T.R.

EGE UNIVERSITY

DEPARTMENT OF CHEMICAL ENGINEERING

KMY 401 CHEMICAL ENGINEERING DESIGN

PROJECT: FORMALIN
PRODUCTION

REPORT: 1

Submitted to: Prof. Dr. H. Ferhan ATALAY Prof. Dr. Firuz BALKA Assist. Dr. Zehra ZELK

Prepared by: 05057361 Gnter KULEOLU 05057274 Duygu BAYRAKTAR 05057288 Sinem ARMAY 05057330 Aya ATA

08.10.2008 BORNOVA/IZMIR

CONTENTS
SUMMARY
i 1 3 5 7 7 7 7 8 8 9 9 11 13 14
16

1.0 INTRODUCTION 2.0 RESULTS

2.1 PHYSICAL PROPERTIES 2.2 CHEMICAL REACTIONS
2.1.1 DECOMPOSITION 2.1.2 POLYMERIZATION 2.1.3 REDUCTION AND OXIDATION 2.1.4 ADDITION REACTIONS 2.1.5 CONDENSATION REACTIONS 2.1.6 RESIN FORMATION

2.3 USAGE AREA 2.4 STORAGE AND TRANSPORTATION 2.5 TOXICOLOGY, OPERATIONAL HEALTH AND PROCESS SAFETY
2.5.1 ACUTE TOXICITY 2.5.2 CANCER EPIDEMIOLOGY 2.5.3 ANIMAL CANCER STUDIES 2.5.4 GENOTOXICITY 2.5.5 FIRE AND EXPLOSION HAZARD 2.5.6 REACTIVITY 2.5.7 EMERGENCY AND FIRST AID PROCEDURES 2.5.8 spll, leak and dsposal procedures 2.5.9 montorng and measurng procedures 2.5.10 protectve equpment and clothng 2.5.11 engneerng and controls 2.5.12 medcal survellance 2.5.13 envronmental ssues

19 19 20 20 20 21 21 22 23 23 24 25 31 32 37 38-45

2.6 economc aspects 2.7 dsposal

3.0 DISCUSSION & CONCLUSIONS 4.0 REFERENCES 5.0 apPendCES

SUMMARY
Formalin is the aqueous form (37 wt%) of formaldeyhde produced mostly from methanol by an oxidation process. Because formaldehyde is highly water soluble, it is usually marketed as a liquid solution, typically at 37 weight percent formaldehyde solution, combined with water and up to 16 percent methanol. Recently, the production volume of formaldehyde has grown rapidly with increasing demand in manufacturing sector for resins including phnolic, urea, melamin, acetal many additives. Other additional application areas of formaldehyde include surface coating, leather tanning, bindery applications, laminates, insulation materials, etc. Also, formaldehyde is a preservative disinfection of bacteria.

Formalin is mainly manufactured by methanol oxidation of which processes are excess methanol process and excess air process and combined cataylst process. The basic difference between them is the catalyst applied. The methanol excess process, called the silver process, employs silver as the catalyst while the air excess process (molybdenum process) uses metallic oxides of iron and molybdenum. In considering higher investment cost and more complicated operation than the silver process, it is recommended to use the silver process.

Uses of formalin can be summarized as follows: Phenol resin and adhesives, urea and melamine adhesives Urea resin, melamine resin, hexamethy lenetetramine Pentaerythritol, paraformaldehyde Medicines and agricultural chemicals Polyacetal resin Hemiformal

Moreover, use of formaldeyhde derivatives and formalin are explained comprehensively in Results part. Manufacturing processes of formalin are studied and the flow sheets of the processes are given in the Appendix part. Also, there are known effects of formaldehyde and its derivatives, therefore the needed information about its toxicology, exposure even occupatioanl health and environmental issues are given in the Results section.

1.0 INTRODUCTION
Since Blums proposal of formalin as a useful general biological fixative in 1893 it has become an unsurpassed standard. For 119 years zoologists, botanists, histologists, and pathologists have used formalin to preserve their materials for a detailed anatomical, histological or cytological study. To pathologists it represents until now the only admissible standard, in spite of the denounced toxicity of the product. Formalin is an aqueous solution of formaldehyde. The typical concentration is 37 - 40 %. That is, it is expected that a commercial formalin has 370 - 400 g of formaldehyde in each 1000 g of commercial solution. The intended dilution is w/w, not vol/vol. Formaldehyde is a nearly colorless gas with a pungent, irritating odor even at very low concentrations (below 1 ppm). Its vapors are flammable and explosive. Because the pure gas tends to polymerize, it is commonly used and stored in solution. Formalin, the aqueous solution of formaldehyde (30% to 50% formaldehyde), typically contains up to 15% methanol as a stabilizer. As formaldehyde is self-reactive, and continues to oxidize in aqueous solution producing formic acid, and in older solutions may even form a precipitate of paraformaldehyde (a solid polymerized formaldehyde). Formalin solutions thus really contain formaldehyde, paraformaldehyde, formic acid, and methanol. Formaldehyde is used in the manufacture of plastics; urea-formaldehyde foam insulation; and resins used to make construction materials (e.g., plywood), paper, carpets, textiles, paint, and furniture. The first industrial process for production of formalin, an aqueous solution of formaldehyde, was based on oxidative dehydrogenation of methanol over a copper catalyst. Improvements in catalyst technology resulted in substitution of the copper catalyst for an unsupported silver catalyst, which is the formula still used today. In the 1950s a competing process for production of formaldehyde was developed. This process was based on selective (partial) oxidation of methanol over an Fe-Mo (molybdenum and iron) oxide catalyst. The two processes, (Oxidation-dehydrogenation using a silver catalyst involving either the complete or incomplete conversion of methanol; and the direct oxidation of methanol to formaldehyde using metal oxide catalysts (Formox process)), referred to as silver and oxide processes respectively, are used today for the production of formalin on the industrial scale. Each process accounts for about 50% of the total production of formalin, which today amounts to about 20Mton per annum, expressed as 37 wt% HCHO in water.

In the silver process, vapourised methanol with air and steam is passed over a thin bed of silver-crystal catalyst at about 650oC. Formaldehyde is formed by the dehydrogenation of methanol. The heat required for the endothermic reaction is obtained by burning hydrogen contained in the off-gas produced from the dehydrogenation reaction. The other process, oxide process, involves the oxidation of methanol over a catalyst of Fe-Mo oxide. A mixture of air and methanol is vapourised and passed into catalyst-packed reactor tubes. The reaction which takes place at 350oC is highly exothermic and generates heat to provide steam for turbines and process heating. Yields from both processes are around 90% to 92% but the oxide process has a lower reaction temperature and the metal catalyst is cheaper than silver. However, the silver process is still the most prevalent. A wide range of alternative feedstocks have been considered but not found to be economic. For example, a tiny amount is produced from the non-catalytic oxidation of propane-butane mixtures. Formaldehyde can be produced from methane but a mixture of products needs to be separated. It is also a byproduct of the oxidation of naphtha to acetic acid. Formaldehyde can cause irritation of the eyes, nose, and throat, even at low levels for short periods. Longer exposure or higher doses can cause coughing or choking. Severe exposure can cause death from throat swelling or from chemical burns to the lungs. Direct contact with the skin, eyes, or gastrointestinal tract can cause serious burns. Drinking as little as 30 mL (about 2 tablespoons) of formalin can cause death. Formate, a formaldehyde metabolite, can cause death or serious systemic effects. Generally, more serious the exposure to formaldehyde is the more severe are the symptoms. Previously sensitized persons may develop a skin rash or breathing problems from very small exposures. Formaldehyde has low cost, high purity, and variety of chemical reactions, so it has become one of the worlds most important industrial and reasearch chemicals. More than 50 branches of industry now use formaldehyde, mainly in the form of aqueous solutions and formaldehyde-containing resins. Worldwide production of formaldehyde is 3 10 6 t / a .

2.0 RESULTS
Formaline process description information and other related information found in literature during feasibility study is composed in a logical order. Firstly process description is given as a result: The direct synthesis of formaldehyde from hydrocarbons has not yet resulted in cost reductions and because of the reactivity of formaldehyde, its handling and separation, as well as its direct preparation from hydrocarbons, are difficult. These factors, in the past, have exerted considerable influence on the pattern of formaldehyde growth. Currently, the only and competing production technologies for formaldehyde of commercial significance are based on the partial oxidation and dehydrogenation of methanol using a silver catalyst, or partial oxidation of methanol using a metal oxide-based catalyst since nearly all of the world's formaldehyde is made from methanol. In the silver catalyst route, which is also known as Methanol Excess Process, vaporized methanol with air and steam is passed over a thin bed of silvercrystal catalyst at about 650C. Formaldehyde is formed by the dehydrogenation of methanol. The heat required for the endothermic reaction is obtained by burning hydrogen contained in the off-gas produced from the dehydrogenation reaction. The other route, which is also known as Air Excess Process, involves the oxidation of methanol over a catalyst of molybdenum and iron oxide (Formox Process - developed and licensed by Reichhold Chemicals). A mixture of air and methanol is vaporized and passed into catalyst-packed reactor tubes. The reaction which takes place at 350C is highly exothermic and generates heat to provide steam for turbines and process heating. A high pressure version of the Formox Process called as Perstorp Process also exists, which can be retrofitted to existing plants to boost capacity. The high conversion rate of the process eliminates the need for methanol recovery via distillation, and it can produce formaldehyde at concentrations up to 57%.
SILVER CATALYST PROCESS:

The silver catalyst process employs two main reactions,

which are given below, to convert methanol to formaldehyde: Dehydrogenation and Partial Oxidation. CH 3OH HCHO + H 2 CH 3OH + 1 O2 HCHO + H 2O 2

The equilibrium conversion in the dehydrogenation reaction is highly temperature dependent. The amount of process air controls the temperature by supplying oxygen to the exothermic reactions, including oxidation of hydrogen. The addition of inert materials such as water or nitrogen can also aid conversion by permitting the use of higher methanol concentrations relative to oxygen without entering the explosive region. These techniques permit variations in the process: Incomplete conversion plus separation and recycle of unreacted methanol, Complete conversion. The usual commercial form of the silver catalyst process involves incomplete conversion of methanol at lower temperatures, which minimizes byproducts, followed by distillation to remove and recycle the methanol. This allows the fine-tuning of the amount of methanol in the final product. Formaldehyde product may be produced at concentrations of up to 52- 55% by adjusting the amount of water added in formaldehyde absorption. Methanol concentrations can be adjusted as required (normally less than 1%) by distillation. In some cases, an ion exchange unit is needed to reduce the formic acid concentrations, but most commercial processes claim a figure of 0.06% without ion exchange. The methanol conversion per pass is typically 75- 85%, and overall process yield of formaldehyde from methanol is 90- 92 mol percent. Impurities, particularly iron, determine the catalyst life. The catalyst bed has a tendency to become matted under conditions of high temperature and throughput. Catalyst life is typically one year and it may be electrolytically regenerated. Although steam is generated internally, with most designs there is a net steam import requirement. At a temperature of around 700C, methanol conversion is sufficiently high to dispense with the final distillation column. A complete conversion process plant is similar to that described for incomplete conversion, described above, in most other respects.
METAL OXIDE CATALYST PROCESS:

The basis of the metal oxide catalyst process is the

vapor-phase oxidation of methanol with excess oxygen (from air) at temperatures of 250400C.

Metal oxides in the catalyst are typically molybdenum and iron at a molar ratio of 1.5 to 2.0 (Mo:Fe). Small amounts of oxides of vanadium, cobalt, phosphorus, chromium and copper may also be included.

Further reactions can occur to some extent, depending on temperature. These include the continued oxidation of formaldehyde to formic acid and carbon monoxide, and dehydration of methanol to dimethyl ether.

A significant variation on this process is the absorption of the formaldehyde into a urea solution to make urea-formaldehyde precondensate. This can be used for the production of urea-formaldehyde resins, the largest single use of formaldehyde.

Recycle of inerts permits the use of relatively high methanol concentrations without creating an explosive mixture. Oxygen concentration is kept to approximately 10%, whereas methanol is around 6- 9%, both on a molar basis.

The Fe/Mo oxide catalyst is relatively insensitive to impurities such as iron carbonyls in the methanol feedstock. In a typical design, the catalyst is supplied as rings, and a very constant temperature profile is maintained by the use of a number of layers with different catalytic activities. A typical catalyst life is 18 months.

Export steam from the process is around 0.5 pound per pound of product. Licensors claim methanol conversion per pass of 92- 94%. Therefore, no distillation column is required to recover and recycle methanol in the product stream. Maximum methanol content ranges from between 0.5 and 1.0 percent for 37 weight percent product to 1.5 percent for 50 weight percent product. The formaldehyde solution typically contains 0.02- 0.04 percent formic acid. If required, the formic acid concentration can be further reduced in an ion exchangers.
2.1 PHYSICAL PROPERTIES

Formaldehyde, CH2O, formula weight 30.03 is the first member of the series of aliphatic aldehydes, is a colorless gas at ambient temperature that has a pungent, suffocating odor and an irritant action on the eyes and skin.

Formaldehyde gas is flammable, its ignition temperature is 430 C; mixtures with air are explosive. At ca. 20 C the lower and upper explosive limits of formaldehyde are ca. 7 and 72vol% (87 and 910 g/m3), respectively. Flammability is particularly high at a formaldehyde concentration of 65-70 vol %. At a low temperature, liquid formaldehyde is miscible in all proportions with nonpolar solvents such as toluene, ether, chloroform, or ethyl acetate. Polar solvents, such as alcohols, amines or acids, either catalyze the polymerization of formaldehyde or react with it to form methylol compounds or methylene derivatives. Since pure formaldehyde is a gas at ordinary temperatures and cannot be readily isolated or handled in this state, it is marketed chiefly in the form of its aqueous solutions. Monomeric physically dissolved formaldehyde is only present in low concentrations of up to 0.1 wt%. At ordinary temperatures, formaldehyde gas is readily soluble in water, alcohols and other polar solvents. Dissolution of formaldehyde in water is exothermic, the heat of solution (62 kJ/mol) being virtually independent of the solution concentration. Clear, colorless solutions of formaldehyde in water can exist at a formaldehyde concentration up to % wt 95, but the temperature must be raised to 120 C to obtain the highest concentrations. Concentrated aqueous solutions containing more than 30 wt% formaldehyde becomes cloudy on storage at room temperature, because larger poly glycols are formed which then precipitate out. The partial pressure of formaldehyde in equilibrium with the solution is low, due to solvation, and is a function of methylene glycol concentration rather than the total formaldehyde content. Formaldehyde is apparently not appreciable associated in the gaseous state, and its partial pressure may be regarded as the decomposition pressure of the dissolved hydrate. These factors explain the fact that formaldehyde solutions may be concentrated by vacuum evaporation at low temperatures, whereas pressure distillation at high temperatures makes its possible to obtain concentrated distillates from dilute solutions. On distillation at ordinary pressures without rectification, the still residue is always somewhat more concentrated than the distillate solution. Fractional condensation of the vapors of boiling solutions results in increasing ratio of formaldehyde to water in uncondensed vapors since water is the least volatile constituent of the mixed vapor. For more information on physical properties of formalin, see the MSDS given in Appendix.

2.2 CHEMICAL REACTIONS

Formaldehyde is one of the most reactive organic compounds known and, thus, differs greatly from its higher homologues and aliphatic ketones. Formaldehyde will combine chemically with practically every type of organic chemical with the exception of paraffin. It can be employed as in the form of monomer, solution or polymer with essentially equivalent result. In general, the form used is of importance chiefly in its effect on the rate of reaction. Monomeric and polymeric forms are of special value where the presence of water is undesirable. Solutions and polymers are less reactive than the monomer, since they represent lower energy potentials in which the aldehyde has already reacted with itself or water. The most important reactions are treated as below:
2.2.1 DECOMPOSITION

At 150 C, formaldehyde undergoes heterogeneous decomposition to form mainly methanol and CO2. Above 350C, however, it tends to decompose into CO and H2. Metals such as platinum, copper, chromium, and aluminum catalyze the formation of methanol, methyl formate, formic acid, CO 2, and methane.
2.2.2 POLYMERIZATION

Anhydrous monomeric formaldehyde cannot be handled commercially. Gaseous formaldehyde polymerizes slowly at temperatures below 100 C, polymerization being accelerated by traces of polar impurities such as acids, alkalis, or water. Thus, in the presence of steam and traces of other polar compounds, the gas is stable at ca. 20 C only at a pressure of 0.25-0.4 kPa, or at a concentration of up to ca. 0.4 vol% at ca. 20 C and atmospheric pressure. Monomeric formaldehyde forms a hydrate with water; this hydrate reacts with further formaldehyde to form polyoxymethylenes. Methanol or other stabilizers, such as guanamines or melamines, are generally added to commercial aqueous formaldehyde solutions (37-55 wt%) to inhibit polymerization.
2.2.3 REDUCTION AND OXIDATION

Formaldehyde is readily reduced to methanol with hydrogen over a nickel catalyst. For example, formaldehyde is oxidized by nitric acid, potassium permanganate, potassium dichromate, or oxygen to give formic acid or CO, and water, In the presence of strong alkalis or when heated in the presence of acids, formaldehyde undergoes a Cannizzaro reaction with formation of methanol and formic acid. In the presence

of aluminum or magnesium methylate, paraformaldehyde reacts to form methyl formate (Tishchenko reaction).
2.2.4 ADDITION REACTIONS

The formation of sparingly water-soluble sodium formaldehyde bisul-fite is an important addition reaction of formaldehyde. Hydrocyanic acid reacts with formaldehyde to give glycolonitrile. Formaldehyde undergoes an acid-catalyzed Pnns reaction in which it forms a-hydroxy-methylated adducts with olefms .Acetylene undergoes a Reppe addition reaction with formaldehyde to form 2-butyne-l,4-diol. Strong alkalis or calcium hydroxide convert formaldehyde to a mixture of sugars, in particular hexoses, by a multiple aldol condensation which probably involves a glycolaldehyde intermediate. Mixed aldols are formed with other aldehydes; the product depends on the reaction conditions. Acetaldehyde, for example, reacts with formaldehyde to give pentaerythritol, C(CH,OH)4 .
2.2.5 CONDENSATION REACTIONS

Important condensation reactions are the reaction of formaldehyde with amino groups to give Schiff s bases, as well as the Mannich reaction. Amines react with formaldehyde and hydrogen to give methyl-amines. Formaldehyde reacts with ammonia to give

hexamethylenetetramine, and with ammonium chloride to give monomethylamine, dimethylamine, or trimethylamine and formic acid, depending on the reaction conditions. Reaction of formaldehyde with diketones and ammonia yields imidazoles. Formaldehyde reacts with many compounds to produce methylol (-CH2OH) derivatives. It reacts with phenol to give methylolphenol, with urea to give mono-, di-, and trimethylolurea, with melamine to give methylolmelamines, and with organometallic compounds to give metal-substituted methylol compounds. Aromatic compounds such as benzene, aniline, and toluidine combine with formaldehyde to produce the corresponding diphenyl-methanes. In the presence of hydrochloric acid and formaldehyde, benzene is chloromethylated to form benzyl chloride. Formaldehyde reacts with hydroxylamine, hydrazines, or semicarbazide to produce formaldehyde oxime (which is spontaneously converted to triformoxime), the corresponding hydrazones, and semicarbazone, respectively. Double bonds are also produced when formaldehyde is reacted with malonates or with primary aldehydes or ketones possessing a CH2 group adjacent to carbonyl group.

2.2.6 RESIN FORMATION

Formaldehyde condenses with urea, melamine, urethanes, cyanamide, aromatic sulfonamides and amines and phenols to give a wide range of resins.
2.3 USAGE AREA

Formalin is an aqueous solution of formaldehyde. Formaldehyde has been used for many years in consumer goods to deter spoilage caused by microbial contamiantion. It has been used as a preservative in household cleaning agents, dishwashing liquids, fabric softeners, shoe-care agents, car shampoos and waxes, and carpet cleaning agents. Generally the formaldehyde content in these products is less than 1%. Formaldehyde is commercially offered as a 37 wt% to 50 wt% aqueous solution, with 37 wt% (known as formalin or formol) being the most widely used grade which may also contain 0-15 wt% methanol and a polymerisation inhibitor. As formaldehyde is self-reactive, and continues to oxidize in aqueous solution producing formic acid, and in older solutions may even form a precipitate of paraformaldehyde (a solid polymerized formaldehyde). Formalin solutions thus really contain formaldehyde, paraformaldehyde, formic acid, and methanol. Formaldehyde is used as a chemical intermediate in the manufacture of a large variety of organic compounds, ranging from amino and phenolic resins to slow release fertilizers. Products manufactured using organic compounds, where formaldehyde is used as a chemical intermediate in their production, include: plywood adhesives, abrasive materials, insulation, foundry binders, and brake linings made from phenolic resins, surface coatings, molding compounds, laminates and wood adhesives made from melamine resins; phenolic thermosetting, resins curing agents and explosives made from hexamethylenetetramine; urethanes, lubricants, alkyd resins and multifunctional acrylates made from

trimethylolpropane; plumbing components from polyacetal resins; and controlled-release fertilizers made from urea formaldehyde concentrates. Polyacetal plastics produced by polymerization of formaldehyde are incorporated into automobiles to reduce weight and fuel consumption. They are also used in the manufacture of functional components of audio and video electronics equipment. Formaldehyde solutions have also been used for disinfecting dwellings, ships, storage houses, utensils, and clothing. Solutions containing 28% formaldehyde have been used as

germicides to disinfect inanimate objects. Formaldehyde is used as a tissue preservative and disinfectant in embalming fluids. In agricultural industry, formaldehyde has been used as a fumigant, as a preventative for mildew and spelt in wheat, and for rot in oats. It has been used as a preplanting soil sterilant in mushroom houses. Formaldehyde has been used as a germicide and a fungicide for plants and vegetables; as an insecticide for destroying flies and other insects; and in the manufacture of slow-release fertilizers. Approximately 80% of the slow-release fertilizer market is based on urea-formaldehyde-containing products. Formaldehyde continues to be used in the manufacture of glass mirrors, explosives, artificial silk and dyes; for waterproofing fabrics; for preserving and coagulating rubber latex; and for tanning and preserving animal hides. In photography industry, formaldehyde has been used for hardening gelatin plates and papers, toning gelatin-chloride papers, and for chrome printing and developing. Formaldehyde is used as an antimicrobial agent in many cosmetic products, including soaps, shampoos, hair preparations, deodorants, lotions, make-up, mouthwashes, and nail products. Formaldehyde is incompatible with ammonia; alkalies; tannin; iron preparations; and salts of copper, iron, silver, potassium permanganate, iodine, and peroxide. When it is used as a preservative in shampoos, formaldehyde may interact unfavorably with both fragrance components and color additives. Some cosmetics have reportedly contained 0.6% formaldehyde, while concentrations as high as 4.5% have been detected in nail hardeners. Formaldehyde concentrations in dry-skin lotions, creme rinses, and bubble bath oils have reportedly ranged from 0.4 to 0.5%. Formaldehyde has also been found in sun-tan lotion and hand cream, bath products, mascara and eye make-up, cuticle softeners, nail creams, vaginal deodorants, and shaving creams. Trace amounts of formaldehyde found in cosmetic products could also result from its use as a disinfectant of the manufacturing equipment.

Compared to its use in product manufacturing, the use of formaldehyde in the medical fields is relatively small. Consumption in this area averages approximately 1.5% of the total production volume. Some of the earlier, minor, medicinal applications for formaldehyde included its use during vasectomies, as a foot antiperspirant or as a preservative in such products, as a treatment for athletes foot, and as a sterilant for echinococcus cysts prior to their surgical removal. In veterinary medicine, formaldehyde has been used therapeutically as an antiseptic and as a fumigant. It has also been used to treat tympany, diarrhea, mastitis, pneumonia, and internal bleeding in animals. In animal nutrition, formaldehyde is used to

protect dietary protein in ruminants. It is used as a food additive to improve the handling characteristics of animal fat and oilseed cattle food mixtures. Other industries using formaldehyde in their processes include the sugar industry where formaldehyde is used as an infection inhibitor in producing juices; the rubber industry where it is used as a biocide for latex, an adhesive additive, and an anti-oxidizer additive for synthetic rubber; and the food industry where it is used for preserving dried foods, disinfecting containers, preserving fish and certain oils and fats, and modifying starch for cold swelling. It has been use as a bacteriostatic agent in some foods, such as cheese. In the petroleum industry, formaldehyde is used as a biocide in oil well-drilling fluids and as an auxiliary agent in refining. Formaldehyde has been used as an anti- corrosive agent for metals. In the plastics industry, for the preparations of phenol, urea, and melamine resins, where the presence of water could interfere with the production process, paraformaldehyde may be used in place of aqueous formaldehyde solutions. In addition to its use in selected pesticide applications, paraformaldehyde has also been used in making varnish resins, thermosets, and foundry resins, the synthesis of chemical and pharmaceutical products, the preparation of disinfectants and deodorants, and the production of textile products. Formaldehyde was used in the textile industry as early as the 1950s when formaldehyde-based resins were initially used to produce crease-resistant fabrics. Postproduction analysis

indicated that these early resins contained a substantial amount of extractable formaldehyde (more than 0.4% by weight of the fabric. With the introduction of new resins and other process modifications in the 1970s, the level of extractable formaldehyde in crease-resistant fabrics gradually decreased to 0.010.02%.
2.4 STORAGE AND TRANSPORTATION

With a decrease in temperature and/or an increase in concentration, aqueous formaldehyde solutions tend to precipitate paraformaldehyde. On the other hand, as the temperature increases, so does the tendency to form formic acid. Therefore, an appropriate storage temperature must be maintained.

Table 2.1: Storage temperatures for commercial formaldehyde solutions.

Formaldehyde content, wt% 30 37 37 37 50 50

Methanol content, wt%

Storage Temperature, C

1 <1 7 10-12 1-2 1-2

7-10 35 21 6-7 45* 60-65

*Stabilized with 200 mg/kg of isophthalobisguanamine. The addition of stabilizers is also advisable (e.g., methanol, ethanol, propanol, or butanol). However, these alcohols can be used only if they do not interfere with further processing, of if they can be separated off; otherwise, effluent problems may be encountered. The many compounds used for stabilizing formaldehyde solutions include urea, melamine, hydrazine hydrate, methylcellulose, guanamines, and bismelamines. For example, by adding as little as 100 mg of isophthalobisguanamine per kg of solution, a 40 wt% formaldehyde solution can be stored for at least 100 days at 17 C without precipitation of paraformaldehyde, and a 50 wt% formaldehyde solution can be stored for at least 100 days at 40 C. Formaldehyde can be stored and transported in containers made of stainless steel, aliminum, enamel, or polyester resin. Iron container lined with epoxide resin or plastic may also be used, although stainless steel containers are preferred, particularly for higher formaldehyde concentrations. Unprotected vessels of iron, copper, nickel, and zinc alloys must not be used. The flash point of formaldehyde solution is in the range 55-85 C, depending on their concentrations and methanol content. According to German regulations for hazardous substances (Gefahrstoffverordnung, Appendix 6) and Appendix 1 of the EEC (European Economic Community) guidelines for hazardous substances, aqueous formaldehyde solutions used as working materials that contain 1 wt% of formaldehyde must be appropriately labeled. Formaldehyde should be stored in a cool, dry, well-ventilated area and properly labeled. Formaldehyde should never be stored in vehicles except to transport to and from

field during sampling operations. Used formaldehyde, either from spill clean-up or from activities generated from the process of change-out of sample containers must be stored in a properly labeled hazardous waste container and made available for recycling under Resources Conservation Recovery Act (RCRA) protocols. Storage of waste formaldehyde should be in an area not frequented by the general population or duty workers and should be in an area not subject to heat cycles and well ventilated. Formaldehyde should be transported only in original container, fully labeled and stored properly within the vehicle to prevent shifting, spillage or breakage. Formaldehyde should never be opened, mixed or transferred to sample vials at any time inside a closed vehicle. A Materials Safety Data Sheet (MSDS) should be in the possession of the user and made available to those working with this chemical. During operational use and/or during transportation where an accidental spill is likely to occur, each field unit should have as part of their required emergency equipment, sufficient absorbent material to handle small spills. Clean, 1 gallon plastic Nalgene containers with Teflon screw caps, or equivalent, clearly labeled, should be available for small spills and for transporting used formalin from the field to the laboratory for proper disposal. Care should be exercised during clean-up that no person becomes dermally exposed to formaldehyde. If, during the emergency, the spill occurs where there is insufficient ventilation to proceed with clean-up, the area should be vacated immediately and others should be prevented from entering the spill area unless properly suited and with a self- contained air supply. Proper authorities should be notified if the spill occurs on a roadway or has potential to do harm by entering a water supply or other bodies of water where there is a greater exposure potential to humans and/or an aquatic ecosystem. A record of how much of the chemical was spilled and the method of clean-up and proper disposal should be under-taken once the spill has been contained and dealt with, not during the emergency. If exposed to formaldehyde, flush exposed skin with copious amounts of water and remove contaminated clothing as quickly as possible to prevent continued exposure.
2.5 TOXICOLOGY, OCCUPATIONAL HEALTH AND PROCESS SAFETY

Formaldehyde is a colorless, pungent gas which polymerizes slowly at room temperature. The four basic uses for formaldehyde include use as a bactericide or fungicide, in the production of resins, as intermediates in the production of chemicals, and as a

component of end-use consumer items. Formaldehyde is also used as embalming fluid and in textile treating to impart wrinkle-resistance to clothing. Facilities reporting the highest exposures (0.1 to above 1.0 ppm) to formaldehyde include those producing hardwood plywood, particle board, fiberboard and resins as well as foundries, laboratories and funeral services. Industries in textile finishing, apparel

manufacturing, formaldehyde production and plastic molding have the next highest exposures ranging from 0.1 to 1.0 ppm. A long list of facilities have exposures to low concentrations (0.1 - 0.5 ppm), among them being pulp, paper and paperboard mills , softwood plywood manufacturers, manufacturers of various cardboard and paper products, paint, pigment and dye manufacturers, photo finishing labs, hemodialysis units, biology and veterinary labs, and various facilities dealing with electrical devices. Formaldehyde is an essential intermediate in cell metabolism in mammals and humans. All tissues contain measurable amounts of formaldehyde, e.g., human blood 2-3 ppm. Formaldehyde does not accumulate in the environment or in the human body because it is rapidly oxidized or biodegraded. In the body, exogeneous formaldehyde is metabolized with a half-life of 1.5 minutes into formic acid and carbon dioxide.
2.5.1 ACUTE TOXICITY

Formalin (aqueous formaldehyde) is highly acutely toxic with deaths occurring with as little as 30 milliliters (ml, about one once) ingested. The inhalation of high concentrations of formaldehyde is also extremely dangerous, with the IDLH (Immediately Dangerous to Life and Health) concentration being 100 ppm. Accidental splash exposures into the eyes may cause blindness especially in cases where immediate flushing of the eyes with water does not occur. Irritation of eyes, nose, throat and chest is an acute response to formaldehyde that diminishes rapidly upon removal from exposure. OSHA (Occupational Safety and Health Administration) reports that irritation complaints occur from employees manufacturing particle board and molded plastics at levels of 0.4 to 1.0 ppm, by foundry care room workers exposed to more than 1 ppm, by dialysis nurses exposed to 0.26 to 0.4 ppm, by embalmers exposed to 0.25 to 1.39 ppm, by carpenters exposed to formaldehyde treated wood at 0.35 ppm, by textile finishers exposed at 0.16 to 1.2 ppm, and by garment workers with exposures

of 0.42 to 0.50 ppm. In an independent clinical study, irritation at concentrations up to 0.04 ppm in 2% to 4% of those tested was reported. A major effect of formaldehyde on the skin is dermatitis, both irritant dermatitis and "allergic" contact dermatitis which results in a small percentage of the population. Formaldehyde had also been reported to cause hives. Although there is some absorption of formaldehyde through the skin, it is not considered significant. Formaldehyde has also been reported to cause asthma which may develop within minutes of exposure or several hours after the exposure, either during the latter part of the work day or after returning home. The development of asthma may be influenced by

continuous or intermittent exposures. Exposures to high concentrations for a short period may be more hazardous in causing asthma than exposure to low concentrations over an extended period.
Ingestion (Swallowing):

Liquids containing 10 to 40% formaldehyde cause severe irritation

and inflammation to the mouth, throat, and stomach. Severe stomach pains will follow ingestion with possible loss of consciousness and death. Ingestion of dilute formaldehyde solutions (0.03-0.04%) may cause discomfort in the stomach and pharynx.
Inhalation (Breathing):

Formaldehyde is highly irritating to the upper respiratory tract and

eyes. Concentrations of 0.5 to 2.0 ppm may irritate the eyes, nose, and throat of some individuals. Concentrations of 3 to 5 ppm also cause tearing of the eyes and are intolerable to some persons. Concentrations of 10 to 20 ppm cause difficulty in breathing, burning of the nose and throat, cough, and heavy tearing of the eyes; 25 to 30 ppm causes severe respiratory tract injury leading to pulmonary edema and pneumonitis. A concentration of 100 ppm is immediately dangerous to life and health. Deaths from accidental exposure to high concentrations of formaldehyde have been reported.
Skin (Dermal):

Formalin is a severe skin irritant and a sensitizer. Contact with formalin

causes white discoloration, smarting, drying, cracking, and scaling. Prolonged and repeated contact can cause numbness and a hardening or tanning of the skin. Previously exposed persons may react to future exposure with an allergic eczematous and dermatitis or hives.
Eye Contact:

Formaldehyde solutions splashed in the eye can cause injuries ranging from

transient discomfort to severe, permanent corneal clouding and loss of vision. The severity of the effect depends on the concentration of formaldehyde in the solution and whether or not the eyes are flushed with water immediately after the accident.

Note:

The perception of formaldehyde by odor and eye irritation becomes less sensitive with

time as one adapts to formaldehyde. This can lead to overexposure if a worker is relying on formaldehyde's warning properties to alert him or her to the potential for exposure.
2.5.2 CANCER EPIDEMIOLOGY

Lung Cancer:

Several recently published epidemiological studies have been instrumental in the development of the new formaldehyde regulations. Perhaps the most important as well as controversial study was conducted and published by the National Cancer Institute (NCI). In one of the largest cohort mortality analyses, 26561 workers employed prior to January 1, 1966 were studies for excess lung cancer. Investigators compared the mortality of formaldehydeexposed workers with that of the United States population, the local population and nonexposed workers. Although a significant increase in lung cancer was observed in the worker population, the investigators (Blair, et al.) concluded that "these data provide little evidence that mortality from cancer is associated with formaldehyde exposures at levels experienced by workers in this study" primarily due to a lack of correlation between increased cancer risk and increased dose (as measured by cumulative exposure). The investigators' comments were met with much criticism from other scientists who reviewed the raw data from the study. A five member Advisory Panel to the study concluded that, "The finding of a significant increase in the risk for lung cancer...makes up particularly hesitant to characterize this as a study with evidence to exonerate formaldehyde as a carcinogen." Likewise, the National Institute for Occupational Safety and Health (NIOSH -- the research branch affiliated with OSHA) concluded that, "Sufficient evidence exists...to conclude that there are significant excesses of lung cancer...The absence of anexposure-response trend is not sufficient cause to discount the observed lung cancer excesses..." Federal OSHA agreed with both the Advisory Panel and NIOSH stating that a significant increase in lung cancer can determine carcinogenicity even if the study failed to establish a dose-response curve. Two independent researchers (Sterling and Weikam) proceeded to statistically reexamine the data from the NCI study. The researchers reconfirmed a significant lung cancer excess. Among the criticisms submitted primarily by the Formaldehyde Institute and Dupont, their analyses failed to correct for cigarette smoking as well as other items. OSHA

defined their analyses by noting that the percentages of deaths resulting from lung cancer in formaldehyde-exposed workers were excessively high and significant. Another independent researcher (Sielken) took the raw data from the NCI study and correlated the formaldehyde exposure data with the likelihood of dying from cancer of the respiratory system and lung cancer. The United Auto Workers (UAW) reanalyzed a section of the NCI study and concluded an increasing likelihood of death due to lung cancer. They also discovered that persons exposed at the highest cumulative doses were less likely to smoke because of formaldehyde's irritant effects. In summary, OSHA's position was that there was no dose-response relationship in the NCI study due to exposure misclassifications and due to the fact that cigarette smoking was not evident in workers with the highest cumulative doses. OSHA supported the study's finding that there was a significant increase in lung cancer in workers with 20 or more years of latency. They also noted the probability of a trend of an increased risk of lung cancer with an increase in the average level of formaldehyde exposure. OSHA also noted a British study of lung cancer which concluded a significant excess of lung cancer among workers at the highest exposure level (greater than 2.0 ppm) after comparison with national rates of lung cancer. A significant increase in risk of death from chronic bronchitis was also observed. A possible dose-response relationship was noted. Although the authors downplayed the validity of their cancer results due to the high national rates of lung cancer, OSHA discounted their downplay and supported the study's findings.
Nasopharyngeal Cancer:

The NCI study also noted an "increased risk of death from cancer of nasopharynx with an increased cumulative exposure to formaldehyde (however) a not statistically significant (but) a striking dose-response gradient was observed by the authors." OSHA supported the importance of the study in relating formaldehyde concentration to nasopharyngeal cancer. Excursions to levels exceeding 4 ppm were noted. Cancer was also observed in workers exposed to high concentration for less than 1 year. The Formaldehyde Institute and Cyanamid Company criticized the study stating that the formaldehyde exposure was mixed with a particulate exposure, that there were only 3 cancer cases of the 7 total who were exposed for less than 1 year and that there were no cases observed in workers with the highest cumulative exposure. OSHA regarded the criticisms as insignificant. In another study conducted by an independent researcher (Vaughan et al.) in the state of Washington, residents living in mobile homes exposed to formaldehyde through

formaldehyde-treated building materials, as well as occupations dealing with resin and glue work (i.e., carpenters with less than a 0.5 ppm exposure, and furniture assemblers, cabinet makers and sewing machine operators having exposures greater than 0.5 ppm) were studied. Due to the extremely low exposure potential and cancer risk observed in most of the workers, OSHA concluded that is was inappropriate to conclude that the occupational study was negative even though excess cancer was not observed. On the other hand, the residential exposures were greater than the workplace exposures from the standpoint of cumulative dose. Exposures lasting up to 168 hours

(compared to typical 40 hour a week work exposures) were observed with concentrations in new mobile homes of years ago averaging as much as 0.5 ppm. OSHA determined that formaldehyde exposure is probably associated with the development of nasopharyngeal cancer in humans. Although rare, nasopharyngeal cancer existed with a background rate of approximately half of that seen in home residents.
Oral Cancer:

The National Institute of Occupational Safety and Health (NIOSH) conducted a study on workers exposed to formaldehyde in the garment industry manufacturing permanent press garments. Workers were exposed for at least 3 months to concentrations of o.14 to 0.17 ppm. The investigators reported excess oral cancer. OSHA, however, severely criticized the study stating that "some evidence of an association between formaldehyde exposure and oral cancer (existed) but not necessarily a causal relationship." OSHA criticized the study for limited latency periods, a middle-aged female population and a low percentage (5.5%) of deaths from cancer.
Brain Cancer:

Brain cancer has been reported in pathologists, anatomists, morticians, embalmers and funeral directors exposed to embalming fluid or other tissue preservatives containing formalin. Exposure concentrations were not given. OSHA stated that the exposure

"probably" contributed to the excess risk of brain cancer observed in professional workers but was unable to reach a determination that brain cancer is caused by exposure to formaldehyde.
Other Cancers:

Leukemia has been reported in embalmers. OSHA's position was similar to that stated above for reports of brain cancer.

2.5.3 ANIMAL CANCER STUDIES

Several laboratories have studied cancer in animals. The one of greatest interest was conducted by Battelle Columbus Laboratories for the Chemical Industry Institute of Toxicology (CIIT). 120 male and female animals of each of two species, one rat and one mouse, were exposed for 6 hours/day, 5 days a week at concentrations averaging 2.0, 5.6, and 14.3 ppm in an inhalation experiment for 24 months (the average lifespan of a rodent). In the rats, there was a significant increase in nasal cancers at the highest concentration. The numbers of nasal cancers in mice was insufficient to show statistical significance, but were considered formaldehyde related due to pathological examination. No increases in leukemia, lymphomas, or brain cancer were observed. Other studies support their finding of nasal cancer. New York University conducted studies in which formaldehyde was administered in a strain of rats different from that used in the CIIT study. OSHA concluded that the NYU studies confirmed that exposure to

formaldehyde can cause cancer in animals. An independent inhalation animal study (Tobe et al.) also reported nasal cancer after formaldehyde exposure even though only a small number of animals were used in the experiment. An inhalation hamster study conducted by yet another independent laboratory reported no tumors, but due to the many scientific flaws in the study (decreased rodent survival time, limited experience at detecting tumors) OSHA discounted the study. Other studies have been conducted demonstrating that formaldehyde applied topically to the skin of laboratory animals does not cause cancer. OSHA concluded that the finding of nasal cancer in two strains of rats in three independent studies on formaldehyde alone to be extremely strong and reproducible evidence that formaldehyde is an animal carcinogen. Evidence of a dose-response relationship, finding cancers of identical cell-type and location in two species and evidence that formaldehyde is genotoxic strengthens the scientific relationship of formaldehyde exposure causing cancer.
2.5.4 GENOTOXITY

Formaldehyde appears to be capable of binding to DNA, a well known mechanism by which chemicals cause cancer. Formaldehyde appears to be both an initiator and a late stage cancer causing chemical.

2.5.5 FIRE AND EXPLOSION HAZARD

Moderate fire and explosion hazard when exposed to heat or flame. The flash point of 37% formaldehyde solutions is above normal room temperature, but the explosion range is very wide, from 7 to 73% by volume in air. Reaction of formaldehyde with nitrogen dioxide, nitromethane, perchloric acid and aniline or peroxyformic acid yields explosive compounds.
Extinguishing Media:

Use dry chemical "alcohol foam", carbon dioxide, or water in

flooding amounts as fog. Solid streams may not be effective.

2.5.6 REACTIVITY

Stability: Formaldehyde

solutions may self-polymerize to form white precipitates. Strong oxidizing agents, caustics, strong alkalis,

Incompatibility (Materials to Avoid):

isocyanates, anhydrides, oxides, and inorganic acids. Formaldehyde reacts with hydrochloric acid to form the potent carcinogen, bis-chloromethyl ether. Formaldehyde reacts with nitrogen dioxide, nitromethane, perchloric acid and aniline, or peroxyformic acid to yield explosive compounds. A violent reaction occurs when formaldehyde is mixed with strong oxidizers. Hazardous Combustion or Decomposition Products: Oxygen from the air can oxidize formaldehyde to formic acid, especial when heated. Formic acid is corrosive.
2.5.7 EMERGENCY AND FIRST AID PROCEDURES

Employees and students must notify their immediate supervisor or instructor of all illness and injuries related to exposure to hazardous chemicals. Contact your supervisor if you have any questions regarding the procedure for treating a non-serious injury or illness.
Ingestion (Swallowing):

If the victim is conscious, dilute, inactivate, or absorb the ingested

formaldehyde by giving milk, activated charcoal, or water. Any organic material will inactivate the formaldehyde. Keep affected person warm and at rest. Get medical attention immediately. If vomiting occurs, keep head lower than hips.
Inhalation (Breathing):

Remove the victim from the exposure area to fresh air

immediately. Do not enter areas with high levels of formaldehyde. Wait for rescuers with appropriate respiratory protection equipment. If breathing has stopped, give artificial respiration. Keep the affected person warm and at rest until ambulance arrives.

Skin Contact:

Remove contaminated clothing (including shoes) immediately. Wash the

affected area of your body with soap or mild detergent and large amounts of water until no evidence of the chemical remains (at least 15 to 20 minutes). Get medical attention after washing affected area.
Eye Contact:

Wash the eyes immediately with large amounts of water occasionally lifting

lower and upper lids, until no evidence of chemical remains (at least 15 to 20 minutes). Get medical attention immediately. If you have experienced appreciable eye irritation from a splash or excessive exposure, you should be referred promptly to an ophthalmologist for evaluation.
2.5.8 SPILL, LEAK, AND DISPOSAL PROCEDURES

Occupational Spill: Take up small spills with absorbent material and place the waste into properly labeled containers for later disposal. In the event of a large spill, alert personnel in the area that a spill has occurred. Do not attempt to handle a large spill of formaldehyde. Vacate the laboratory immediately and call for assistance.
2.5.9 MONITORIG AND MEASUREMENT PROCEDURES

Monitoring Requirements:

If the exposure to formaldehyde exceeds 0.5 ppm action level

or the 2 ppm STEL, employer must monitor the exposure. Employer need not measure every exposure if a "high exposure" employee can be identified. This person usually spends the greatest amount of time nearest the process equipment. If you are a "representative employee", you will be asked to wear a sampling device to collect formaldehyde. This device may be a passive badge, a sorbent tube attached to a pump, or an impinger containing liquid. You should perform your work as usual, but inform the person who is conducting the monitoring of any difficulties you are having wearing the device.
Evaluation of 8-hour Exposure:

Measurements taken for the purpose of determining time-

weighted average (TWA) exposures are best taken with samples covering the full shift. Samples collected must be taken from the employee's breathing zone air.
Short-term Exposure Evaluation:

If there are tasks that involve brief but intense exposure

to formaldehyde, employee exposure must be measured to assure compliance with the STEL. Sample collections are for brief periods, only 15 minutes, but several samples may be needed to identify the peak exposure.

Monitoring Techniques: OSHA's

only requirement for selecting a method for sampling and

analysis is that the methods used accurately evaluate the concentration of formaldehyde in employees' breathing zones. Sampling and analysis may be performed by collection of formaldehyde on liquid or solid sorbents with chemical analysis. Sampling and analysis may also be performed by passive diffusion monitors and short-term exposure may be measured by instruments such as real-time continuous monitoring systems and portable direct reading instruments.
Notification of Results:

Your employer must inform you of the results of exposure

monitoring representative of your job. You may be informed in writing, but posting the results where you have ready access to them constitutes compliance with the standard.
2.5.10 PROTECTIE EQUIMENT AND CLOTHING

Clothing:

Material impervious to formaldehyde is needed if the employee handles

formaldehyde solutions of 1% or more. Other employees may also require protective clothing or equipment to prevent dermatitis.
Respiratory Protection: Contact Protective Gloves:

Supervision if you believe respirators are required.

Wear protective (impervious) gloves provided by your employer, at no

cost, to prevent contact with formalin. Y our employer should select these gloves based on the results of permeation testing and in accordance with the ACGIH Guidelines for Selection of Chemical Protective Clothing.
Eye protection:

If you might be splashed in the eyes with formalin, it is essential that you

wear goggles or some other type of complete protection for the eye. You may also need a face shield if your face is likely to be splashed with formalin, but you must not substitute face shields for eye protection. (This section pertains to formaldehyde solutions of 1% or more.)
Other Protective Equipment:

You must wear protective (impervious) clothing and

equipment provided by your employer at no cost to prevent repeated or prolonged contact with formaldehyde liquids. If you are required to change into whole-body chemical protective clothing, your employer must provide a change room for your privacy and for storage of your street clothing. If you are splashed with formaldehyde, use the emergency showers and eyewash fountains provided by your employer immediately to prevent serious injury. Report the incident to your supervisor and obtain necessary medical support.

2.5.11 ENGINEERING CONTROLS

Ventilation is the most widely applied engineering control method of reducing the concentration of airborne substances in the breathing zones of workers. There are two distinct types of ventilation.
Local Exhaust:

Local ventilation is designed to capture airborne contaminants as near to the

point of generation as possible. To protect you, the direction of contaminant flow must always be toward the local exhaust system inlet and away from you.
General (Mechanical):

General dilution ventilation involves continuous introduction of

fresh air into the workroom to mix with the contaminated air and lower your breathing zone concentration of formaldehyde. Effectiveness depends on the number of air changes per hour. Where devices emitting formaldehyde are spread out over a large area, general dilution ventilation may be the only practical method of control.
Work Practices:

Work practices are an important part of a control system. If you are asked

to perform a task in a certain manner to limit your exposure to formaldehyde, it is extremely important that you follow these procedures.
2.5.12 MEDICAL SURVEILLANCE

Medical surveillance helps to protect employees' health. Your employer must make a medical surveillance program available at no expense to you and at a reasonable time and place if you are exposed to formaldehyde at concentrations above 0.5 ppm as an 8-hour average or 2 ppm over any 15 minute period. You will be offered medical surveillance at the time of your initial assignment and once a year afterward as long as your exposure is at least 0.5 ppm (TWA) or 2 ppm (STEL). Even if your exposure is below these levels, you should inform your employer if you have signs and symptoms that you suspect, through your training, are related to your formaldehyde exposure because you may need medical surveillance to determine if your health is being impaired by your exposure. The surveillance plan includes: (a) A medical disease questionnaire. (b) A physical examination if the physician determines this is necessary. If you are required to wear a respirator, your employer must offer you a physical examination and a pulmonary function test every year. The physician must collect all information needed to determine if you are at increased risk from your exposure to formaldehyde. At the physician's discretion, the medical examination may include other tests, such as a chest x-ray, to make this determination. After a

medical examination the physician will provide your employer with a written opinion which includes any special protective measures recommended and any restrictions on your exposure. The physician must inform you of any medical conditions you have which would be aggravated by exposure to formaldehyde. All records from your medical examinations, including disease surveys, must be retained at your employer's expense.
2.5.13 ENVIRONMENTAL ISSUES

Formaldehyde is a naturally occurring substance in the environment made of carbon, hydrogen and oxygen. According to the U.S. Environmental Protection Agency, natural processes in the upper atmosphere may contribute up to 90 percent of the total formaldehyde in the environment (WHO, International Programme on Chemical Safety, Concise International Chemical Assessment Document: Formaldehyde). Since formaldehyde is a byproduct of combustion, cars and trucks emit formaldehyde, as does burning wood. Formaldehyde does not accumulate in the environment, because it is broken down within a few hours by sunlight or by bacteria present in soil or water. Humans metabolize formaldehyde quickly, so it does not accumulate in the body. Formaldehyde manufacture and use represent only a partial source of formaldehyde in the environment. Formaldehyde in the atmosphere results primarily from incomplete

combustion of hydrocarbons, as well as photochemical oxidation of unconverted hydrocarbons from combustion sources.
Table 2.2 - Contribution to atmospheric formaldehyde

Emission Source Motor vehicle and aircraft exhausts Photochemical reactions (largely from hydrocarbons in exhausts) Combustion plants, incinerators Petrochemical refineries Formaldehyde production plants

Percent 53-63 19-32

13-15 1-2 1

Indoor formaldehyde levels are also of concern. It is known that formaldehyde-based products such as resins and UF foam insulations contribute small amounts of formaldehyde to the air. Some representative products include carpeting, floor and ceiling tiles, pressed wood products, and linedair ducts. With time, formaldehyde decomposes in both the atmosphere and normal nonsterile water. The initial oxidation product, formic acid, is a component of acid rain. Because of its high solubility there will be efficient transfer into rain and surface water which may be an important sink. Additional quantities are removed by dry deposition or by dissolving in the ocean and other surface waters. Although discharges to watercourses are strictly limited in most countries, formaldehyde is not subject to the stringent controls that apply to bioaccumulating substances. Specific concerns about formaldehyde are largely focused on the health impact on humans of atmospheric formaldehyde in the workplace or home. The International Agency for Research on Cancer (IARC), part of the World Health Organization, recently has reclassified formaldehyde from group 2A probably carcinogenic to humans to group 1 carcinogenic to humans. This move was made based on a finding of sufficient evidence that formaldehyde causes nasopharyngeal cancer in humans, affecting the nasal cavity and paranasal inuses. As a result of health concerns, most countries in the developed world classify formaldehyde as a toxic compound and require strict handling procedures and labeling of products. Many countries have imposed stringent limits on the concentration of

formaldehyde, both in the workplace and home, and have also imposed standards on products such as particle board. The product standards may be expressed as a direct limit on the formaldehyde concentration, or as a maximum emission value for the product.
2.6 ECONOMIC ASPECTS:

Formaldehyde is one of the most important basic chemicals and is required for the manufacture of thousands of industrial and consumer products. It is the most important industrially produced aldehyde. The formaldehyde industry provides thousands of jobs where workers are employed directly in producing the chemical and managing its marketing, sale and distribution. These workers operate and maintain the formaldehyde production facilities, and have responsibility for management, research and development, sales and marketing. Beyond these jobs derived direcly from formaldehyde, hundreds of thousands of workers are supported indirectly through formaldehyde.

Formaldehydes chemistry makes it an extremely versatile contributor to the production of hundreds of items that improve everday life. Some studies have made and the results shows that, in the United States, production of formaldehyde and formaldehydecontaining goods accounts for more than five percent of the yearly U.S. Gross National Product (GNP) or about $500 billion out of a GNP exceeding $10 trillion. Formaldehydes wide-ranging use makes it essential to operations of nearly 50,000 U.S. facilities in 17 major industries, and it serves as a basic raw material in another 70 industries. Annual U.S. formaldehyde production exceeds five million metric tons. Formaldehyde is the most important commercially aldehyde (class of highly reactive organic chemical compounds obtained by oxidation of primary alcohol), according to the most recent CEH Marketing Research Report on Formaldehyde from SRI International. More than half of all formaldehyde is used primarily to make urea-, phenol-, melamineformaldehyde (UF, PF and MF) resins and polyacetal resins- altogether a business valued at nearly $ 10 billion. If urea formaldehyde resins were not available to the industries that use them, the additional cost to consumers in the United States and Canada would approach $3.5 billion annually. If phenol formaldehyde resins were not available to the building, construction, automotive and other industries that use them, the additional cost to consumers in the United States and Canada would approach $4.65 billion annually. If melamine formaldehyde resins were not available to the textile, surface coatings and other industries that use them, the additional cost to consumers in the United States and Canada would approach $365 million annually. If polyacetal resins were not available to the numerous industries that use them, the additional cost to consumers in the United States and Canada would approach $220 million annually.
Manufacturing Regions of Formalin:

China (mainland), Iran, India, South Korea, Taiwan, United Arab Emirates, Vietnam, Philippines,

Indonesia, Japan, Pakistan, Russian Federation, Turkey, Ukraine, Egpyt Germany,

Hungary, Myanmar Netherlands, Singapore

Markets: kets Main Export Markets

Western Europe, North America, Africa, South America, Mid East, Southeast Asia, Eastern Asia, Eastern Europe, Ocenia

Some formaldehyde manufacturers in the U.S. are:

Borden Chemical, Georgia-Pacific Resins, Inc., Capital Resin Corporation, GEO Specialty Chemicals, Inc., Celenase Ltd. Chemicals Division, Hercules Incorporated, Perstorp Polyols, D.B. Western, Inc., Praxair, Inc., Dupont Chemical Solutions Enterprise, Solutia Inc., Dynea USA, Inc., Wright Chemical Corporation.

Table 2.3 - Producers and their capacities

PRODUCER Borden Chemical, (18 sites) Capital Resin, Columbus, OH Celanese, Bishop, TX; Rock Hill, SC D.B. Western, Virginia, MN Degussa, Theodore, AL DuPont, LaPorte, TX; Parkersburg, WV Geo Specialty Chemicals, (Trimet) Allentown, PA Georgia-Pacific (14 sites) Hercules (Aqualon), Louisiana, MO ISP, Calvert City, Ky.; Texas City, TX Neste Resins (5 sites) New Mexico Adhesives, Las Vegas, NM Perstorp, Toledo, OH Praxair, Geismar, LA Solutia, Alvin, TX Wright Chemical, Riegelwood, NC Total

CAPACITY* 4,600 100 1,730 40 215 900 135 2,510 170 200 900 50 450 140 200 160 12,500

*Millions of pounds per year on a 37 percent basis. Commercial production is from methanol either by silver catalyst or metal oxide catalyst processes. 70 to 80 percent of formaldehyde output is used captively. In 1998 Geo Specialty Chemicals purchased Trimet from Mallinckrodt and Borden Chemical acquired Spurlock Industries and its plants in Waverly, VA, and Malvern, AR, adding another 275 million pounds of capacity. In 2000, Borden Chemicals and Plastics sold its formaldehyde business, including the recently upgraded, 1,470 million pound Geismar, LA facility, to Borden Chemical. In 1999, International Specialty Products ended formaldehyde production in Calvert City, KY, and closed the Texas City, TX plant the next year, eliminating 200 million pounds per year in total. Perstorp expanded its Toledo plant by 140 million pounds, increasing capacity at the site to 450 million pounds in 1999.

In 2000, Georgia-Pacific acquired the formaldehyde of Celanese, but not the production facility at Rock Hill, SC According to a long-term manufacturing agreement, Georgia-Pacific will utilize the formaldehyde output of the Rock Hill plant to supply third parties including former customers of Celanese. Subsequent to the formaldehyde acquisition from Celanese, Georgia-Pacific announced it is divesting its chemicals division and intends to sell the division as a single unit. The business includes formaldehyde and its derivative resins. No buyer has thus far been identified. Seven producers in Canada have combined total capacity for about 1,800 million pounds per year of formaldehyde; Mexico's capacity totals about 510 million pounds from eleven
Demand in 1999:

producers. 9,623 million pounds; 2000: 9,702 million pounds; 2004: 10,096 million

pounds, projected. Demand equals production plus imports (1999: 82 million pounds; 2000: 62 million pounds) less exports (1999: 21 million pounds; 2000: 18 million pounds).
GROWTH GROWTH Historical (1995 - 2000): PRICE Historical (1995 - 2000):

1.8 percent per year; 1.0 percent per year through 2004. High, $0.24 per pound, 37 percent methanol-free

(uninhibited) tanks, f.o.b. Gulf; low, $0.13, same basis. Current: $0.21, same basis.
STRENGTH STRENGTH: ENGTH

Formaldehyde use in production of acetylenic chemicals (butanediol), MDI and

acetal resins continues growing at about 5 percent. These uses currently account for one-third of formaldehyde demand.
WEAKNESS:

In March, housing starts fell another 1.3%, to an annual rate of 1.61 million

units. In 2000, the rate stood approximately at 1.70 million units. This decrease depresses demand for formaldehyde in urea- and phenol-formaldehyde resins used in particleboard and plywood, respectively. These two classes of thermosetting resins consume more than onethird of formaldehyde demand.
OUTLOOK:

Formaldehyde demand is softening as housing and construction have declined.

Most large-volume formaldehyde contracts are tied to methanol and natural gas pricing, so major customers are generally paying twice what they did a year ago, even though list pricing for 37 percent material is $0.21 per pound. Natural gas remains around $5.25 to $5.50 per

million BTUs, down substantially from its high of $9 to $10 winter in 2000, but still around twice its traditional value. Some analysts expect gas prices to continue falling, but others warn that a summer surge in electricity demand could send gas back up around $7. Formaldehyde capacity has always exceeded demand by a substantial margin, and this situation will continue Prices of formaldehyde are closely linked to and generally track its methanol feedstock. In Europe, formaldehyde is usually traded regionally over small distances and so prices vary according to country and are unofficially set on a quarterly contract basis. In the US, most large volume formaldehyde contracts are tied to methanol and natural gas pricing, sometimes leading to a large delta between contract and spot prices. Companies in formaldehyde sector in Turkey are: alayan Kimya San.Tic.LTD.T., Topu Kimya Nak. ve Tic., Saf Su Oya Kimya, Turca Kimyevi Maddeler Tic. LTD., Mars Kimya, Kur Kimya, Sz Kimya LTD.T., Joco Kimya, But, for production of formaldehyde there are totally 6 registered companies in Turkey: 1 in Bursa, Hatay, stanbul, Kastamonu and 2 producers in Kocaeli. Datas from TOBB; Production Capacity TO S

City

Registered Producer E T

Workers F W AD Total 73 32 23 9 13 9 3 2 120 47 30 16 516

Area (m2) Closed Area 17,157 2,000 2,805 1,673 Open Area

BURSA HATAY ISTANBUL

1 1 1

16 12 6 2 4 1 0 0 2 4 0 2

104,980 * 24,743 7,148 7,779 * * *

KASTAMONU 1 KOCAELI TOTAL 2 6

17 16 13 388 82

122,444 335,222 * 146,079 479,872 292,765

40 30 25 525 109 729

E: Engineer; T: Technician; F: Foreman;W: Worker; AD: Administrative;

2.7 DISPOSAL

The Resource Conservation and Recovery Act (RCRA) identifies formaldehyde as a toxic waste if it discarded as a commercial product, manufacturing intermediate, or offspicification commercial chemical product. Formaldehyde is identified as the hazardous constituent in waste assigned the hazardous wate number U122 under RCRA. Spilled or used formaldehyde is considered a hazardous waste and must be handled as a solid waste under RCRA. The generator-be it in the field office or the district office-must contact a hazardous waste contractor for appropriate disposal under RCRA regulations. An Environmental Protection Agency (EPA) identification number must be obtained for each site from which disposal of a regulated material or waste will be made and records must be maintained on the amounts of waste formaldehyde, storage time, and the contractor involved in the hazardous waste recycling.

3.0 DISCUSSION & CONCLUSIONS

At ambient temperatures, formaldehyde exists in a gaseous state, emitting a familiar sharp odor, irritating the eyes and skin. This gas is relatively stable at temperatures between 80C and 100C, but slowly polymerizes at lower temperatures, and is not sold commercially. Because formaldehyde is highly water soluble, it is usually marketed as a liquid solution, typically at 37 weight percent formaldehyde solution, combined with water and up to 16 percent methanol. Besides, pure formaldehyde is a gas at ordinary temperatures and cannot be readily isolated or handled in this state, it is marketed chiefly in the form of its aqueous solutions. Therefore, and all production comparisons shown in this report are made on a 37 percent basis. However, higher concentrations are sold and are required for the production of some derivative products such as polyacetal resins. The market trend is to sell solutions at higher concentrations to reduce shipping costs. Stabilizers are usually required when shipping higher concentrations of formaldehyde solutions. Unreacted methanol in solution helps inhibit formaldehyde polymerization; however, this is highly time and temperature dependent. Other product impurities include formic acid (less than 0.03 percent) and iron compounds (less than 0.5 ppm) in a 37 percent solution. For the manufacture of formaldehyde; a wide range of alternative feed stocks have been considered but not found to be economic. For example, a tiny amount of formaldehyde is produced from the non-catalytic oxidation of propane butane mixtures. Formaldehyde can be produced from methane but a mixture of products needs to be separated. It is also a byproduct of the oxidation of naphtha to acetic acid. Yields for both processes (Oxidation-dehydrogenation using a silver catalyst involving either the complete or incomplete conversion of methanol; and the direct oxidation of methanol to formaldehyde using metal oxide catalysts (Formox process)) are around 90 to 92 percent but the oxidation route has a lower reaction temperature and the metal catalyst is cheaper than silver. However, the partial oxidation dehydrogenation route is still the most prevalent. The basic difference between them is the catalyst applied. The methanol excess process, called the silver process, employs silver as the catalyst while the air excess process (molybdenum process) uses metallic oxides of iron and molybdenum. In considering higher investment cost and more complicated operation than the silver process, we

recommend that our clients use the silver process But, in considering higher investment cost and more complicated operation than the silver process, it is recommend to use the silver process. Recent improvements in the metal oxide catalyst process have aimed at process simplification, more extensive use of carbon steel equipment to reduce capital investment, and modifications of the catalyst to increase catalyst life. The most radical improvements in the silver catalyst process have been made by BASF and are now used commercially. A different form of the catalyst, a higher reaction temperature, and changes in reactor feed composition have made possible a high methanol conversion; thus, it is no longer necessary to recover unreacted methanol. Maximum size of a production unit has also been increased by these changes. Silver-catalyzed processes for making formaldehyde from methanol can be characterized according to the number of catalytic stages used to effect the conversion. Single stage operation is quite widely used but suffers from the disadvantage that rather high amounts of unconverted methanol are contained in the product emerging from the catalyst bed. This phenomenon is customarily referred to as methanol leakage. Since for many applications methanol is an undesirable contaminant, it must be separated from the formaldehyde solution. This entails a substantial investment in distillation facilities and energy to carry out such separations. Because of the nature of the process, methanol and air concentrations are strictly controlled to avoid potential explosions. An excess of methanol is used in production to maintain concentration levels above the explosive limits. A concentrated aqueous solution of formaldehyde can only be used for certain applications, since it can neither be stored, nor transported, for extended periods. The most usual concentration is of the order of magnitude of from 30 to 37% by weight, especially the latter figure, since this represents a solution of optimum concentration which proves stable over extended periods, without precipitation of paraformaldehyde. Such solutions are required for the manufacture of phenolic resins. On the other hand, solutions of maximum concentration have advantages for other applications, e.g. to save transport costs, if the time for transport is relatively long and to save

evaporation costs in subsequent processes, e.g. the manufacture of urea-formaldehyde condensation resins or the manufacture of butynediol by reaction with acetylene. There has been significant research activity to develop new processes for producing formaldehyde. Even though this work has been extensive, no commercial units are known to exist based on the technologies discussed in the following. One possible route is to make formaldehyde directly from methane by partial oxidation. This process has been extensively studied. The incentive for such a process is reduction of raw material costs by avoiding the capital and expense of producing the methanol from methane. Another possible route for producing formaldehyde is by the dehydrogenation of methanol which would produce anhydrous or highly concentrated formaldehyde solutions. For some formaldehyde users, minimization of the water in the feed reduces energy costs, effluent generation, and losses while providing more desirable reaction conditions. A third possible route is to produce formaldehyde from methylal that is produced from methanol and formaldehyde. The incentive for such a process is twofold. First, a higher concentrated formaldehyde product of 70% could be made by methylal oxidation as opposed to methanol oxidation, which makes a 55% product .This higher concentration is desirable for some formaldehyde users. Secondly, formaldehyde in aqueous recycle streams from other units could be recovered by reacting with methanol to produce methylal as opposed to recovery by other more costly means, eg. distillation and evaporation. Development of this process is complete.

ECONOMICS AND COMPARISON OF THE PROCESSES:

The production costs of 37%

aqueous formaldehyde solution by the production processes (metal oxide catalyst process, the silver catalyst process) are summarized in the following figure.

Figure 3.1 - Formaldehyde production cost comparison, 37% basis, U.S. Gulf Coast, 1st Qtr 2005 (120 million pounds per year capacity)

The higher capital cost of the metal oxide catalyst plant is compensated for by better process yields from methanol. The silver catalyst process without recycle has the next lowest estimated cost plus return on capital employed (ROCE); however, the product has a higher methanol content than the product resulting from the metal oxide and silver catalyst with recycle processes. The price of methanol has a dramatic effect on formaldehyde economics, since cost for methanol feedstock represents 80 to 86 percent of cash cost and 67 to 72 percent of cost plus ROCE for the commercial processes studied. Sensitivities show the effect of methanol price over the range 45 to 125 cents per gallon. Concentration of the formaldehyde solution is an important consideration for three reasons: downstream derivative requirements, shipping costs, and energy requirements to remove excess water. Polyacetal resins, for example, are direct polymers of formaldehyde, and require as concentrated a solution as possible to achieve polymerization. Resins are usually supplied as a solution of 60 percent solids or more, for which formaldehyde feedstock at more than 50 percent concentration is desirable. Where concentrated formaldehyde is required, the metal oxide process has the advantage. Conversely, in some cases, such as the highly exothermic production of phenol formaldehyde resins, a more dilute solution is actually desirable. The silver process with distillation offers a certain amount of flexibility which is appropriate for a plant supplying a complex and varied market. On the other hand, the metal oxide process has an advantage in serving the single largest formaldehyde market in its ability to form urea-formaldehyde precondensate directly in the absorption column. Existing

production capacity is dominated by the silver catalyst process, whereas the majority of new plants being built employ the metal oxide process. This is due to the higher formaldehyde yields on methanol and higher product concentration achieved.
DEMAND: DEMAND

The current consumption of formaldehyde stands at around 20 million metric tons

per year (37 wt. percent basis), representing the largest use of methanol globally. The substantial costs associated with movement of formaldehyde over larger distances have caused almost all of the formaldehyde plants globally to be integrated with appropriate downstream plants. This has been possible owing to the versatility of formaldehyde end uses. As can be seen in Figure 3.2, amino resins, which include mainly urea- and melamineformaldehyde resins, currently constitute slightly more than one-third of the total global formaldehyde consumption. Phenolic resins are the second largest area of consumption.

Figure 3.2 - Breakdown of Global Formaldehyde End Uses (2005).

Global consumption growth is estimated for nine end use categories through 2015.

SUPPLY: SUPPLY Figure

3.3 shows the dominance of Western Europe in formaldehyde capacity. The

producers in the developed countries tend to have larger capacities distributed over a number of production lines. The producers in developing countries tend to have much smaller production production opportunistic. capacities, tends and to the be

When margins are

good the plants operate flat out, but when margins are poor, the plants operate only to support the

consumption in the downstream plants.

Figure 3.3 - Share of Key Regions in Overall Formaldehyde Capacity (2005).

SUPPLYBALANCE: SUPPLY-DEMAND BALANCE

The overall operating rate of the plants globally is expected

to increase from the upper 70s in 2005 to the lower 90s by 2015. Fragmentation in the market that has led to poor margins in the past is expected to reduce with the closure of some of the small, relatively uneconomical facilities. Individual supply/demand balances are also provided for North America, Western Europe, China, Japan, and Rest of the World. In Turkey, just 6 companies produce totally, 292765 tons of formaldehyde in a year. These values are too small when compared with the formaldehyde production in Canada and United States. Also, there are many distributors in Turkey, so it can be understood that formaldehyde production in Turkey does not meet the all requirements.

4.0 REFERENCES
[1] Ullmann, Ullmanns Encyclopedia of Industrial Chemistry, Fifth Completely Revised

Edition, Volume A11, page 619-647. [2] Othmer K., Kirk Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol

11, page 929-947. [3] [4] [5] www.formaldehyde.org www.the-innovation-group.com http://www.microscopy-uk.org.uk/mag/indexmag.html?http://www.microscopy-

uk.org.uk/mag/artoct02/toptips12.html [6] [7] [8] [9] [10] [11] http://www.sefsc.noaa.gov/HTMLdocs/appendix-I.htm http://cameochemicals.noaa.gov/chemical/17291 http://www.sriconsulting.com/PEP/Reports/Phase_77/RP023A/RP023A.html http://www.freepatentsonline.com/4119673.html http://www.dsir.gov.in/reports/techreps/tsr137.pdf http://www.mechatropia.or.kr/bbs/jck99/sp_3_034.pdf

5.0 APPENDICES
APPENDIX A SILVER CATALYST PROCESS IN DETAIL

The following process produces 50000 tons/year of formalin from methanol using the Silver Catalyst Process given in Figure A.1.

Formaldehyde and water required for the production are formed in the following reaction: CH 3OH + 1 O2 HCHO + H 2O 2 Reaction rate expression can be simplified to: H rxn = 37.3 kcal / mol

rm [mole / gr catalyst hour ] =

k1 p m 1 + k 2 pm

where where p is a partial pressure in atm, and m refers to methanol. The rate expression is only valid when oxygen is present in excess. The catalyst bulk density is 100 lb/ft3 and the above constants are defined as:
log k1 = 11.43 where T is in Kelvin. 3810 T log k 2 = 10.79 7040 T

Fresh methanol, Stream 2, at 30C and 14.7 psia mixes with recycled methanol, Stream 15, at 68.3C and 16 psia. Stream 3 (recycled and fresh methanol) is at 35.4C and 14.7 psia. Pump, P-101, raises the pressure up to 35 psia. Stream 4 enters a heat exchanger where the methanol is vaporized. Stream 5 is then at 150C and 29 psia. Fresh air is available at 25C and 14.7 psia in Stream 1. Compressor, C-101, raises the pressure to 35 psia in Stream 5. This stream is then heated by medium-pressure steam. The temperature is raised to 150C in Stream 7. Stream 6 and Stream 7 mix at a pressure of 29 psia. The combined mixture is at 149.6C and 28 psia in Stream 8. The reactor converts 87.4% of the methanol. The exit reactor temperature is 343C. Heat is removed by making high-pressure steam from boiler feed water. The outlet, Stream 9, is at 343C and 25 psia. A valve drops the pressure of this stream to 5 psia before it enters the absorber, T-101. Fresh water is sent through the T101 at 30C and 20 psia. T-101 is set to absorb 99% of the formaldehyde that enters. Stream 13 is then heated to 102C before entering T-102, the formalin distillation column. T-101 recovers a 37 wt% solution of formaldehyde in water. Most of the methanol is recovered in the distillate. Stream 15, the distillate, is recycled back to the inlet of fresh methanol at 68.3C

and 16 psia. The bottoms, Stream 16 is pumped, by P- 103, up to 38.5 psia for storage. Deionized water at 30C in Stream 18 is added to achieve the 37 wt% solution of formaldehyde in water. Storage of formalin is tricky. At high temperatures, undesirable polymerization of formaldehyde is inhibited, but formic acid formation is favored. At low temperatures, acid formation is inhibited, but polymerization is favored. With 2 wt% methanol, the storage tank contents must be maintained between 35C and 45C.

Equipment description for the process described in Figure A.1 can be made as: P-101: Methanol Pump, E-101: Methanol Vaporizer, C-101: Air Compressor, E-102: Air Heater R-101: Fluid Bed Reactor, T-101: Formalin Absorber, E-103: Heater, T-102: Formalin Distillation Column, E-104: Methanol Condenser, E-105: Formalin Reboiler, P-102: Reflux Pump, V-101: Reflux Drum, P-103: Formalin Pump, E-106: Formalin Cooler.
Table A.1 Stream table for the production of formalin

Table A.1 (Continued) Stream table for the production of formalin

Process flowsheet of the diagram is given in the following page:

Figure A.1 Production of formalin from methanol using silver catalyst process

APPENDIX B A SAMPLE FORMALIN PRODUCTION PLANT

Characteristic properties for a formalin production plant are gathered together and given in this section. For the process flow diagram of

the plant see Figure B.1 first.

Figure B.1 Process flow diagram for a sample formalin production plant with a production capacity of 4000 m3 formalin/day

Typical equipments that will be needed for such a plant are listed below: Reactor, Absorber, Air Filter, Suction Filter, Gas Mixer, Gas-Water Separator, FML Filter, Drain Separator, Evaporator, Mixed Gas Filter, M.V. Preheater, Air Preheater, Formalin Cooler, Start-Up Heater, Flame Arrester, Air Blower, Air Compressori RG Blower, RG Preheater, Cooling Tower, Various Tanks for Raw Feed Materials and Products, Various Pumps. Production capacity of the plant is 4000 m3/day and working condition is 12 hours/day. Raw material and utility consumption for the plant and for the production of one tone of 37% formalin is given in the following table:

Table B.1 Raw material and utility consumption

Assuming that no unexpected complications are faced, such a plant is built in 18 months after the beginning of the construction scheadule. Required land area for a plant of the given capacity is 3000 m2 and 1000 m2 of that area is covered by facilities and buildings requred for manufacturing.

Plant layout for the sample formalin production plant is given in Figure B.2 in the following page:

Figure B.2 Plant layout

Operation manpower for the sample plant is also estimated and given to be such as in the following table:
Table B.2 Raw material and utility consumption