Description
Furfural is an essential renewable, non-petroleum based, chemical feedstock which is primarily composed of various agricultural byproducts, including oat husks, wheat bran, corncobs, and sawdust. Chemically, furfural is an organic compound belonging to an aldehyde of furan with the odor of almonds. It is typically produced for industrial purposes, which can be used as a selective solvent in the process of refining lubricating oils and used in the manufacture of transportation fuels to improve the characteristics of diesel fuel and catalytic cracker recycle stocks. Besides, furfural is applied widely for producing resin-bonded abrasive wheels and purifying butadiene needed for the manufacture of synthetic rubber. It is also used to make other furan chemicals, such as furoic acid and furan itself. Other products of furfural include weed killer, fungicide, other solvents and etc.
References
https://en.wikipedia.org/wiki/Furfural
https://www.britannica.com/science/furfural
https://pubchem.ncbi.nlm.nih.gov/compound/2-Furaldehyde#section=Top
http://www.wisegeek.com/what-is-furfural.htm
Description
Furfural is a colourless to amber-like oily liquid with an almond-like odour. On exposure
to light and air, it turns reddish brown. Furfural is used in making chemicals,
as a solvent in petroleum refining, a fungicide, and a weed killer. It is incompatible with strong acids, oxidisers, and strong alkalis. It undergoes polymerisation on contact
with strong acids or strong alkalis. Furfural is produced commercially by the acid
hydrolysis of pentosan polysaccharides from non-food residues of food crops and wood
wastes. It is used widely as a solvent in petroleum refining, in the production of phenolic
resins, and in a variety of other applications. Human exposure to furfural occurs during
its production and use, as a result of its natural occurrence in many foods and from the
combustion of coal and wood.
Chemical Properties
Furfural is a colorless to yellow aromatic het erocyclic aldehyde with an almond-like odor. Turns amber
on exposure to light and air.
Chemical Properties
Furfural has a characteristic penetrating odor typical of cyclic aldehydes. Furfural is prepared industrially from pentosans that are contained in cereal straws and brans; these materials are previously digested with diluted H2S04, and the formed furfural steam is distilled.
Physical properties
Colorless to yellow liquid with an almond-like odor. Turns reddish brown on exposure to light and
air. Odor and taste thresholds are 0.4 and 4 ppm, respectively (quoted, Keith and Walters, 1992).
Shaw et al. (1970) reported a taste threshold in water of 80 ppm.
Occurrence
Reported found in several essential oils from plants of the Pinaceae family, in the essential oil from Cajenne linaloe, in the oil from leaves of Trifolium pratense and Trifolium incarnatum, in the distillation waters of several essential oils, such as ambrettee and angelica seeds, in Ceylon cinnamon essential oil, in petitgrain oil, ylang-ylang, lavender, lemongrass, calamus, eucalyptus, neroli, sandalwood, tobacco leaves and others Also reported found in many foods including apple, apricot, citrus peel oils and juices, berries, guava, grapes, pineapple, asparagus, kohlrabi, celery, onion, leek, potato, tomato, cinnamon, mustard, bread, cheeses, meats, fsh, cognac, rum, whiskies, cider, grape wine, cocoa, coffee, tea, barley, peanuts, popcorn, pecans, oats, honey, soybeans, passion fruit, plums, mushroom, mango, tamarind, fruit brandies, whiskey malt, white bread, rum, bourbon, cardamom, coriander seed, calamus, corn oil, malt, wort and other sources
Uses
Solvent refining of lubricating oils,
resins, and other organic materials; as insecticide,
fungicide, germicide; an intermediate for
tetrahydrofuran, furfural alcohol, phenolic and
furan polymers
Uses
Commercially, furfural is produced through hydrolysis of
pentosan in agricultural byproducts (e.g., crop wastes). It has
a diverse applications which include as a solvent in various
manufacturing industries (e.g., petroleum and automotive
products), accelerant for vulcanization of rubber, raw material
for manufacturing furan derivatives (e.g., tetrahydrofurfuryl
alcohol) and synthetic resins, wetting agent, flavoring ingredient
for foods (e.g., roasted coffee), fragrance in consumer and
personal care products (e.g., fragrance cream, bath products,
toiletries), and pesticides for controlling unwanted microorganisms,
fungi, weeds, insects, and nematodes. The application
methods for pesticidal use include drip irritation, spray boom,
sprinkler, and low-pressure back-pack spray.
Uses
In the manufacture of furfural-phenol plastics such as Durite; in solvent refining of petroleum oils; in the preparation of pyromucic acid. As a solvent for nitrated cotton, cellulose acetate, and gums; in the manufacture of varnishes; for accelerating vulcanization; as insecticide, fungicide, germicide; as reagent in analytical chemistry. In the synthesis of furan derivatives.
Definition
ChEBI: An aldehyde that is furan with the hydrogen at position 2 substituted by a formyl group.
Definition
furfural: A colourless liquid,C
5H
4O
2, b.p. 162°C, which darkenson standing in air. It is the aldehydederivative of furan and occurs invarious essential oils and in fuseloil. It is used as a solvent for extractingmineral oils and natural resinsand itself forms resins with somearomatic compounds.
Preparation
Industrially prepared from pentosans that are contained in cereal straws and brans; these materials are previously digested with diluted H2SO4, and the formed furfural steam is distilled.
Production Methods
Furfural is obtained commercially by treating pentosan-rich agricultural residues (corncobs, oat hulls, cottonseed hulls, bagasse, rice hulls) with a dilute acid and removing the furfural by steam distillation. Major industrial uses of furfuraldehyde include: (1) the production of furans and tetrahydrofurans where the compound is an intermediate; (2) the solvent refining of petroleum and rosin products; (3) the solvent binding of bonded phenolic products; and (4) the extractive distillation of butadiene from other C4 hydrocarbons.
When pentoses, e.g., arabinose, xylose, are heated with dilute HCl, furfuraldehyde is formed, recognizable by deep red coloration with phloroglucinol, or by the formation, with phenylhydrazine, of furfuraldehyde phenylhydrazone C4H3O·CH : NNHC6H5, solid, mp 97 °C.
Reactions
Aside from a darkening in color, furfural is relatively stable thermally and does not exhibit changes in physical properties after prolonged heating up to 230°C. The reactions of furfural are typical of those of the aromatic aldehydes, although some complex side reactions occur because of the reactive ring. Furfural yields acetals, condenses with active methylene compounds, reacts with Grignard reagents, and provides a bisulfite complex. Upon reduction, furfural yields furfural alcohol; upon oxidation, it yields furoic acid. It can be decarbonylated to furan.
Taste threshold values
Taste characteristics at 30 ppm: brown, sweet, woody, bready, nutty, caramellic with a burnt astringent nuance.
Synthesis Reference(s)
The Journal of Organic Chemistry, 45, p. 3449, 1980
DOI: 10.1021/jo01305a015
General Description
Colorless or reddish-brown mobile liquids with a penetrating odor. Flash points 140°F. Denser than water and soluble in water. Vapors heavier than air. May be toxic by ingestion, skin absorption or inhalation.
Air & Water Reactions
Flammable. Furfural is sensitive to light and air. Soluble in water, with mixing.
Reactivity Profile
Furfural reacts with sodium hydrogen carbonate. Furfural also can react with strong oxidizers. An exothermic resinification of almost explosive violence can occur upon contact with strong mineral acids or alkalis. Furfural forms condensation products with many types of compounds, including phenol, amines and urea. .
Hazard
Absorbed by skin; irritant to eyes, skin,
and mucous membranes. Toxic by skin absorption;
questionable carcinogen.
Health Hazard
Vapor may irritate eyes and respiratory system. Liquid irritates skin and may cause dermatitis.
Fire Hazard
Special Hazards of Combustion Products: Irritating vapors are generated when heated
Flammability and Explosibility
Non flammable
Industrial uses
Also known as furfuraldehyde, furol, and pyromuclealdehyde,furfural is a yellowish liquidwith an aromatic odor, soluble in water and inalcohol, but not in petroleum hydrocarbons. Onexposure, it darkens and gradually decomposes.Furfural occurs in different forms in variousplant life and is obtained from complex carbohydratesknown as pentosans, which occur insuch agricultural wastes as cornstalks, corncobs,straw, oat husks, peanut shells, bagasse,and rice. Furfural is used for making syntheticplastics, as a plasticizer in other synthetic resins,as a preservative in weed killers, and as aselective solvent especially for removing aromaticand sulfur compounds from lubricatingoils. It is also used for the making of butadiene,adiponitrile, and other chemicals.
Various derivatives of furfural are not used,and these, known collectively as furans, are nowmade synthetically from formaldehyde andacetylene, which react to form butyl nedole.
Mechanism of action
Fumigant, inhibits fungal and bacterial growth
Safety Profile
Confirmed carcinogen.
Poison by ingestion, intraperitoneal,
subcutaneous, intravenous, and
intramuscular routes. Moderately toxic by
inhalation and sktn contact. Human
mutation data reported. A skin and eye
irritant. Mutation data reported. The liquid is
dangerous to the eyes. The vapor is irritating
to mucous membranes and is a central
nervous system poison. However, its low
volatility reduces its toxicity effect. Ingestion
of furfural has produced cirrhosis of the
liver in rats. In industry there is a tendency
to minimize the danger of acute effects
resulting from exposure to it. This is
particularly true because of its low volathty. Flammable liquid when exposed to heat or
flame; can react with oxidizing materials.
Moderate explosion hazard when exposed
to heat or flame or by chemical reaction. An
exothermic polymerization of almost
explosive violence can occur upon contact
with strong mineral acids or alkalies. Keep
away from heat and open flames. Mixture
with sodium hydrogen carbonate ignites
spontaneously. To fight fire, use alcohol
foam, CO2, dry chemical. When heated to
decomposition it emits acrid smoke and
irritating fumes.
Potential Exposure
Furfural is used for lube oil refining
and butadiene extraction; as a solvent for wood resin,
nitrated cotton, cellulose acetate, and gums; in the produc tion of phenolic plastics, thermosetting resins, refined
petroleum oils, dyes, and varnishes; in the manufacture of
pyromucic acid, vulcanized rubber, insecticides, fungicides,
herbicides, germicides, furan derivatives, polymers, and
other organic chemicals.
First aid
If this chemical gets into the eyes, remove anycontact lenses at once and irrigate immediately for at least15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts theskin, remove contaminated clothing and wash immediatelywith soap and water. Seek medical attention immediately. Ifthis chemical has been inhaled, remove from exposure,begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR ifheart action has stopped. Transfer promptly to a medicalfacility. When this chemical has been swallowed, get medical attention. Give large quantities of water and inducevomiting. Do not make an unconscious person vomit.
Carcinogenicity
The IARC evaluated furfural
and determined that there was inadequate evidence in
humans for the carcinogenicity of furfural. There is limited
evidence in experimental animals for the carcinogenicity of
furfural.
Source
Furfural occurs naturally in many plants including rice (90,000–100,000 ppm), lovage
roots (2 to 20 ppm), caraway, strawberry leaves, cilantro, java cintronella, cassia, ylang-ylang,
sweetflag, Japanese mint, oat husks (100,000 ppm), anise, broad-leaved lavender, myrtle flowers
(0–1 ppm), lemon verbena, Karaya gum (123,000 ppm), nutmeg seeds (15,000 ppm), West Indian
lemongrass, licorice roots (2 ppm), cinnamon bark (3 to 12 ppm), Hyssop shoots (1–2 ppm),
periwinkle leaves, rockrose leaves, and garden dill (Duke, 1992).
Identified as one of 140 volatile constituents in used soybean oils collected from a processing
plant that fried various beef, chicken, and veal products (Takeoka et al., 1996).
The gas-phase tailpipe emission rate from California Phase II reformulated gasoline-powered
automobile without a catalytic converter was 1.70 mg/km (Schauer et al., 2002).
Environmental Fate
Biological. Under nitrate-reducing and methanogenic conditions, furfural biodegraded to
methane and carbon dioxide (Knight et al., 1990). In activated sludge inoculum, following a 20-d
adaptation period, 96.3% COD removal was achieved. The average rate of biodegradation was
37.0 mg COD/gh (Pitter, 1976).
Photolytic. Atkinson (1985) reported an estimated photooxidation half-life of 10.5 h for the
reaction of furfural with OH radicals in the atmosphere.
Chemical/Physical. Slowly resinifies at room temperature (Windholz et al., 1983). May
polymerize on contact with strong acids or strong alkalies (NIOSH, 1997).
storage
Color Code—Blue: Health Hazard/Poison: Storein a secure poison location. Furfural must be stored to avoidcontact with oxidizing materials (such as perchlorates, peroxides, chlorates, nitrates, and permanganates) and strongacids because violent reactions occur. Store in tightly closedcontainers in a cool, well-ventilated area away from heat.Sources of ignition, such as smoking and open flames areprohibited where furfural is used, handled, or stored in amanner that could create a potential fire or explosion hazard. Before entering confined space where this chemicalmay be present, check to make sure that an explosive concentration does not exist.
Shipping
UN1199 Furaldehyde, Hazard class: 6.1; Labels:
6.1-Poisonous materials, 3-Flammable liquid.
Purification Methods
Furfural is unstable to air, light and acids. Impurities include formic acid, .-formylacrylic acid and furan-2-carboxylic acid. Distil it in an oil bath from 7% (w/w) Na2CO3 (added to neutralise acids, especially pyromucic acid). Redistil it from 2% (w/w) Na2CO3, and then, finally fractionally distil it under vacuum. It is stored in the dark. [Evans & Aylesworth Ind Eng Chem (Anal ed) 18 24 1926.] Impurities resulting from storage can be removed by passage through chromatographic grade alumina. Furfural can be separated from impurities other than carbonyl compounds by the bisulfite addition compound. The aldehyde is steam volatile. It has been purified by distillation (using a Claisen head) under reduced pressure. This is essential as is the use of an oil bath with temperatures of no higher than 130o which is highly recommended. When furfural is distilled at atmospheric pressure (in a stream of N2), or under reduced pressure with a free flame (caution: because the aldehyde is flammable), an almost colourless oil is obtained. After a few days and sometimes a few hours, the oil gradually darkens and finally becomes black. This change is accelerated by light and occurs more slowly when it is kept in a brown bottle. However, when the aldehyde is distilled under vacuum and the bath temperature kept below 130o during the distillation, the oil develops only a slight colour when exposed to direct sunlight during several days. The distillation of very impure material should NOT be attempted at atmospheric pressure; otherwise the product darkens very rapidly. After one distillation under vacuum, a distillation at atmospheric pressure can be carried out without too much decomposition and darkening. The liquid irritates mucous membranes. Store it in dark containers under N2, preferably in sealed ampoules. [Adams & Voorhees Org Synth Coll Vol I 280 1941, Beilstein 17/9 V 292.]
Toxicity evaluation
The limited data in animals are insufficient for deriving
a plausible mechanism of toxicity. Nevertheless, aldehyde
functional group is intrinsically reactive and low molecular
weight aldehydes such as formaldehyde are known to interact
with biologically important macromolecules such as DNA,
structural proteins, and enzymes. This supposition is consistent
with the toxic effects observed at multiple sites, i.e., respiratory
system, nervous system, liver, and kidneys.
Incompatibilities
May form explosive mixture with air.
Acids and bases can cause polymerization, causing fire or explosion hazard. Reacts violently with oxidants.
Incompatible with strong acids; caustics, ammonia, ali phatic amines; alkanolamines, alromatic amines; oxidizers.
Attacks many plastics.
Toxics Screening Level
The initial risk screening level (IRSL) is 0.06 μg/m3 with an annual averaging time.
Waste Disposal
Dissolve or mix the material
with a combustible solvent and burn in a chemical incinera tor equipped with an afterburner and scrubber. All federal,
state, and local environmental regulations must be
observed. Consult with environmental regulatory agencies
for guidance on acceptable disposal practices. Generators
of waste containing this contaminant (≥100 kg/mo) must
conform with EPA regulations governing storage, transpor tation, treatment, and waste disposal.
Pesticide Type
Fungicide; Nematicide
