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Millar, Graeme & Collins, Mary

(2017)
Industrial production of formaldehyde using polycrystalline silver catalyst.
Industrial & Engineering Chemistry Research, 56(33), pp. 9247-9265.

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https://doi.org/10.1021/acs.iecr.7b02388
 Industrial Production of Formaldehyde using Polycrystalline Silver Catalyst
*Graeme J. Millar and 1Mary Collins

Institute for Future Environments, and 1School of Chemistry, Physics & Mechanical
Engineering, Science and Engineering Faculty, Queensland University of Technology (QUT),
Brisbane, Queensland 4000, Australia. Email: [email protected]

We report the first comprehensive review of the industrial process for the catalytic partial
oxidation of methanol to formaldehyde using silver catalyst. Formaldehyde remains a key,
large volume industrial chemical which is ubiquitous to household, commercial, aviation,
pharmaceutical and automotive products due to its high reactivity and versatility. Critical
analysis of the various technological approaches used to manufacture formaldehyde,
characteristics of silver catalysts employed, process conditions, and performance values has
been presented. The three common plant types are: almost complete conversion (BASF
type); incomplete conversion followed by distillation (ICI type); and the off-gas recycle
process which dominates world production due to its extensive use in China. Polycrystalline
silver remains the most popular catalyst, with only minimal use of alternate supported
catalysts or gauze materials. Catalyst physical properties such as bulk density, purity,
mechanical strength, size fraction and shape are important in relation to overall
formaldehyde synthesis performance. Process yields majorly range from ca. 82 to 92 % and
catalyst lifetimes vary from 4 weeks to 12 months. There is a research need to not only
raise overall yields consistently to in excess of 90 % but to also maximise catalyst life.
Aspects which should be taken into account include: purification of feed components;
development of a systematic means for catalyst bed design; improvement and
standardization of process configuration; equipment optimization; investigation of the
benefits of feed or catalyst additives; protection of the catalyst bed from poisoning events
and discovery of preferred process operating conditions. In the near term, focussing on
optimization of the current formaldehyde synthesis industry is seen as more prospective
from a commercial point of view, than longer term investigation of alternate pathways for
manufacturing formaldehyde from methane or carbon dioxide which may not be viable for
at least a decade.

1
 Key Words: silver catalyst; methanol; oxidation; formaldehyde; engineering; chemistry
1. Introduction
Formaldehyde remains one of the most important chemicals produced in the world today
due to its unparalleled reactivity and versatility 1. Primarily, formaldehyde is employed in
the production of resins for the wood panel industry, with urea formaldehyde (UF), phenol
formaldehyde (PF) and melamine formaldehyde (MF) resins and their variants representing
the major formulations 2-5. Formaldehyde is also used to make chemicals such as polyacetal
or polyoxymethylene (POM) 6, pentaerythritol 7, 8, paraformaldehyde 9, acetylenic chemicals
10 11 12-14
, hexamine and methylal (dimethoxymethane) . Consequently a wide range of
industrial applications depend upon formaldehyde such as construction, automotive,
aviation, pharmaceuticals and cosmetics 1.

In the early twentieth century the manufacture of formaldehyde on a small scale was
initiated in Europe and the USA 15. The development of high-pressure synthesis of methanol
16
by BASF in 1923 allowed the production of formaldehyde on a true industrial scale .
Initially, gauze made of silver wire was used as the catalyst element 17. However this type of
catalyst has almost entirely replaced by a shallow catalyst bed of silver crystals 18. Further
19
development resulted in the mixed iron oxide-molybdenum oxide catalyst which now
competes with the silver process, accounting for approximately forty-five percent of the
20
world’s production of formaldehyde . Other processes that employ oxidation of
hydrocarbons or hydrogenation of carbon monoxide are not industrially significant since
they compare unfavourably with methanol conversion either in terms of cost or decreased
yield 21, 22.

A concentration of 37 wt % formaldehyde is used as a standard for pricing or production

data, although in reality industrial plants typically make formaldehyde solutions of up to 55
wt % concentration 1. The silver catalyst based process for formaldehyde manufacture
proceeds by two pathways, a partial oxidation reaction [Equation 1] and a dehydrogenation
reaction [Equation 2].
Equation 1: 𝐶𝐻3 𝑂𝐻 + 12𝑂2 → 𝐻2 𝐶𝑂 + 𝐻2 𝑂
Equation 2: 𝐶𝐻3 𝑂𝐻 → 𝐻2 𝐶𝑂 + 𝐻2
Despite the considerable importance of formaldehyde to our daily lives until this point there
has not been a comprehensive review of the industrial synthesis using polycrystalline silver
catalyst. Despite lower yields of formaldehyde compared to the metal oxide process the
silver process continues to grow in popularity. This latter situation is at least in part due to
inherently cheaper production plants as the ability to operate with excess methanol results
in substantially smaller units than the metal oxide process which requires excess air. In
addition, catalyst costs are normally less with silver compared to metal oxide and silver
catalysts can be regenerated on site, which is not the case with the oxide materials. Utilities
consumption is also less with silver based formaldehyde plants due primarily to the reduced
need for electricity to drive the air blowers. Consequently, this study will present
information regarding the industrial practices employed, silver catalyst properties, process
engineering and operating principles. Ultimately, this review will provide an insight into the
challenges to optimise formaldehyde synthesis and produce the next generation of
formaldehyde manufacturing technology.

2. Process Definitions
The formaldehyde industry employs a variety of terms to describe the efficiency of the
methanol oxidation process. These terms are quantifiable measurements of the process
efficiency and include methanol conversion, selectivity, formaldehyde yield, production
ratio and catalyst life.

2.1 Selectivity
When converting the methanol feed it is important to produce valuable formaldehyde and
not by-products such as carbon dioxide, carbon monoxide, and formic acid. Formaldehyde
selectivity is a measure of the amount of formaldehyde produced per unit of methanol
reacted and is defined as in Equation 3.

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 ×100

Equation 3: % 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 =
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐼𝑛−𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑂𝑢𝑡
Also of interest is an understanding of the quantities of carbon dioxide and carbon
monoxide as they give an indication of the extent of methanol combustion and
formaldehyde decomposition during the formaldehyde synthesis process [Equations 4 & 5].

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑎𝑟𝑏𝑜𝑛 𝐷𝑖𝑜𝑥𝑖𝑑𝑒 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 ×100

Equation 4: % 𝐶𝑎𝑟𝑏𝑜𝑛 𝐷𝑖𝑜𝑥𝑖𝑑𝑒 𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 =
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐼𝑛−𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑂𝑢𝑡

Equation 5:
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑎𝑟𝑏𝑜𝑛 𝑀𝑜𝑛𝑜𝑥𝑖𝑑𝑒 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 ×100
% 𝐶𝑎𝑟𝑏𝑜𝑛 𝑀𝑜𝑛𝑜𝑥𝑖𝑑𝑒 𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 =
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐼𝑛−𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑂𝑢𝑡

2.2 Methanol Conversion

The cost of methanol is the most critical parameter with respect to formaldehyde
production economics. Typically, ca. 70 % of the manufacturing cost is attributable to
methanol feedstock. Therefore, it is crucial to convert as much methanol as possible into
formaldehyde during the industrial reaction. The percentage methanol conversion is
defined as in Equation 6.

(𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑖𝑛 – 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑜𝑢𝑡) 𝑥 100

Equation 6: % 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑖𝑛

Alternatively, methanol conversion can be calculated from knowledge of the composition of

the product in the absorber bottoms (most useful when dealing with plants equipped with
distillation units) [Equation 7].

Equation 7:
% 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 =
% 𝑓𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑖𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑥 1.067
((% ) 𝑥100
𝑓𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑖𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑥 1.067)+% 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑖𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

As a worked example, consider an absorber bottoms composition of 44 wt% formaldehyde

and 15 wt% methanol [Equation 8].

44 𝑥 1.067
Equation 8: % 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 = ((44 ) 𝑥100 = 75.8%
𝑥 1.067)+15
2.3 Formaldehyde Yield
Formaldehyde yield can be defined as shown in Equation 9.

Equation 9:
% 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑥 % 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛
% 𝑀𝑜𝑙𝑎𝑟 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑌𝑖𝑒𝑙𝑑 =
100

Yield is the most often quoted parameter in formaldehyde plants and can range from 82 to
92%, depending on the quality of the plant operation. Even a one per cent change in yield
can represent significant financial benefit to formaldehyde producers.

Many formaldehyde plants use “production ratio” as the key performance indicator which is
defined as “kg of methanol required to make 1 tonne of 37 wt% formaldehyde”. The
theoretical minimum value is 394.7 kg of methanol per tonne of 37 wt% formaldehyde. For
formaldehyde plants which produce high concentration formaldehyde solutions, the
production ratio is also defined as “kg of methanol required to make 1 tonne of 50 wt%
formaldehyde”, which in turn means the theoretical minimum methanol consumption is
533.3 kg of methanol per tonne of 50 wt% formaldehyde. Finally, the Indian formaldehyde
marketplace favours calculation of the production ratio in terms of “tonnes of 37 wt%
formaldehyde made from 1 tonne of methanol”, with theoretical limit of 2.53 tonnes of 37
wt% formaldehyde. A summary of the relationship between the various yield definitions is
illustrated in Table 1.

Table 1: Demonstration of the relationship between formaldehyde yield and production

ratios
Formaldehyde Yield Production Ratio (kg Production Ratio (kg Production Ratio
(%) of MeOH to make 1 of MeOH to make 1 (tonnes of 37 wt% FA
tonne of 37 wt% FA) tonne of 50 wt% FA) made from 1000 kg
of MeOH)
82 481 650 2.08
83 476 643 2.10
 84 470 635 2.13
85 464 627 2.15
86 459 620 2.18
87 454 613 2.20
88 449 606 2.23
89 443 599 2.25
90 439 593 2.28
91 434 586 2.31
92 429 580 2.33

Table 2 displays an example of operating data from a formaldehyde plant using silver
catalysts along with appropriate calculation of performance parameters.
Table 2: Example of performance values from an operating formaldehyde plant
Methanol Consumption 30,000 kg/day
Formaldehyde Produced 50,824 kg/day
Formaldehyde in Product 48 wt %
Methanol in Product 1.5 wt %
Formaldehyde Produced 65,934 37 wt% basis/day
Production Ratio 455 kg of methanol per tonne
37wt% formaldehyde
Formaldehyde Selectivity 89.24 %
Methanol Conversion 97.15 %
Formaldehyde Yield 86.7 %

2.4 Catalyst Life

Silver catalysts typically operate in a formaldehyde plant for a period of between a few
months and a year. Silver sinters at the high reaction temperatures, thus resulting in
elevation of pressure drop over the bed and usually decreased performance. It is preferable
for catalysts to last as long as possible, however, there is a point where the lower
productivity, higher power costs and safety considerations outweigh the cost of replacing
the catalyst. The life of silver catalyst is highly dependent upon the operating conditions of
the formaldehyde reactor. For example, the catalyst life is usually longer when the catalyst
is operating at relatively low temperatures and comparatively small plant loads. The form of
the silver catalyst used has also been observed to play a critical role in terms of provision of
longer useful operating life as can be seen in Table 3.

Table 3: Examples of catalyst life for two types of silver catalyst in a range of formaldehyde
plants
Silver Catalyst Type 1 Life (days) Silver Catalyst Type 2 Life (days)
Plant 1 180 100
Plant 2 100 75
Plant 3 43 23
Plant 4 110 42
It has been proposed that the water ballast process (BASF) promotes longer catalyst life as
introduction of water with its associated high heat capacity promotes homogenous
distribution of heat over the catalyst bed and thus minimises sintering and coke formation
23
. The consequences of catalyst poisoning cannot be ignored and may be a major factor in
relation to catalyst life. A catalyst with a design life of six months can be significantly
24
compromised due to the quality of methanol . If the methanol feedstock has a high
permanganate reactivity the catalyst life was found to be reduced to only two months.

At the end of its useful life, silver catalyst is normally returned to the catalyst supplier for
reprocessing. Therefore, essentially the silver bullion component is loaned to the
formaldehyde producer and fabrication costs are incurred for the conversion of the silver to
the catalyst form. Some formaldehyde producers have suggested that only the uppermost
25
section of the silver bed should be removed and replaced with fresh silver catalyst .
However, it has not been demonstrated that this latter approach is beneficial in terms of
maintaining overall catalyst performance since the lower portion of the bed may have
sintered or been poisoned during the previous operational campaign.

3. Industrial Process Designs for Methanol Oxidation to Formaldehyde using Silver

Catalysts
3.1 Almost Complete Conversion of Methanol
Gerloff 26 described the single pass, almost complete conversion of methanol method which
27
is often referred to as the “BASF process”. Sperber intimated that the operating
temperature of the silver catalyst was in the range 600 to 700 oC, and that formaldehyde
yields were as high as 87.5 %. A mixture of air, steam and methanol was supplied to the
silver catalyst in the gas phase, with the methanol/water mass ratio typically 60/40. Hence,
23
why the BASF process is also termed the water ballast method . The process for the
almost complete conversion of methanol to formaldehyde is shown in Figure 1. A mixture
of methanol and water is typically fed into the evaporator vessel wherein air is sparged into
the solution. The gaseous feed mixture is subsequently superheated to ensure the presence
of liquid is eliminated prior to being fed to the reactor where it flows through a 20-30 mm
thick bed of silver crystals. A gas filter system may be present immediately prior to the
reactor entrance as is usually a flame arrestor for safety reasons.
To Off-Gas
Incineration

Process Water
Absorber
Dilution Water

Steam
Distributor

Reactor

Superheater Gas Filter

Water Pump & Flame Arrestor

Waste Heat
Boiler
Absorber Absorber
Column 1 Column 2

Evaporator

Air Blower

Methanol Pump Air

Product Formaldehyde Solution

Methanol

Figure 1: Almost complete conversion process for methanol oxidation to formaldehyde

The product formaldehyde gas is thermally unstable and thus rapid cooling of the gaseous
mixture is achieved by passage through a waste heat boiler system containing pressurized
water 28. The exit gas stream is normally in the range 120 to 200 oC and this is then passed
into an absorption tower which contains appropriate packing material. The high
concentration formaldehyde solution is withdrawn from the bottom of the column and the
non-condensable gases (off-gas) exit from the final stage which is usually a bubble-capped
28
system . To aid the production of high concentration formaldehyde solutions the water
quantity required for the feed is often initially added to the top of the absorber column and
29
then drained from the exit of the final stage . This process modification has two main
benefits: (1) the volume of water added to the absorber is 200 to 500 % greater than in
normal operation which means that the emissions of formaldehyde and methanol from the
column are minimized; (2) the water contains recaptured methanol and formaldehyde
which are recycled to the reactor and ultimately enhance process yield. An example of
operating parameters for an almost complete conversion formaldehyde unit is shown in
Table 4.

Table 4: Typical operating parameters for an almost complete conversion formaldehyde

plant
Air Flow Rate 6040 Nm3/h
Air Flow Rate 6,040,000 L/h
Molar Air Flow Rate 269643 mol/h
Methanol Flow Rate 4667 kg/h
Methanol Purity 99 %
Methanol Quantity 4620 kg/h
Molar Methanol Flow Rate 144375 mol/h
Molar Air/Methanol Ratio 1.87
Water Flow Rate 2364 kg/h
Water Purity 94 %
Actual Water Flow 2222 kg/h
Steam/Methanol Mass Ratio 0.48

3.2 Incomplete Conversion of Methanol Followed by Distillation

An alternative approach to formaldehyde synthesis is to operate the production unit with a
large excess of methanol such that distillative recovery of methanol is required to meet
product specifications [Figure 2]. This approach has the advantage that comparatively low
reaction temperatures are often employed which may suppress undesirable secondary
reactions. For example, Eek-Vancells reacted a methanol/air/steam mix at 560 oC to obtain
an effluent comprising of 1000 kg/h formaldehyde, 782.2 kg/h methanol and 470 kg/h water
(in addition to non-condensable products) 30. Distillation facilitated production of a solution
containing 55 wt% formaldehyde and <1 % methanol. Methanol recovered at the top of the
column was recycled to the evaporator. However, the main drawback of distillation is that it
represents not only additional capital expenditure when constructing the formaldehyde
plant but also it consumes a significant quantity of steam. Table 5 provides an example of
typical operating parameters for an incomplete conversion followed by distillation process.
 To Off-Gas
Incineration
Methanol Return

Process Water
Absorber
Dilution Water

Steam
Distributor

Reactor
Distillation
Superheater Gas Filter Tower
Water Pump & Flame Arrestor

Waste Heat
Boiler
Absorber
System

Evaporator

Air Blower

Methanol Pump Air

Formaldehyde/Methanol
Solution

Methanol Product Formaldehyde

Solution

Figure 2: Incomplete conversion followed by distillation process for methanol oxidation to

formaldehyde
Table 5: Typical operating parameters for an incomplete conversion followed by distillation
formaldehyde plant

Air Flow Rate 2130 Nm3/h

Air Flow Rate 2,130,000 L/h
Molar Air Flow Rate 95,089 mol/h
Methanol Flow Rate 2484 kg/h
Methanol Purity 99 %
Methanol Quantity 2459 kg/h
Molar Methanol Flow Rate 76,844 mol/h
Molar Air/Methanol Ratio 1.23
Water Flow Rate 414 kg/h
Water Purity 99 %
Actual Water Flow 410 kg/h
Methanol Flow Rate 2484 kg/h
Methanol Purity 99 %
Actual Methanol Flow 2459 kg/h
Steam/Methanol Mass Ratio 0.17

3.3 Off-Gas Recycle

The off-gas recycle process involves replacement of a portion of the water in the feed
31
stream by off-gas from the absorber column [Figures 3 & 4]. In theory, this approach
allows production of higher concentrations of formaldehyde as inherently dilution of the
formaldehyde product has been mitigated. Off-gas from the absorber column normally
contains a mixture of nitrogen, hydrogen, carbon dioxide, carbon monoxide, formaldehyde,
methane, unreacted oxygen and methanol, in addition to lesser quantities of argon and
other inert gases 30.
 Figure 3: Off-gas recycle process for methanol oxidation to formaldehyde

(a) (b)

Figure 4: Off-gas recycle formaldehyde plant (a) Absorber towers and off-gas burning facility
(b) gas filter and reactor

Halbritter et al. 31 demonstrated the use of a feed-stream comprising of 14.6 parts air, 6.28
parts methanol, 1.57 parts steam and 10.05 parts off-gas, which resulted in a formaldehyde
yield of 89.88 % and a product containing a formaldehyde concentration of 50.4 wt% and
32
methanol content of 0.085 wt%. Qi and Li simulated an off-gas recycle process and
determined that a further improvement in energy efficiency of 18.7 % and reduction in cold
utility requirements of 10.4 % was possible by modification of standard plant designs.

4. General Process Parameters and Conditions

4.1 Feed Materials
4.1.1 Methanol
Methanol is made using a two stage process: (1) natural gas (or coal) is steam reformed to
produce a syngas mixture (CO, CO2 and H2) in the presence of a nickel based catalyst 33; (2) a
copper/zinc oxide/alumina catalyst converts the syngas to methanol at ca. 250 oC and 50 to
34-37
100 atm pressure . The resultant crude methanol also contains small quantities of by-
product hydrocarbons such as dimethyl ether, acetone and methyl formate. Consequently,
a multi-stage distillation process is applied to the “crude methanol” to convert it to 99 %
purity 38. Greene & Baber indicated that removal of the light end impurities was sufficient
39
to facilitate good formaldehyde synthesis performance . Their solution was to use a
topping column consisting of any suitable packed tower or plate column of about four
theoretical plates. Initially, the crude methanol was dosed with 5 M NaOH until pH 7-9 and
then introduced to the column. The resultant liquid was withdrawn and then fed to a
single-plate flash boiler to separate volatile components from the salt residue. This latter
patent illustrated that catalyst efficiency of up to 94.4 % could be achieved using
40
appropriate levels of water in the feed. Similarly, BASF also revealed that distillation to
remove the lower-boiling fraction relative to methanol was sufficient to provide acceptable
formaldehyde synthesis performance. Interestingly, they showed that conventional
methanol purity tests such as boiling point range, permanganate solution discoloration, and
discoloration by sulfuric acid addition all failed when using the distilled crude methanol yet
formaldehyde yield was apparently unaffected.

A portion of the methanol required as the feed for formaldehyde production can also be
obtained from a co-located resin plant. Wolf et al. 41 advocated the use of condensate from
urea formaldehyde synthesis which comprised of 0.4 to 5 % methanol and formaldehyde in
aqueous solution. However, it was revealed that it was necessary to add substantial
quantities of sodium hydroxide prior to distillative recovery of the methanol.

42
Yuichi recommended that methanol should be purified by a combination of Teflon
cartridge filters to remove particulate matter and an ion exchange resin to remove dissolved
cations such as sodium, iron, calcium and potassium.

4.1.2 Water
Water for the formaldehyde manufacturing process is often sourced from bores, local
municipal supplies or surface water resources. As such there is usually a requirement to
purify the water prior to introduction into the formaldehyde plant. Normally reverse
osmosis units are employed as are ion exchange demineralization systems in combination
with sand filters, microfiltration and other common water purification strategies.

4.1.3 Air
Air is introduced into the formaldehyde plant via an air blower. Air inherently contains
impurities such as particulate matter, volatile organic chemicals, acidic gases, salts and
various other substances dependent upon the plant location. As a minimum, air is usually
passed through a dust filter and other options employed to purify the air include washing
with either water or a sodium hydroxide solution 43.

4.2 Evaporation of Water & Methanol

Prior to entry to the reactor unit, both water and methanol must be vaporized and mixed
with the incoming air stream. Practically, three common approaches are used to achieve
this latter goal: absorber column, vaporizer (evaporator) and methanol reboiler with steam.
The overarching issue is to produce a gas mixture which is not flammable [Figure 5] and
44
great care must be taken to ensure safety considerations are always met . These
approaches are described below.
 Water

0
100
10
90
20
80
30 Flammable
70
40
60 Region at 100 oC
50
50
60
40
70
30
80
20
90
10
100
0
Air 0 10 20 30 40 50 60 70 80 90 100 Methanol

Col 2 vs Col 3 vs Col 4

Figure 5: Phase diagram for methanol/air/water mixtures showing explosive region

4.2.1 Absorber Column

BASF have advocated the use of an absorber column to achieve complete saturation of air
45
with methanol [Figure 6]. For example, Aicher et al. described a column which
incorporated a multitude of angled bubble-cap sieve plates. When compared with a column
containing only non-inclined sieves the formaldehyde yield was increased from 86.3 to 88 %
and catalyst life extended from 70 to 100 days. The underlying reason for the enhanced
performance was the proposition that the column design more effectively removed
particulate matter, fine liquid droplets (mist) and catalyst poisons compared to alternate
designs.

4.2.2 Vaporizer Vessel

Mixtures of methanol and water are fed to an evaporator wherein the liquid is heated by
means of a steam bundle and the air is flowed through a sparger system [Figure 7]. The
concentration of methanol in the vaporizer is often calculated using an empirical
relationship between liquid density and methanol content. Heat is supplied by means of a
tube bundle wherein steam generated in the waste heat boiler section of the plant is used.
The liquid level is maintained such that it fills approximately 50 % of the vessel. Operating
temperatures for the evaporator depend upon the precise composition of the liquid in the
vessel and relate to vapour liquid equilibrium diagrams of the methanol-water-
formaldehyde mixture 46-48. As mentioned in Section 3.1, formaldehyde may be found in the
vaporizer unit due to passage of the feed water though the absorber column prior to
entering the evaporator. To prevent the passage of liquid droplets a demister pad is usually
placed at the exit of the evaporation unit.

Figure 6: Absorber column for saturation of air with methanol

Figure 7: Vaporizer configuration in a formaldehyde plant

Once the gas mixture leaves the demister pad a superheater is present to raise the
temperature to ca. 120 oC. With the evaporator design illustrated in Figure 7, several
problems can occur. For example, the development of foams in the evaporator vessel is
known and this phenomenon results in increased pressure and potential carryover of foam
to the silver catalyst which can cause a decrease in performance 49. One solution proposed
was the addition of “thick oil” (comprised of various long chain alcohols and ethers) to the
vaporizer section which was apparently successful in eliminating foam accumulation. The
presence of material deposits in evaporation units is also found during most shutdown
periods when the vessels are usually cleaned prior to plant re-start.

4.2.3 Methanol Reboiler and Steam

Off-gas recycle formaldehyde plants commonly vaporize the feed components in separate
streams and then combine all four components together in a mixing chamber [Figure 8].

Figure 8: Separate feed streams in an off-gas recycle formaldehyde plant

The outlined approach has the advantage of allowing precise control of the feed mixture
composition due to each individual component being present in separate streams.
4.3 Feed Additives
Several studies have suggested that small concentrations of specific chemicals can be added
to the gaseous feed-stream in order to promote the formaldehyde synthesis process.

4.3.1 Amines
Diem et al. 50 indicated that the addition of amines such as dimethylamine, diisobutylamine
and piperidine could be added to the gaseous feed mixture at small concentrations (0.00007
to 0.0001 moles amine to every mole of methanol). Depending upon reaction conditions
evidence was provided that up to 1 % increase in formaldehyde yield could be achieved by
the presence of the amine. Notably, the most significant impact appeared to be a reduction
in the quantity of formic acid in the final product. A reduction in formic acid content can
51
promote storage stability of the formaldehyde solution. Zhou et al. studied the
interaction of dimethylamine, oxygen and formaldehyde on a silver single crystal. These
authors found that the dimethylamine readily adsorbed on silver surfaces modified by the
presence of atomic oxygen and could react with formaldehyde to make N,N-
dimethyformamide with high selectivity.

4.3.2 Halides
Similarly to addition of amines, improvements in the synthesis of formaldehyde have been
claimed through the introduction of halogen-containing compounds into the mixture 52. Up
to 500 ppm of either CH2Br2, HBr, C3F8, CH3CH2I, BF3 and CH2Cl2 were introduced by
Branecky and Harris 52 to a methanol/air stream fed to a silver catalyst of 25.4 mm depth. In
general, the addition of the halide containing compound appeared to promote methanol
conversion (0.82 to 4.31 %) and increase formaldehyde selectivity (0.67 to 2.79 %).

The fundamental reason for the promotional effect of iodide species in silver oxidation
catalysts has been examined by Dai et al. 53 who used in situ Raman spectroscopy to probe
the reaction of methanol and oxygen on an iodide modified silver surface. These authors
concluded that exposure of silver catalyst to methyl iodide inhibited the coverage of oxygen
species responsible for combustion and promoted the sorption of methanol on the silver
surface. Wang et al. 54 applied density functional theory (DFT) to understand the influence
of iodide upon oxygen sorption to a Ag (100) surface. It was discovered that both iodide
and atomic oxygen species competed for the same fourfold hollow sites on the silver. As a
consequence, iodide modification of the surface could minimise the coverage of surface
atomic oxygen species thought to be responsible for non-selective oxidation of methanol.
In addition, iodide changed the electronic properties of the silver substrate and enhanced
the binding strength of atomic oxygen adsorbed on the silver surface, which again was
proposed to increase formaldehyde selectivity. In relation to subsurface oxygen (Oγ) which
is widely reported to be the active species responsible for dehydrogenation of methanol to
formaldehyde, iodide was suggested to shorten the distance between the subsurface
oxygen species and the silver surface.

55
Qian et al. performed microreactor tests of methanol oxidation on polycrystalline silver
catalyst wherein 100 ppm of methyl iodide was introduced to the feed-stream. Introduction
of CH3I was found to limit methanol conversion but enhance formaldehyde selectivity. The
overall effect of the halogen addition was a decrease in formaldehyde yield but a positive
aspect was the suppression of formic acid production.

4.3.4 Nitrous Oxide

56
Diercks et al. considered the possibility of adding nitrous oxide to the feed-stream in a
formaldehyde synthesis facility. It was suggested that from 1 to 50 % N2O could be added
and an example was provided which indicated the yield of formaldehyde was 93.3 % with
methanol conversion of 99.1 % and formaldehyde selectivity of 94.1 %. In comparison,
without the presence of nitrous oxide the formaldehyde yield was 90.2 % with a methanol
conversion of 97.9 % and formaldehyde selectivity of 92.2 %. The latter results appeared
impressive but the obvious drawback relates to the substantial increase in cost of nitrous
oxide compared to air which is essentially free apart from the power to operate the blower.

4.4 Gas Mixing & Filtration

Yu et al. outlined the need for a quaternary mixer which blends the four components of an
57
off-gas recycle plant . There also exists the possibility of contamination of the silver
catalyst from foreign material in the feed gas stream and as such filters are often present
prior to the methanol oxidation reactor. BASF patented a baffle system for the removal of
impurities such as liquid droplets and particulate matter present in a vaporized crude
methanol stream 58. In practice, the baffle arrangement was found to be effective in that
both formaldehyde yield (81.6 to 82.5 %) and catalyst life (25 to 80 days) was improved.
Solid deposits collected from the baffle plates were found to comprise of a mixture of
sodium formate, sodium carbonate, and compounds of iron, calcium, magnesium, sulfur and
silicon.

4.5 Formaldehyde Reactor Designs

Generically, there are two basic formaldehyde reactor designs which can be classed as
“side” or “top” entry. There is no consensus as to which design has any advantages albeit it
should be pointed out that a major consideration is to ensure even flow distribution over
the catalyst bed surface. As such the feed mixture is not usually directed to the catalyst bed
without a means to distribute the gas stream evenly over the silver surface. For example, Ye
59
et al. illustrated the use of a side entry reactor wherein the influent gas was forced to
traverse around a conical structure with an entry port at the uppermost apex. Regardless of
which location the feed enters the reactor vessel the catalyst bed is circular and ranges from
0.9 to 3 m in diameter [Figure 9].

(a) Silver catalyst bed prior to use (b) Operating silver catalyst bed

Figure 9: Images of silver catalyst bed as (a) prepared and (b) during operation

Immediately above the catalyst bed may be a baffle system to aid the aforementioned gas
distribution, thermocouples and pressure gauges and a means to initiate the catalytic
reaction during plant start-up (see section 4.12). The metallurgy of the reactor vessel has
 60
been raised as a pertinent issue in optimizing formaldehyde synthesis. Dubois et al.
advised that the reactor material chosen should be able to form a protective oxide layer
during reaction conditions.

Within the reactor unit is placed silver catalyst which is usually applied in several layers with
specified mesh sizes (see Section 5.4). In turn the silver catalyst is supported on a series of
meshes which can either be located on top of the underlying boiler tube sheet or on a base
plate with holes cut out to allow gas flow to the gas cooling system (see Section 4.6) [Figure
10].

Figure 10: Representation of silver catalyst bed configuration

It is important to lay the silver catalyst in the reactor in the correct manner. It is logical that
61
the silver bed depth should be kept as uniform as possible. As such Chen described the
use of a specially constructed tool which was designed to press the silver catalyst bed in
such a manner as to make the bed height even.

The majority of formaldehyde plants simply use a one stage reactor process to convert
62
methanol, however McMillan et al. advocated the use of two reactors in series which
both contained silver catalyst. The first stage was operated at comparatively low
temperature to ensure that the methanol was not completely reacted and ideally had
formaldehyde to methanol molar ratio in the reactor effluent of 1.7:1 to 2.5:1. Air was
typically introduced between the two stages and the second stage reactor was operated at a
higher temperature than the first stage. A key difference in operation of the reactor stages
was the use of a gas hourly space velocity in the range 90,000 to 180,000 h-1 in stage 1 and a
corresponding range of 130,000 to 270,000 h-1 in stage 2.

4.6 Support Gauze and Base Plate

4.6.1 Support Gauze
Gauze is typically placed either on top of a base plate or directly on the top of the waste
heat boiler tube sheet [Figure 10 & 11] 63, 64. The selection of gauze material for which the
silver catalyst is arranged is important in terms of maximising performance. BASF have
proposed that the use of a stainless steel support gauze is more beneficial, in that not only
does it minimise sintering of the silver catalyst but also if 1.5-2.5 % molybdenum is
65
incorporated in the steel, carbon deposition on the catalyst surface is also reduced .
Mitsubishi Gas Chemicals also indicated that a copper carrier containing 0.1 to 0.6 % arsenic
inhibits catalyst deterioration 66.

Figure 11: Images of fresh (left) and used (right) copper support gauze
Another support plate consists of quartz sand, wherein the pressure drop is preferably 1.5
to 5 times that of the catalyst bed 67. Claimed benefits include more uniform gas flow and
suppression of side reactions.

The sizes and numbers of support gauzes to employ is not standardized throughout the
formaldehyde industry. The basic premise is to prevent the finest silver grains passing
through the gauze structure; hence it is common to encounter mesh of a similar spacing as
the smallest silver catalyst mesh fraction employed. In many plants, more than one gauze is
applied to support the silver but no scientific rationale has been published to elucidate
which is the optimal approach.

4.6.2 Support Plate

The support plate (or base plate) may perform several functions, such as supporting the
catalyst and promoting uniform gas flow without adding too much pressure drop or reacting
with the catalyst. Copper support plates have the advantage of a thermal expansion
coefficient similar to that of the silver catalyst bed, so that thermal stresses don’t cause
cracks that would lead to bypassing. However, copper plates tend to react with silver to
form alloys, or cause sintering and are also prone to becoming brittle in the presence of
hydrogen formed in the reaction 65.

4.6.3 Configuration of Catalyst in Relation to Waste Heat Boiler Tube Sheet

The residence period which the product formaldehyde spends in the reaction “hot zone”, is
very important with regards to the obtained formaldehyde yield (due to the gas phase
decomposition of formaldehyde to carbon monoxide and hydrogen). BASF indicated that if
the distance from the baseplate to the tube sheet of the downstream heat exchanger was 4
68
cm, then the concentration of carbon monoxide was 0.6 % . Alternatively, the catalyst
could simply be directly placed on top of gauze supports which are laid on top to the tube
sheet. The benefit of placement of flow directing supports on top of the tube sheet of a
tubular heat exchanger system has been described 69. The outlined concept design in Figure
12 was targeted at reducing the residence time of the product gases at high temperature
conditions, thus avoiding side reactions such as the gaseous decomposition of
formaldehyde.
Figure 12: Illustration of the use of flow directing supports underneath silver catalyst beds

4.7 Waste Heat Boiler

It is essential to cool the product formaldehyde mixture as rapidly as possible to avoid
70
decomposition of gaseous formaldehyde to produce carbon monoxide and hydrogen .
The reaction product leaves the catalyst layer at ~600 to 700 °C and is required to be cooled
to less than 350°C as rapidly as possible to avoid formation of by-products 71. Vitvitskii and
72
Averbukh determined that the decomposition of formaldehyde was not only dependent
upon temperature but also residence time, with reaction times of 0.01 s or less
recommended. Maux 71 proposed that reinjection of a portion of the off-gas emitted from
the absorber columns should be conducted immediately underneath the silver catalyst bed.
The objective was to enhance the rate of cooling of the product gases and ultimately
increase process yield. A serpentine arrangement of cooling coils located close the exit of
the catalyst bed has also been suggested as being an efficient means of removing heat
effectively in order to minimise side reactions 73. Linzer et al. 74 described a novel design of
waste heat boiler which could reduce the exit gas temperature to < 300 oC in 60 ms. A
horizontal tube heat exchanger was employed and the presence of a spray unit also allowed
for the gas temperature to be further reduced to 80 oC. The use of ceramic inserts in the
boiler tubes is also claimed to aid the rate of heat transfer 62.
4.8 Absorber Design and Operation
The object of the absorber stage is to condense formaldehyde, unreacted methanol, and
water to produce concentrated solutions ranging from 37 to 55 wt% formaldehyde. A
typical design is shown in Figure 13 for the absorber unit. In practice, 3 or 4 recirculation
stages are employed wherein heat is removed from the solution by normally plate heat
exchangers 75.

Figure 13: Schematic representation of a formaldehyde absorber unit

The inlet temperature of the gaseous mixture which comprises mainly of nitrogen,
formaldehyde, hydrogen, unreacted methanol and water vapour is typically in the range of
120 to 160 oC depending upon formaldehyde plant configuration 29
. Winkelman et al. 76

presented a computational study which modelled commercial absorbers used in the

production of formaldehyde. The model which was able to accurately simulate industrial
data from operating formaldehyde plants and the main factors identified which promoted
the absorption process were: relatively large volumes of make-up water; recycling of liquid
in the column stages at high ratios; and reduced temperatures for the recycled liquid.
Yoshikawa et al. 29 described a means to produce high strength formaldehyde solutions (up
to 60 wt%) by adding a volume of make-up water equal to the amount of steam required in
the feedstream and then taking a side cut from an upper section of the absorber column
(often a tray type structure such as a bubble-cap) which was then added to the feed
mixture. The fundamental idea was to enhance the recovery of methanol while not
significantly diluting the formaldehyde product, which was in harmony with the calculations
of Winkelman et al. 76 which indicated that increasing the make-up water volume enhanced
the column efficiency. The resultant process water contained small percentage amounts of
methanol and formaldehyde.

4.9 Off-Gas Composition

Ideally, the off-gas which exits the absorber column should comprise of carbon dioxide,
carbon monoxide, nitrogen, hydrogen and perhaps some oxygen. Normally, some methanol
71
and formaldehyde may also be present due to absorber inefficiencies . Methylal
(dimethoxymethane) and methyl formate are also often present in amounts less than 1 v/v
%. BASF reported that the percentage of gases in the off-gas stream from an almost
complete methanol conversion formaldehyde plant was 3.5 % for carbon dioxide, 0.11 to
0.18 % for carbon monoxide, 17.3 to 18.2 % for hydrogen and 0.3 to 0.6 % oxygen with the
balance being nitrogen 77.

4.10 Distillation
Formaldehyde plants equipped with distillation units typically aim to produce consistent
product compositions such as 50/1 or 54/0.5 (wt % formaldehyde/wt % methanol). To
achieve this standard of product requires control of the solution composition made in the
initial conversion step over the catalyst bed. In relation to the catalytic reaction it is also
desirable to increase the formaldehyde yield and as such optimization of the formaldehyde
plant requires an understanding of the relationship between the absorber bottoms
composition and the expected distillation product composition in order to determine the
78
boundaries within which the formaldehyde plant can be operated. Ott et al. not only
simulated the distillation of formaldehyde solutions but also compared the postulated
performance with laboratory data. An important aspect of the latter study was the
inclusion of the complex solution behaviour of formaldehyde wherein it forms a range of
species such as methylene glycol, poly(oxymethylene) glycols, hemiformal and
poly(oxymethylene) hemiformals. Although the correlations were in some instances in
accord with experimental data it was concluded that equilibrium stage models were not
optimal and that the impact of reaction kinetics should also be considered. Terelak et al. 79
scaled up distillation tests with formaldehyde solutions to pilot plant level and discovered
that their physicochemical fluid property model simulated the pilot plant data to a high
degree of accuracy. Žilnik et al. 80 used ASPEN software to model the distillation process for
formaldehyde solutions and found that the predictions were not accurate due to the
influence of chemical kinetics and mass transfer.

4.11 Off Gas Burning

81
Baumann et al. detailed the generation of electricity from the off-gas produced during
formaldehyde synthesis which made use of the inherent fuel value of the hydrogen and
methanol present. Combustion of the off gas also had the benefits of reducing
environmental emissions, potentially attracting carbon capture credits due to the reduced
demand for fossil fuel based energy, in addition to supplying a portion of the formaldehyde
plant electricity needs. The question arises to the economic viability of the latter approach
as it would require significant capital investment, and is also dependent on the percentage
of hydrogen present in the off-gas which can vary significantly between different
formaldehyde units.

4.12 Reaction Light-Off

It is desirable for silver catalysts to produce formaldehyde solutions within specification as
soon as possible after being introduced to the industrial reactor in order to minimise
product which does not meet customer requirements. In the best instance, suitable product
is made within several hours but examples of 24 hours or more are not uncommon.

4.12.1 Hot Nitrogen Gas

Catalyst activation involving the use of hot nitrogen gas which is flowed over the catalyst
bed has been described. The nitrogen gas is externally heated by any type of suitable heat
exchanger and the aim is to preheat the catalyst bed to a temperature between 280 and
350 oC before introduction of the methanol/steam/air mixture 31
. This latter method has
the advantage of being relatively clean as minimal possibility of contamination of the
catalyst with carbon, copper oxide or rust during the catalyst activation process can occur.
In addition the entire volume of the reactor head is heated to high temperature, therefore
there is practically zero chance of methanol or water condensation during start-up which
can impact catalyst performance. No overheating of the parts of the catalyst surface
happens in contrast to methods involving the use of flames (as outlined below).

4.12.2 Heating with a Flame

Some formaldehyde plants have the methanol oxidation reaction initiated by exposing the
silver catalyst surface to a flame [Figure 14]. Compressed air is typically introduced to an
ignition system located immediately above the catalyst bed which in turn makes the
air/methanol ratio enter a region where combustion occurs. This method has not only the
disadvantages of uneven heat distribution across the bed surface, potential health and
safety issues as a flame is present but also it is typically not a fast process in terms of
achieving light-off in the reactor vessel.

(a) (b)

Figure 14: Examples of start-up procedures involving (a) flame (b) electrical means to
generate heat
4.12.3 Electrical Heating
Electrical heating is commonly used in Chinese designed formaldehyde plants and is a rapid
means of heating the catalyst with typical light off of the bed occurring within 2 minutes
[Figure 14]. An electrical coil is placed upon an insulating support framework as close to the
catalyst surface as possible to aid rapid light-off.

4.12.4 Acceleration of Bed Light-Off

In situations where difficulty in achieving reaction “light-off” is encountered, doping of the
catalyst bed with a fine layer of silver oxide (Ag2O) has been reported to exhibit beneficial
82
effects . Sprinkling of very fine silver powder (0.1-1 micron) on top of the silver bed,
permitted the reaction to start at 205-230 oC 83
. Millar et al. 84
employed both
Environmental Scanning Electron Microscopy (ESEM) and Raman microscopy to characterise
the interaction of methanol/air mixtures with silver (I) oxide. The silver oxide was
discovered to decompose to form very finely divided silver grains which were noted to be
exceptionally active due to a combination of the crystal faces exposed and the number of
intergrain boundaries created. Alternate approaches to alleviating the problem of slow
reaction light-off include construction of multilayered beds of silver catalyst with different
particle sizes 24. Using this latter invention it was claimed that light-off can be achieved at
temperatures of 553-573 K. In general, smaller silver grains were found to exhibit greater
85
activity , however due to sintering and plugging effects a bed cannot be entirely
constructed of these relatively small particles.

4.13 Process Conditions

4.13.1 Space Velocity & Methanol Loading
Space velocity is considered an important factor in improving the yield of formaldehyde.
The highest yields are obtained at relatively high space velocities, which is probably due to
the shortened contact time inhibiting side reactions. Gas Hourly Space Velocity (GHSV) is
defined as the number of times bed volume is swept out with reactant gas per hour (h-1).
Consequently, the residence time is defined as time the reactant/product stays within the
catalyst bed [Equation 10].
 1
Equation 10: 𝑅𝑒𝑠𝑖𝑑𝑒𝑛𝑐𝑒 𝑡𝑖𝑚𝑒 = × 3600
𝐺𝐻𝑆𝑉

The useful operating region for space velocity is typically 100,000 to 250,000 h-1. The
precise space velocity which provides optimum process benefits depends upon the plant
configuration. When the space velocity is less than the minimum recommended value then
problems can occur due to side reactions which typically produce carbon deposits.
Formaldehyde is not stable under normal reaction conditions and will decompose to form
carbon monoxide in the gas phase. Carbon monoxide can undergo further changes via the
Boudouart Reaction to make carbon and carbon dioxide.

Methanol loading on the catalyst bed is another useful measure when operating the
formaldehyde plant. A typical value for catalyst loading is 2.0 metric tons of methanol per
hour per m2 of catalyst bed area which equates to 25 kg/min/m2 86. Table 6 provides an
illustration of the variation of methanol loads encountered in industrial formaldehyde
plants.

Table 6: Examples of process conditions in a range of formaldehyde plants

MeOH flow Area of Bed Surface Methanol Load
(kg/min) (m2) (kg/min/m2)
Plant 1 15.625 0.697 22.4
Plant 2 23.6 0.697 34
Plant 3 36.11 1.33 27.2
Plant 4 33.33 1.21 27.5
Plant 5 64.17 2.27 28
Plant 6 43.05 1.17 36.8
Plant 7 31.25 1.13 27.7

4.13.2 Feed Ratios

Szustakowski 85 examined the importance of oxygen/methanol molar ratio during methanol
oxidation on a silver catalyst. He found that both methanol conversion and formaldehyde
yield were promoted when the O2/CH3OH ratio was increased from 0.25 to 0.40.
Waterhouse et al. 87 found that a molar ratio of methanol to oxygen of 2.25 was optimal in
terms of degree of methanol conversion and formaldehyde selectivity of polycrystalline
silver catalyst. These latter authors ascribed the relationship between feed stoichiometry
and catalyst performance in terms of the presence of various oxygen species on the silver
catalyst. For example, at low CH3OH/O2 ratios the dominance of the non-selective Oα
species was postulated. Lefferts et al. 88 noted that increasing oxygen concentration in the
feed generally enhanced formaldehyde production while also promoting carbon monoxide
and carbon dioxide formation. Use of higher reaction temperatures appeared to diminish
the amount of carbon dioxide formed.

It has been recognised for some time that addition of water to the reactor feed improves
conversion and yield. The oxygen concentration in the feed can be raised without causing
overheating, because some of the reaction heat is absorbed by water. The higher oxygen
concentration uses a larger proportion of hydrogen formed in the endothermic
formaldehyde synthesis reaction, and thus favourably shifts the equilibrium. The addition of
water can also activate the catalyst and extend the catalyst life. Lightly bound catalyst
poisons are often stripped off at high water addition rate. The optimal yield usually occurs
at a 60/40-weight ratio of methanol/water 86. Water fed to the reactor can be supplied as
moisture in the air, as water in the methanol feed, or as a separate stream. Water to be
added to the reactor feed can also be supplied be recycling dilute formaldehyde solution
from the top section of the absorber.

4.13.3 Dehydrogenation/Oxidation ratio

An insight to the formaldehyde plant operating conditions can be determined by calculation
of the dehydrogenation/oxidation ratio which can be estimated as shown in Equation 11.
Equation 11:

𝐷𝑒ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛𝑎𝑡𝑖𝑜𝑛/𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑖𝑜
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐷𝑒ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛𝑎𝑡𝑒𝑑 𝑡𝑜 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
=
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑂𝑥𝑖𝑑𝑖𝑠𝑒𝑑 𝑡𝑜 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒

Nagy and Mestl 89 proposed that surface embedded atomic oxygen (Oγ) was responsible for
the direct dehydrogenation of methanol reaction to produce formaldehyde and hydrogen,
and that surface adsorbed atomic oxygen (Oα) was responsible for the non-selective
oxidation of formaldehyde. Examination of the hydrogen content of the product gas
revealed that at elevated temperatures the direct dehydrogenation reaction dominates and
this result was in accord with the discovery that surface atomic oxygen species were largely
desorbed by this point.

4.13.4 Effect of Reaction Temperature

As the reaction temperature is raised from 200-700 °C the conversion of methanol increases
88
along with the production of formaldehyde . An increasing rate of the side reaction to
form carbon monoxide is also observed due to gaseous decomposition of formaldehyde.
Carbon dioxide is also formed, with relatively more at temperatures less than 350 oC
compared to when temperatures typical of industrial formaldehyde synthesis are employed
88
. The maximum yield of formaldehyde lies at the temperature at which the sum of the
losses due to unreacted methanol and from the formation of side products is at minimum.
Temperature is normally controlled by adjusting the amount of air that is supplied.

5. Polycrystalline Silver Catalyst

5.1 Pure Silver Catalyst
Polycrystalline silver catalyst is typically made by metal refiners. Examination of various
commercially available silver catalysts has revealed that they are not the same in terms of
physical properties [Figure 15]. This latter observation is at least partially due to the fact
that formaldehyde producers usually only request that the silver is at least 99.99 % pure and
of specified mesh fractions, hence there is often insufficient quality control in terms of silver
catalyst synthesis as desirable properties for formaldehyde synthesis are not explicitly part
of the customer specification.
 High Bulk Density Medium Density

Figure 15: SEM images of two types of polycrystalline silver catalyst

The basic properties of importance when considering metallic catalysts include: (1) purity;
(2) surface area; (3) packing density; (4) porosity; (5) shape; (6) mechanical strength and (7)
thermal conductivity. In China, two types of silver catalyst are used, the first is a high
density product termed “crystal silver” which is similar to the high bulk density material
illustrated in Figure 14. The second material is termed “foam silver” and this has an almost
wire like appearance and is characterized by a low bulk density (ca. 1 g/mL). Although the
“foam silver” has the highest surface area its performance is hindered by the exceptionally
low mechanical stability which leads to limited lifetimes in the order of only a few weeks.

Silver gauze was one of the original catalysts used for formaldehyde synthesis, but it is rarely
90
if ever used today. Nevertheless, recently Baltes et al. described a silver gauze catalyst
which exhibited improved formaldehyde yields which correlated with decreasing wire
diameter. Importantly the formaldehyde selectivity was said to increase from 87 to 90 %
when changing from a polycrystalline silver catalyst to a wire mesh silver material.
Methanol conversion in each instance was 99 %. It was noted however that no catalyst
lifetime information was provided and as such it is not known if the mechanical stability of
the silver mesh was sufficient for industrial implementation.

5.2 Modified Silver Catalyst

Several efforts to promote the catalytic performance of silver catalyst for formaldehyde
synthesis have been described. Claus et al. 91 proposed that silver catalyst could be doped
with Pd, Pt, Rh, Ru and Ir in addition to oxides such as alumina which were stable at
elevated reaction temperatures of up to 720 oC. An example of a 2 wt% doped silver
catalyst was presented wherein the formaldehyde yield was claimed to be 90.4 %. Esumi 92
suggested that silver alloyed with either platinum, palladium or rhodium may be suitable
93
methanol oxidation catalysts. Silver-lead catalyst has also been revealed by Gerberich
and under conditions where incomplete methanol conversion was achieved the
formaldehyde selectivity was reported as 91.8 %. Silver catalysts modified by the addition
94
of barium, strontium, calcium, and/or indium may be beneficial for oxidation reactions .
BASF promoted the idea of doping the surface of silver catalyst with phosphate species 95-97.
Diercks et al. 96 described the application of Na2P2O7 species on silver catalyst and proposed
that the activation time was shortened during catalyst light-off conditions.
Supported catalysts have also been proposed with silver supported on pumice stone widely
98 99
reported to have been used in the Russian formaldehyde industry . Chen et al.
proposed that silver coated on ceramic microspheres was an effective catalyst for methanol
oxidation to formaldehyde with methanol conversion stated to be in the range 90 to 98 %.
100
Diem et al. similarly indicated that silver deposited on porcelain spheres could be
101
employed in formaldehyde synthesis reactions. In another patent, Diem et al.
demonstrated that silver particles on an alumina support could also be considered for
methanol oxidation purposes.

5.3 Electrochemical Synthesis of Polycrystalline Silver

Two electrochemical cell configurations are employed to manufacture polycrystalline silver
catalyst [Figure 16]. A Balbach-Thum cell consists of horizontal cast silver anodes, which are
located in a top basket lined with cloth that is designed to collect anode slime and thus
prevent contamination of produced silver crystals. In the cell bottom is usually either a
carbon or more routinely a stainless steel cathode plate onto which the silver dendrites are
deposited. The electrolyte is typically prepared by dissolution of silver in concentrated nitric
acid and ultimately may contain from 10 to 200 g/L of silver following dilution with RO
water. Other metal ions are present in the electrolyte as a result of migration from the
anode material and species may include copper, lead, bismuth, and cadmium. Removal of
the product silver crystals is achieved by manual scraping of the cathode plate.
 Balbach-Thum Cell
Moebius Cell

Figure 16: Balbach-Thum and Moebius cells for electrocrystallization

Moebius first patented a process in 1884 using silver nitrate as a conducting media for the
electrolytic production of silver crystals. In the Moebius system, the anodes are cast, drilled
and bolted to hanger bars before being immersed in the electrolyte. A woven cloth bag of
controlled porosity is carefully placed about the anodes to catch any anode slime produced.
Normally, mechanically operated scrapers move back and forth over the cathode surface
and thus dislodge silver crystals which then fall to the bottom of the cell and can
subsequently be periodically removed.

In general, polycrystalline silver can be obtained by operation of an electrochemical cell, for

example the conventional Moebius or Balbach-Thum cells [Figure 16], using a silver nitrate
electrolyte in the pH range 1-4 containing between 5 and 100 g/L dissolved silver, a cell
temperature of 10-80 oC, a current density between 100 and 3000 A/m2 and a cell voltage
102
between 0.2 and 9 volts . In particular, preparation methods specifically related to
polycrystalline silver catalysts include the continuous electrolytic refining of silver in an
aqueous solution of silver nitrate and nitric acid at 24 oC, 3.1 volts and a current density of
1.2 amp/dm2 103
wherein silver grains of 0.2 to 2.5 mm in size are stripped from a slowly
rotating polypropylene anode. Also known is the addition of organic inhibitors to the
electrochemical cell to modify the structure of the silver crystals deposited. For example,
the addition of thiourea at the solubility limit produces crystals of the unorientated
dispersion type 104.
5.4 Silver Catalyst Bed Design
Silver catalyst beds are typically composed of a range of mesh fractions with the general
rule being that the largest granules are placed on the bottom of the bed, medium grains in
the middle section and fine silver on the top of the bed. Bed depths range from 1.5 to 3 cm
for the majority of catalyst beds in operation today. It is claimed that greater yields can be
70
achieved through use of several layers of catalyst, characterised by differing grain size .
For example, a double layer catalyst comprising both coarse and fine grains has been
105 24
recommended . Aicher et al. explored the concept of grain size distribution and bed
layer thickness and suggested three or more layers should be employed and specified an
overall total layer thickness of 15 to 25 mm. Laying of silver grains only at the outer edge of
the silver bed has also been described, presumably to minimize the possibility of the a
portion of the feed bypassing the catalyst due to inefficient sealing against the reactor wall
24
. Szustakowski 85 determined that smaller silver catalyst particles enhanced the degree of
methanol conversion and formaldehyde yield, an observation which may relate to the
increased silver surface area available for reaction to occur. However, it has also been
shown that beds with predominantly large crystals (80 to 90 % from 0.75 to 3 mm crystals)
relative to beds containing smaller silver granules (0.2 to 1 mm) gave a significantly higher
yield (90.8 % compared to 86.8 %) 77.

Dual bed designs incorporating two different catalysts have also been claimed to be
106
advantageous. Anita suggested that placing a metal oxide catalyst (iron molybdenum
107
oxide) on top of a silver catalyst can promote formaldehyde synthesis. Zhang et al.
proposed that the upper layer of the bed should be silver catalyst and that the lower portion
should be comprised of copper granules. The preferred ratio of copper to silver ranged
108
from 5:1 to 1:1. Wachs and Wang also suggested a similar arrangement wherein the
upper layer was silver and the lower layer was copper.

6. Mechanism for Formaldehyde Synthesis

It is beyond the scope of this article to review the fundamental catalytic science studies in
fine detail, however, a brief summation of the main features will be presented here.
6.1 Oxygen Chemistry
The oxygen chemistry with silver catalysts is critical in terms of the industrial partial
109
oxidation of methanol to form formaldehyde. Rocha et al. used in situ XPS to examine
the interaction of oxygen with either silver foil, silver powder or single crystals. Five distinct
oxygen species were detected and denoted Oα1, Oα2, Oα3, Oβ and Oϒ: Oα1 is ascribed to the
formation of oxygen induced reconstruction of crystal faces on silver; Oα2 is weaker in oxidic
character than Oα1 and is proposed to be an oxide located at steps and edges on the silver
surface; Oα3 is an “electrophilic oxygen” as described by Buhktyiarov and co-workers; Oβ is
assigned to oxygen atoms located in the bulk silver structure; Oϒ is stable at high
temperatures similar to those encountered during industrial methanol oxidation processes,
110
and is assumed to be the active site for formaldehyde synthesis . A range of surface
science investigations have been completed using various silver single crystals to determine
how oxygen interacts under different conditions. Ertl and co-workers [116, 117]
demonstrated that the dominant oxygen species present at industrial conditions were those
located in subsurface locations. Incorporation of oxygen species in the silver catalyst
promoted the formation of a distinct terrace and facets along with a series of small pits in
the surface 111. Scanning Tunnelling Microscopy (STM) images revealed that the Oϒ species
was located in the uppermost silver surface layer and this was due to the similar radius of
112
atomic oxygen and metallic silver . Raman spectroscopy has also been used to identify
84, 113, 114
the molecular and atomic oxygen species present on silver catalyst . The surface
embedded Oϒ species was characterized by a vibration at ca. 810 cm-1 and dissolved atomic
oxygen by a band at ca. 610 to 640 cm-1 115. Temperature Programmed Desorption (TPD) of
oxygen species present on polycrystalline silver as a function of various heat treatments has
shown that Oϒ was stable until at least 600 oC, whereas dissolved atomic oxygen (Oβ)
desorbed at ca. 380 oC 116.

6.2 Methanol Oxidation

Contact of only gaseous methanol with silver catalyst does not result in discernible interaction
with the surface, but the presence of adsorbed atomic oxygen was demonstrated by Wachs
117
and Madix to promote chemisorption and subsequent reaction to create methoxy,
formaldehyde and formate species. Isotopic labelling revealed that the initial step was the
interaction of methanol with atomically adsorbed oxygen to produce a methoxy species.
Subsequent loss of hydrogen produced formaldehyde and also potentially formate species
which were thought to be an intermediate in the combustion process to make carbon dioxide
and water. The basic steps in the catalytic reaction are shown below which agree with the
work of Wachs & Madix 117.

The Partial Oxidation of Methanol to Formaldehyde

Equation 12: 𝐶𝐻3 𝑂𝐻 (𝑔) + 𝑂 (𝑎) → 𝐶𝐻3 𝑂 (𝑎) + 𝑂𝐻 (𝑎)
Equation 13: 𝐶𝐻3 𝑂𝐻 (𝑔) + 𝑂𝐻 (𝑎) → 𝐶𝐻3 𝑂 (𝑎) + 𝐻2 𝑂 (𝑎)
Equation 14: 𝐻2 𝑂 (𝑎) → 𝐻2 𝑂 (𝑔)
Equation 15: 𝐶𝐻3 𝑂 (𝑎) → 𝐶𝐻2 𝑂 (𝑎) + 𝐻 (𝑎)
Equation 16: 𝐶𝐻2 𝑂 (𝑎) → 𝐶𝐻2 𝑂 (𝑔)

Carbon Dioxide Production

Equation 17: 𝐶𝐻2 𝑂 (𝑎) + 𝑂 (𝑎) → 𝐻𝐶𝑂𝑂 (𝑎) + 𝐻 (𝑎)
Equation 18: 𝐻𝐶𝑂𝑂 (𝑎) → 𝐶𝑂2 (𝑔) + 𝐻 (𝑎)
Equation 19: 2 𝐻 (𝑎) + 𝑂 (𝑎) → 𝐻2 𝑂 (𝑔)

Methyl Formate
Equation 20: 𝐶𝐻2 𝑂 (𝑎) + 𝐶𝐻3 𝑂 (𝑎) → 𝐻2 𝐶𝑂𝑂𝐶𝐻3 (𝑎)
Equation 21: 𝐻2 𝐶𝑂𝑂𝐶𝐻3 (𝑎) → 𝐻𝐶𝑂𝑂𝐶𝐻3 (𝑎) + 𝐻 (𝑎)
Equation 22: H𝐶𝑂𝑂𝐶𝐻3 (𝑎) → 𝐻2 𝐶𝑂𝑂𝐶𝐻3 (𝑔)

Formic acid is normally produced at ppm levels in the silver catalyst process [Equation 22]
and excessive amounts can cause problems relating to storage of product formaldehyde.

Equation 23: 𝐶𝐻2 𝑂 + 12𝑂2 → 𝐶𝐻𝑂𝑂𝐻

Other undesirable reactions, which must be avoided by proper control of temperature and
other factors if high yield are to be obtained, include the previously mentioned thermal
decomposition of formaldehyde to form carbon monoxide and hydrogen. The microkinetic
modelling of Andreasen and co-workers 118, 119 supported the findings of Wachs and Madix
117
. Practically, the operating temperatures for methanol oxidation are commonly in the range
550 to 700 oC and thus the coverage of atomically adsorbed oxygen under these conditions has
been suggested to be relatively small 89. Hence, it has been argued that embedded atomic
oxygen (Oϒ) is the active species for direct dehydrogenation of methanol to formaldehyde 87, 89.
Sun et al. 120 applied density functional theory and found that the OH bond formed by reaction
of embedded atomic oxygen (Oϒ) with methanol was weaker than the corresponding OH bond
created by interaction of methanol with surface atomic oxygen. As a result, the propensity to
form hydrogen was enhanced and thus promoted the dehydrogenation pathway for
121
formaldehyde synthesis. Temporal-Analysis-of-Products research by van Veen et al.
regarding methanol oxidation on polycrystalline silver also supported the idea that embedded
atomic oxygen (Oϒ) was indeed highly selective to formaldehyde and hydrogen, whereas
surface atomic oxygen was able to oxidise methanol to form carbon dioxide and water.
Schubert et al. 112, 122 reported that the reaction with surface oxygen was of limited selectivity,
a point also emphasised by Lefferts et al. 123 who indicated that weakly bound oxygen was the
cause of methanol combustion. As such the following reactions may apply [Equations 23 to
27].

Equation 24: 𝐶𝐻3 𝑂𝐻 (𝑎𝑑𝑠) + 𝑂 (𝑠𝑢𝑏) → 𝐶𝐻3 𝑂(𝑎𝑑𝑠) + 𝑂𝐻 (𝑠𝑢𝑏)

Equation 25: 𝐶𝐻3 𝑂 (𝑎𝑑𝑠) → 𝐶𝐻2 𝑂(𝑎𝑑𝑠) + 𝐻 (𝑎𝑑𝑠)

Equation 26: 𝑂𝐻 (𝑠𝑢𝑏) + 𝑂𝐻 (𝑠𝑢𝑏) → 𝐻2 𝑂(𝑠𝑢𝑏) + 𝑂 (𝑠𝑢𝑏)

Equation 27: 𝐻 (𝑎𝑑𝑠) + 𝑂𝐻 (𝑠𝑢𝑏) → 𝐻2 𝑂(𝑠𝑢𝑏)

Equation 28: 𝐻2 𝑂 (𝑠𝑢𝑏) → 𝐻2 𝑂(𝑔) + "𝑝𝑖𝑛 ℎ𝑜𝑙𝑒"

However, Andreasen et al. 118 argued that their microkinetic model for formaldehyde synthesis
did not require the assumption of more than one active oxygen species. Instead they indicated
that selectivity was related to kinetics and not thermodynamics. At higher temperatures such
as those encountered for industrial formaldehyde synthesis it was proposed that consumption
of oxygen for formaldehyde production resulted in unavailability of oxygen to cause unwanted
side reactions.
Regardless of the debate regarding the fundamental mechanism for formaldehyde synthesis,
“pin hole” defects have been widely reported to be apparent on the silver surface during
methanol oxidation conditions in accord with Equation 27 110, 124. For example, Millar et al. 18
used Environmental Scanning Electron Microscopy (ESEM) to observe the formation of “hill-
like” structures as the reaction temperature was elevated to ca. 450 oC before widespread
production of “pin-holes” at temperatures above ca. 600 oC. Closer inspection of the pin-hole
defects using Field Emission Scanning Electron Microscopy revealed the presence of debris
comprised of small silver particles in the immediate vicinity of each pin-hole thus confirming an
“explosion” of water vapour from the subsurface region of the catalyst occurred 114.

7. Catalyst Poisons
Industrially, one of the most critical issues with relation to catalyst performance is poisoning
of the silver surface which can result in diminished methanol conversion, reduction in
selectivity to formaldehyde, enhanced sintering of silver crystals and blockage of the
catalyst bed. Inherently, polycrystalline silver catalyst is of low surface area and thus it is
particularly susceptible to the effects of even low concentrations of impurities in the feed
stream.

7.1 Rust
Catalytic performance of silver can be compromised when iron is present on the surface 125,
126
. Iron (rust) contamination can arise from degradation of plant components and also be
125
present in feed materials. Deng et al. deposited iron nitrate on a polycrystalline silver
surface and investigated the impact by a variety of surface science techniques. As the
extent of iron present on the silver surface was raised, the formaldehyde selectivity
decreased and the methanol conversion increased. Consequently it was inferred that the
iron species promoted the combustion of methanol. X-ray photoelectron spectroscopy
revealed that the oxidation state of the iron species increased as the amount of iron present
was enhanced and this behaviour corresponded with increasing production of carbon
127
monoxide and subsequently carbon dioxide during reaction conditions. Jede et al.
further illuminated the situation with regards to iron poisoning of silver catalyst by
determining that even a 2 % monolayer coverage of the catalyst surface with iron species
was sufficient to promote combustion of methanol.
7.2 Silica
Silica is usually introduced as a catalyst poison through the feed water supply. Without a
water purification process the silver catalyst can become spoiled by the deposition of silica
on the silver surface. As a result the formaldehyde yield can decrease due primarily to a
reduction in methanol conversion. Figure 17 shows a Scanning Electron Microscope (SEM)
image of silica deposits on a silver catalyst as confirmed by energy dispersive spectroscopy.

(a) (b)

Figure 17: Example of silica deposition on a silver catalyst surface (a) SEM image of silver
catalyst grain (b) EDS trace for observed impurities

7.3 Carbon
Carbon is almost always found either in the used catalyst bed or in the area immediately
below the catalyst bed [Figure 18]. One pathway to carbon formation is via the
decomposition of formaldehyde gas.
Equation 29: 𝐻2 𝐶𝑂 (𝑔) ↔ 𝐻2 (𝑔) + 𝐶𝑂 (𝑔)

The decomposition of formaldehyde is favoured at the high reaction temperatures normally

encountered and the extent of this reaction depends upon the residence time of the hot
formaldehyde gas in the bed. The Boudouard reaction can then occur to produce
carbonaceous deposits.
Equation 30: 2 𝐶𝑂 ↔ 𝐶𝑂2 + 𝐶
In some instances, carbon is observed as a distinct layer in the silver catalyst bed cross
section [Figure 18] directly below an uppermost “white layer” of silver. This behaviour may
be due to issues with the feed ratios employed which may accelerate carbon deposition.

Figure 18: Examples of carbon decomposition in a silver catalyst bed

8. Future Directions
It is clear from this review that the formaldehyde synthesis process using silver catalyst
represents a fascinating challenge to improve performance. Key issues which should be
addressed include: (1) process optimization to maximise formaldehyde yield and further
reduce utilities consumption; (2) development of improved silver catalysts which are
tailored specifically for reaction conditions; (3) elimination of poisoning of silver catalysts;
(4) creation of a detailed economic model for formaldehyde production with silver catalysts
and comparison to the alternate metal oxide process.
Efforts will still be directed towards development of synthesising formaldehyde directly
128 129
from methane or carbon dioxide , but it should be remembered that a substantial
amount of capital has been invested in formaldehyde infrastructure hence any substantial
changes in the formaldehyde synthesis industry may take many years to appear. As such it
is more prospective to optimise current techniques such that the payback to industry could
be obtained immediately.

There exists a threat to the formaldehyde industry in terms of the development of non-
formaldehyde based resins 130. As this latter market is the major consumer of formaldehyde
in many global locations, it would be prudent for the formaldehyde industry to attempt to
diversify the uses for formaldehyde. One such example is the oxidation of formaldehyde to
formic acid which is a catalytic process which can be added to existing formaldehyde
production facilities 131.

9. Conclusions
Formaldehyde synthesis from methanol using a silver catalyst is a well-established
technology that continues to be widely employed industrially, with its continual growth in
popularity greatly attributed to the dominance of this process in the Chinese market. There
are three commonly employed process variations with the off-gas recycle process variant
considered state of the art technology due to reported higher formaldehyde yields and
production of high strength formaldehyde concentrations. However, there is no consensus
as to the best design of formaldehyde plants with considerable differences in equipment
specifications apparent.

Operating conditions are somewhat varied and there is a distinct need to understand the
fundamentals of formaldehyde synthesis to a greater degree if enhancement of
formaldehyde yields to levels which are comparable with the metal oxide catalysed
methanol oxidation process is to be gained. Academic literature has focussed on
fundamental studies of catalyst mechanisms on silver catalyst but only rarely addressed
problems which are industrially important such as catalyst bed design, design of improved
catalysts which are industrially viable, impact of catalyst poisoning and how to mitigate
these effects, and optimization of process design. It is generally agreed that high space
velocities are required to minimise side reactions and that reaction temperature should be
maintained as low as possible.

Polycrystalline silver catalyst made electrochemically dominates the formaldehyde industry

but it is evident that the quality is not consistent and that physical parameters such as high
surface area, good porosity, excellent mechanical strength, acceptable thermal conductivity,
and a medium bulk density are not always adhered to. The major drawback of
polycrystalline silver catalysts is their extreme sensitivity to catalyst poisons due to the
inherently low surface area present in metallic catalysts. A means to protect the silver
catalyst surface from contamination is desirable.

All too often, poor formaldehyde yields or unsatisfactory catalyst lifetimes have been
ascribed to undesirable catalyst properties despite the fact no catalyst autopsy was
performed or investigation of plant operation completed. Consequently, there exists
considerable scope to introduce and apply state of the art catalyst science and standardised
engineering methods to the formaldehyde industry.
10. Acknowledgements
We would like to thank all the formaldehyde producers, formaldehyde equipment suppliers,
and personnel who have shared their knowledge with us and allowed us to gain an insight
into the fascinating world of industrial methanol oxidation over silver catalyst.
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