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If the phenol is to remain colorless for as long as possible, the walls of the
containers must be made of s stainless steel. Pure phenol is therefore stored
predominantly in stainless steel tanks, which are insulated to avoid heat losses. On
storing liquid phenol it must be ensured that the temperature remains below 70 C.
The lower explosion limit for phenol air mixtures is reached at a saturation
temperature of 73 C, corresponding to a phenol vapor fraction in the mixture of 1.3
vol%. At storage temperatures below 70 C the tank gas volume is blanketed with
Ullmann's Encyclopedia of Industrial Chemistry, Vols. 1 to 39
Formaldehyde can be stored and transported in containers made of stainless steel,
aluminum, enamel, or polyester resin. Iron containers 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.

Ullmann's Encyclopedia of Industrial Chemistry, Vols. 1 to 39

Raw Materials
Phenol, formalin (formaldehyde aqueous solutions: formaldehyde concentration is
usually 3055%), and other main raw materials are generally stored in raw material
tanks made of iron and stainless steel. The tanks for some raw materials, whose
melting points are higher than room temperature, are heated by various methods
such as warm water, steam or hot oil. The tank for formalin is also kept warm
(around 50_C) to prevent paraformaldehyde from separating out and preventing
formalin from being oxidized to formic acid.
Phenolic Resins: A Century of Progress

Phenolic Resins
Solid phenolic resins which are sold in broken pieces, flakes, pastilles, or granules,
can be packed in sacks, drums, or large containers. If the resins (e.g., rosin-modified
types), have a tendency towards autoxidation, they should be stored in the absence
of oxygen. Phenolic resin solutions are not corrosive and can therefore be stored in
iron containers, if a possible coloration of the resin is acceptable. Otherwise the
containers must be coated on the inside. Liquid phenolic resins are transported in
tank cars, containers, or tank pallets. When stored at room temperature, aqueous
alkaline resol solutions often lose their viability after a few days or weeks. These
solutions must be kept cool during transportation and stored in refrigerated areas.
The storage life of solid resols at room temperature is generally longer: it is
nevertheless advisable to keep all resols cool during storage. Certain phenolic resins
have relatively low softening temperatures and compact during storage which
impairs their storage stability.
Ullmann's Encyclopedia of Industrial Chemistry, Vols. 1 to 39

Commercial production of phenolic resins is presently carried out in batches of
about 1-50 tonnes; the reactors used for this purpose can have capacities of about
1-60 cubic meters. From Baekeland's tiny cooker unit from 1910 (Fig. 3.1) to largescale, computer controlled production facilities of today (Figs. 3.2 and 3.3), a long
arduous route of development has been achieved through extensive diligence and
technical competence. Since appropriate, safe handling and control of the heat
evolved by the exotherrnie reaction represent the main problems encountered in
phenolic resin synthesis when the batch size is increased, the utilization and
removal of this heat must be considered as the key issue of all phenolic resin
technology. The water contained in the 30-55% formaldehyde solutions used mainly
as reactants tagether with the phenolic raw materials represents a heat sink for the
liberated heat of condensation that is utilized tagether with other energy to sustain
the reaction. As shown in the flow diagram in Fig. 3.4, the core of a resin production
line is thus a sealed reactor that is capable of operating under vacuum, includes an
agitator and heating jacket, and is further equipped with a reflux condenser, chiller,
and receiver. The materials currently used for these vessels are, ideally, various
grades of alloyed steel that prevent discoloration of the resins that can occur by
even traces of iron. The reaction may be carried out in a single step or as a
multistage process; the water may be decanted if appropriate, but is generally
removed by distillation (for example during production of novolaks), or may in part
remain in the resin (aqueous resoles). At present, reduction of the free phenollevel
by special distillation procedure (particularly in the case of novolaks) and reduction
of the free formaldehyde level in aqueous resoles also represent important process

considerations. The size of reactor tobe used also depends on the reactivity of the
reactants and that of the finished resin at elevated temperatures. Thus, solid resoles
are produced in small batches that can be quickly discharged into special chiHing
equipment (such as slab chillers). Liquid aqueous resoles and phenolic resin
solutions are generally produced in medium-size batches; high volume utilization of
the resin reactor is possible, the amount depending on the resin content of the
product. Decanting and washing processes may be necessary to achieve
particularly high final product purity levels in production of special-purpose products
such as coatings and adhesives resins, for example alkylphenolics and etherified
Today, standard phenolic novolaks and aqueous resoles (for example wood
adhesives or fiberbonding resins) can be produced in large batches, although this
requires detailed control of all individual operations involved in the overall synthesis
by means of computer programs. Malten phenolic novolak is discharged onto chilled
conveyer belts, possibly following interim storage in heated containers. The resins
are then crushed, and if appropriate for further processing, mixed with curing
agents and miscellaneous additives before being milled in powder resin grinding
equipment to yield highly dispersed powder resins. Based on the above description
it follows that a modern largescale plant for production of phenolic resins can be
divided into the following segments: novolak plant, plant for aqueous resoles, resin
solution plant, plant for solid resoles and modified resins, and possibly a powder
resin plant. Novolaks (molar ratio of phenol to formaldehyde about 1:0.7-1 :0.9)
were previously manufactured using the one-stage process (small batch sizes), i.e.,
the reaction components and catalyst were charged to the reactor, and the reaction
initiated. As the reactor volume increased, it became necessary to control the
temperature by means of gradual addition of formaldehyde. Dilute hydrochloric
acidwas frequently used as a catalyst for production of novolaks, but this led to an
increased tendency to corrosion of the reactor.
Phenolic Resins Chemistry, Applications, Standardization, Safety and Ecology 2nd
completely revised edition
Reactors are double walled, closed vessels which are jacketed into separate heating
and cooling sections (Fig. 5.2). Stainless steel alloy reactors and auxiliary equipment
are used; sometimes nickel clad reactors are utilized. These particular materials do
not promote the discoloration of resins. Copper and copper alloys also exhibit good
resistance to phenol but Iead to discoloration. Detailed description of polymerization
reactors regarding theory and applications to various polymer systems is
summarized by Gerrens 11>.
In the batch process16l phenol, which is stored in tanks of alloyed steel at
approximately 60 ac, is transferred to the reaction vessel via a scale and heated to
95 cc.
Phenolic Resins Chemistry, Applications and Performance Future Directions

Steel Belt Conveyor

The finished novolak is discharged from the reactor into two types of commercial
novolak products: solid novolak and liquid novolak. A solid novolak in the molten
state must be cooled and solidified. For this purpose, steel belt conveyers, with
belts that are cooled by chilled water, are usually used to solidify the novolak into
the shape of a flake. However, the flaked novolak has a tendency to sinter if its
melting point is low. In those cases, a pastillator can be used. If the viscosity of the
molten novolak is too high to discharge using steel belt conveyers, then the novolak
can be discharged into resin basins or trays. Liquid novolaks, which are dissolved in
appropriate solvents after distillation, are transferred to storage tanks or directly
discharged to drums, containers, or cans after cooling in the reactor.
Phenolic Resins: A Century of Progress

Materials of Construction.
Compatibility of the materials of construction and the process chemicals is
extremely important. The reactors are usually made of stainless steel alloys. Copper
is avoided because of the possible presence of amines. Glass-lined reactors are
occasionally used for nonalkaline resins. Because the use of HCl has been largely
discontinued, material requirements are less stringent. The reactor contains a
bottom discharge, which for solid heat-reactive resins must be large. Solid resole
resins are discharged for rapid cooling in order to quench the thermosetting
reactions. Resin coolers are made up of vertical plates with internally circulating
water. The product can also be discharged to a large cooled surface. Discharges to
belt and drum flakers are highly automated; however they can only be used for lessreactive resins. Novolak resins can be stored molten in heated holding tanks under
nitrogen. Because novolaks are used mainly in pulverized form with hexa and
additives, a process that includes belt flaking and feeding directly into the blending
and pulverizing system is preferred. Liquid and solution resole resins are cooled in
the reactor by using jacket cooling and vacuum refluxing. Discharged products are
filtered and pumped to refrigerated intermediate holding areas or packaged for
shipping. The stability of liquid resole products varies greatly from product to