand for furfural and its derivatives is increasing globally as the end-user industries look for eco-friendly chemicals produced from renewable resources. Industries such as chemicals, pharmaceuticals, plastics, foundry, etc are expected to propel the demand for this alcohol in India as well. Rising demand for bio-based products owing to increasing awareness among consumers coupled with rising environmental regulations is expected to drive the market for furfural and its derivatives in future.
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