Energy 35 (2010) 2528e2534

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Energy
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Silver and oxide hybrids of catalysts during formaldehyde production

Anita Kova
c Kralj*
Faculty of Chemistry and Chemical Engineering, University of Maribor, Smetanova 17, Maribor 2000, Slovenia

a r t i c l e i n f o a b s t r a c t

Article history: Hybrid catalysts are engineered to contain elements of two or more catalysts. Hybrid catalysts are
Received 19 June 2009 providing increasingly important advantages for obtaining novel and desirable catalyst activities and
Received in revised form properties. The nature of a hybrid catalyst can be changed with additional characteristics. The disad-
5 February 2010
vantages can be divided and the advantages multiplied.
Accepted 28 February 2010
This study describes a novel technology for the synthesis of formaldehyde production by using hybrid
Available online 31 March 2010
catalysts. The nature of the hybrid catalyst can be changed by the addition of positive properties. Both
100% oxide and 100% silver formaldehyde production processes can be modified during hybrid processes
Keywords:
Catalyst
by using a limited hybrid catalyst method. The basis of this method is its additional effect on the quality
Hybrid catalysts and/or quantity of available heat and product production by using limited hybrid catalysts. Two studies
Formaldehyde of the best hybrid catalysts are presented:
Silver process 1. Oxide process modification with 80% oxide and 20% silver catalysts.
Metal oxide process 2. Silver process modification with 90% silver and 10% oxide catalysts.
The basic characteristics of the silver and oxide formaldehyde processes can be kept. The hybrid
process has an effect on the quality and/or quantity of available heat and product.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Hybrid catalysts have been used in a wide range of chemical
processes [1, 2]. Constituted by a mixture of two or more compo-
nents, they may catalyze more than one reaction. Hybrid catalysts
increase many products, such as in methanol production.
Commercially, methanol is made from the synthesis of CO/H2 gas
obtained from the steam reforming of natural gas or the gasification
of coal. The technology of methanol conversion to hydrocarbons
provides an indirect means of converting natural gas into fuels. The
Cu-ZnO/SiO2 system is widely used in the production of methanol
from gas synthesis, where the active copper site shows improved
dispersion when supported [3].
The main feature of the technique for preparing hybrid cata-
lysts resides in the embedment of a microporous solid material’s
particles within larger particles of a mesoporous solid material.
This can be carried out by extrusion of the micron-sized or
submicron-sized particles of a zeolite or similar material with the
150e250 mm particles of the meso-porous material. In order
further to strengthen the extrudates, certain clays such as
bentonite may be used; however, the macroporous clay alone
does not have any influence on the conversion or the product’s
* Tel.: þ386 2 2294454; fax: þ386 2 2527774.
E-mail address: anita.kovac@uni-mb.si
selectivities, and thus does not affect the overall catalytic results
of the hybrid catalyst [4].
Different kinds of catalysts such as silver and oxide can be used
during formaldehyde production. Formaldehyde is a chemical
compound with the formula H2CO. It is the simplest aldehyde e an
organic compound containing a terminal carbonyl group: it
consists of exactly one carbonyl. It was first synthesized by the
Russian chemist Aleksander Butlerov, but was conclusively identi-
fied by August Wilhelm von Hofmann [5].
Two important routes are prominent during industrial form-
aldehyde production [6e8]. The first synthesis route is performed
over an electrolytic silver catalyst under lean-air conditions, and
was first commercialized at the beginning of the 20th century. The
second route, industrialized since the late 1959s, is by oxidation in
excess air over a ferric molybdate catalyst. Other routes have not as
yet been commercialized, e.g., the sodium catalyzed dehydroge-
nation of methanol to anhydrous formaldehyde, and the partial
oxidation of methane over silica catalysts. In 2000, about 55% of
the industrial production capacity in Western Europe was based
on the silver-catalyzed route, thus it plays an important role. Its
advantages are the relatively low investment cost, and stable
production.
This study presents the effects of hybrid catalysts on process
energy and product efficiency by using a limited hybrid method
(Section 2.1).

0360-5442/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2010.02.052
 A.K. Kralj / Energy 35 (2010) 2528e2534 2529

3: AX1 þ BX2 %C þ X1 þ X2
Nomenclatures
Note that, whereas X1 and X2 are occupied and regenerated
a number of times, it does not necessarily follow that their cata-
Indices: lyzing ability and/or number remain constant forever. For example,
av available poisons can intervene to slowly remove X1 and/or X2 from the
ox oxide system, thus slowing down the catalytic rate. What distinguishes
this decline in catalytic activity from that of a non-catalytic reac-
Variables tion, in which X1 and X2 are not regenerated, is that the complex-
Con conversion, 1 regenerating sequence occurs a greater number of times before X1
T temperature, K and X2 become inactive. No regeneration of X occurs during the
q mass flow rate, kg/h non-catalytic sequence. Hence, while catalysts can deteriorate,
F heat flow rate, W their active lifetime is far greater than the time required for
X fraction, 1 reaction.
The nature of the support can affect a catalyst’s activity and
selectivity. This effect presumably arises unnecessarily because the
2. The catalysis support can influence the surface structure of the dispersed cata-
lytic agent.
Although the catalyst remains unchanged at the end of the Hybrid catalysts are used more frequently in enzyme catalysis
process change, the material need not take part in the reaction, than in chemical catalysis. The nature of a hybrid catalyst can be
although some theories about catalyst activity do postulate that the changed with additional positive characteristics.
material does actively participate in the reaction. The mechanism of
catalysis is based on lowering the activation the free energy by the
presence of a catalytic material. The catalyst is effective in 2.1. Limited hybrid catalyst methodology
increasing the reaction rate because it makes an alternative
mechanism possible, each step of gas conversion having a lower Hybrid catalyst processes can change the characteristics of
free energy regarding activation than that of the non-catalyzed a basic process. It can enlarge the available heat and/or amount of
process. production.
The combining of or the complexities of the reactant and cata- The limited hybrid catalyst method (Fig. 1) was a very simple
lyst is a widely-accepted basis for explaining catalysis [9]. For method over five stages. Firstly, the advantages and disadvantages
example, suppose an overall reaction of: were analysed for the same product P production process, by using
different catalysts (X1 and X2). Secondly, the analyses needed real or
A þ B%C well-simulated process parameters (temperatures, pressure, mass
flow etc.) for a graphical presentation of the pure catalyst process.
is catalyzed via two active centres, or catalytic sites, X1 and X2,
The pure X1 catalyst data are presented at the left edge of the axis
which form complexities with A and B, respectively. The reaction is
and the pure X2 catalyst data at the right edge. Both points were
truly catalytic if the sequence of steps allows the centres X1 and X2
connected with the linear mathematical function which presented
to regenerate after causing the formation of C. In a general way the
hybrid catalyst processes. Thirdly, the basic characteristics of
process may be written as:
catalyst X1 could be changed by partly adding another catalyst X2
for up to 20%, and vice versa. The addition of the other catalyst was
1: A þ X1 %AX1 limited to 20%, therefore, the pure catalyst process cannot be
changed drastically and can thus retain the basic characteristics of
2: B þ X2 %BX2 the original process. Fourthly, this method includes the criteria of

Adding of another catalyst

Product P production by using Product P production by using

X1catalyst
catalyst X1 X2 X2 catalyst

1. Analysing the pure catalyst process 1. Analysing the pure catalyst process
2. Graphical presentation of catalyst process 2. Graphical presentation of catalyst process

3.
3. Hybrid
Hybrid catalyst
catalyst process
process X
X1 + X2 3. Hybrid catalyst process X2 + X1

4. Choosing the best hybrid catalyst process 4. Choosing the best hybrid catalyst process
5. Simulation of the best hybrid catalyst process 5. Simulation of the best hybrid catalyst process

Fig. 1. Limited hybrid catalyst method.

2530 A.K. Kralj / Energy 35 (2010) 2528e2534

formaldehyde: 250 kg/h

+ non-reacted gases
fresh methanol T = 61 oC
H2O: 3150 kg/h MeOH: 1600 kg/h
p = 1.4 bar
T = 21 oC T = 48 oC
MeOH: 5440 kg/h p = 1 bar p = 1.4 bar
M
T = 15 oC
p = 1,4 bar
water Φcon = − 2447 kW
A
air
B V H R C D
p = 1,4 bar T = 54 oC T = 85 oC o T = 70 Co
T = 150 C

O2: 1130 kg/h Φ = 1784 kW Φ = 212 kW Φ= − 1210 kW Φ= − 1649 kW Φreb = 2451 kW

N2: 4050 kg/h formaldehyde: 3318 kg/h
T = 15 oC water: 3748 kg/h formaldehyde: 3300 kg/h
p = 1 bar MeOH: 1616 kg/h water: 3748 kg/h
T = 66 oC T = 82 oC
p = 1.4 bar p = 1.4 bar

Fig. 2. Simple silver formaldehyde production process.

higher energy analysis of hybrid processes by determining the
exact fraction of adding a second catalyst. Fifthly, the hybrid cata-
lyst process was simulated and analysed once again with all the
advantages and disadvantages.
This method was tested on formaldehyde production by using
silver and oxide catalysts.
3. Case study
Formaldehyde is produced industrially by the catalytic oxida-
tion of methanol [8]. The most common catalysts are silver metal or
a mixture of an iron oxide with molybdenum and vanadium. In the
more commonly used FORMOXÒ process, methanol and oxygen
react at ca 250e400  C in the presence of iron oxide in combination
with molybdenum and/or vanadium to produce formaldehyde,
according to the chemical equation:
2CH3 OH þ O2 /2H2 CO þ 2H2 O
The silver-based catalyst is usually operated at a higher
temperature of about 650  C. Two chemical reactions from it
simultaneously produce formaldehyde: as shown above, plus the
dehydrogenation reaction:
CH3 OH/H2 CO þ H2
Depending on the catalyst’s temperature, the plant is operated
with lower or higher air deficiencies above the upper explosion
limit. This process can be operated with or without methanol
recycling.
Although formaldehyde is a gas at room temperature, it is
readily soluble in water, and it is most commonly sold as a 37%
solution in water known by trade-names, such as formalin or formol.
Formaldehyde is an important chemical used widely by industry
to manufacture building materials and numerous household
products. Its primary use is in the production of resins and as
a chemical intermediate. Urea-formaldehyde and phenol-formal-
dehyde resins are used in foam insulations, as adhesives in the
production of particle board and plywood, and in the treatment of
textiles.
Simple silver and oxide formaldehyde production flow-sheets
are presented in Sections 3.1 and 3.2.

formaldehyde: 417 kg/h

+ non-reacted gases
fresh methanol
T = 46 oC
H2O: 5478 kg/h
M p = 4 bar
T = 10 oC
MeOH: 5440 kg/h p = 1 bar
T = 15 oC
water
p = 1,4 bar
A
air
B V H R C
p = 1,4 bar T = 54 oC T = 85 oC T = 15 oC
T = 150 oC

O2: 4189 kg/h Φ = 1878 kW Φ = 226 kW Φ= − 6411 kW Φ= − 3145 kW

N2: 13801 kg/h formaldehyde: 4675 kg/h
T = 15 oC water: 8508 kg/h
p = 1 bar MeOH: 5 kg/h
T = 48 oC
p = 4 bar

Fig. 3. Simple oxide formaldehyde production process.

 A.K. Kralj / Energy 35 (2010) 2528e2534 2531

Mass flow of oxygen Conversion in reactor

4500 120
y = 3059x + 1130 y = 19x + 80
4000
100
3500
Mass flow of oxygen, kg/h

Conversion in reactor
3000 80

2500
60
2000

1500 40

1000
20
500

0 0
0 0,2 0,4 0,6 0,8 1 0 0,2 0,4 0,6 0,8 1
Fraction of oxide catalyst Fraction of oxide catalyst

Fig. 4. Graphical presentation of oxygen mass flow during both processes. Fig. 6. Graphical presentation of conversion in the reactor during both processes.

The metal oxide process can be described as a two-stage

3.1. Silver process
Fresh methanol (inlet stream M), which must be free of iron
carbonyls and sulphur compounds (catalyst poisons), is combined
with recycled methanol and pumped through a heated vaporizer
(V; Fig. 2). Air (inlet stream air) is drawn through a filter and
compressed in a blower (B) as feed to the process. The methanol
and air mixture is heated in a vaporizer (V) and a pre-heater (H)
before entering the reactor (R), and flows through a silver catalyst
bed, where the conversion of methanol to formaldehyde takes
place. The reaction gases are cooled (C) and enter the absorption
tower (A), where the absorption of formaldehyde takes place in
a counter-flow of four stages by means of aqueous formaldehyde
solution and cold de-mineralized water (inlet stream water). Non-
reacted methanol can be purified in a distillation column (D).
oxidation reaction during the vaporization phase, which involves
an oxidized (Kox) and a reduced (Kredox) catalyst.
Methanol (inlet stream M) is fed into the heated vaporizer (V;
Fig. 3). The process gas, a mixture of fresh air (inlet stream air) from
the atmosphere is drawn through a filter and compressed in
a blower (B). The methanol and air mixture are heated in a vapor-
izer (V) and pre-heater (H) before entering the reactor (R). The
conversion of methanol to formaldehyde takes place in tubes filled
with a metal oxide catalyst. The reaction’s heat is removed by using
steam production or for electricity cogeneration. The reaction gases
are cooled (C) and enter the absorption tower (A), where absorp-
tion of the formaldehyde takes place.
4. Limited hybrid catalyst method for formaldehyde
production

3.2. Oxide process The limited hybrid catalyst method was tested for formaldehyde
production during the fifth stage (Sections 4.1e4.5). Real or well-
Another possibility for formaldehyde production is the metal simulated parameters with real thermodynamic properties are
oxide process. The main differences compared to the silver process needed for analysing the pure process production of formaldehyde.
are: The right thermodynamic properties for oxygen and hydro-
carbon mixtures during process simulation and optimisation can be
 working with excess air; estimated using the Wilson model. In the case-studied formalde-
 type of catalyst; hyde plant, the flow rates of oxygen (O2) and hydrocarbon mixtures
 a lower temperature level. can be simulated using an Aspen Plus simulator [10], but accurate
estimates regarding the thermodynamic properties of oxygen and

Inlet mass flow of methanol Temperature in reactor

6000 700
Inlet mass flow of methanol, kg/h

5000 600
Temperature in reactor, oC

500
4000

400
3000
300
2000 y = -300x + 600
200

1000
100

0 0
0 0,2 0,4 0,6 0,8 1 0 0,2 0,4 0,6 0,8 1
Fraction of oxide catalyst Fraction of oxide catalyst

Fig. 5. Graphical presentation of methanol inlet mass flow. Fig. 7. Graphical presentation of temperature in the reactor during both processes.
2532 A.K. Kralj / Energy 35 (2010) 2528e2534

hydrocarbon mixtures need to be made. In this case study, the Comparison between grand composite curves
model is in relatively good agreement with experimental 450
measurements in the existing formaldehyde production plant.
400 100 % oxide catalyst
Simulated parameters were used in all further analysis.
80 % oxide catalyst
350
60 % oxide catalyst
4.1. Analysing the pure catalyst process

C
300

o
Temperature,
250
The limited hybrid catalyst method was introduced into the
formaldehyde production by using silver and oxide catalysts. Both 200

processes were operated with known advantages and disadvan- 150

tages. The silver process is cheaper when using higher reactor
100
temperatures but produces lower available heat. The oxide process
is expensive with a lower reactor temperature but with higher 50

available heat and product production. Both processes can be 0

improved by using a hybrid catalyst. 0 2000 4000 6000 8000
Enthalpy, kW

4.2. Graphical presentation of catalyst process Fig. 9. Comparison of grand composite curve of oxide hybrids processes.

The pure silver and oxide processes were analysed one by one by
using an Aspen Plus simulator. These values are presented graph-
ically at the edge of the axis, and between them represent hybrid
catalyst designs, which can be presented using mathematical linear
functions. The pure silver and oxide processes are denoted at the
edge of axis with value 0 and 1 of Xoxid. The parameter Xoxid can
denote the amount of oxide catalyst. The pure silver process as
a zero fraction of the oxide process amount (Xoxid ¼ 0). The oxide
process is presented as a total fraction of the oxide process amount
(Xoxid ¼ 1). Different hybrid processes use different catalytic
amounts as ratios between the silver and oxide processes.
4.3. Hybrid catalyst process
The adding of another catalyst to the basic catalyst was limited
to 20%, therefore, the basic process kept the important original
operational characteristics. The most important parameters (char-
acteristics) for the pure oxide and silver processes when analysing
were:
The processes used different inlet mass flows of oxygen
regarding raw materials (Fig. 4). The silver process used 1130 kg/h
of oxygen. The oxide process used 4189 kg/h of oxygen. Hybrid
processes use different catalytic amounts and use different inlet
oxygen mass flows between 1130 and 4189 kg/h. The mathematical
approximation Eq. (1) of the oxygen’s mass flow rate (qox) for
hybrid was:
qox ¼ 3059Xoxide þ 1130 (1)
Inlet mass flow rate of methanol (qM ¼ 5440 kg/h) was the same
during both processes (Fig. 5).
Conversion in the reactor was different; the oxide process had
higher conversion (Fig. 6). The oxide process had 99% conversion
and the silver process 80% conversion. The hybrid processes, using
different catalytic amounts, had different conversions between 80%
and 99%. The mathematical approximation Eq. (2) of the conversion
in reactor (Con) for hybrid was:
Con ¼ 19Xoxide þ 80 (2)

 inlet oxygen’s mass flows; The temperature in the reactor was higher during the silver
 inlet methanol mass flows; process (Fig. 7). The silver process had an approximate temperature
 conversion in the reactor; of about 600  C. The oxide process had an approximate
 temperature in the reactor and
 available heat. Comparision between grand composite curve
160
Graphical and mathematical linear functions (Figs. 4e8) for
different hybrid processes were carried out for all these parameters. 140

120
Available heat
o
C

10000 100
y = 7238x + 2149
Temperature,

9000
80
8000
60
Available heat, kW

7000

6000 40

5000 20
4000
0
3000 0 1000 2000 3000 4000 5000
2000 Enthalpy, kW
1000 100 % silver catalyst 90 % silver + 10 % oxide
0 catalysts
0 0,2 0,4 0,6 0,8 1 80 % silver + 20 % oxide
Fraction of oxide catalyst catalysts

Fig. 8. Graphical presentation of available heat during both processes. Fig. 10. Comparison of grand composite curve of silver hybrids processes.
 A.K. Kralj / Energy 35 (2010) 2528e2534 2533

formaldehyde: 41 kg/h
+ non-reacted gases
fresh methanol
T = 10 oC
H2O: 5478 kg/h
M p = 4 bar
T = 10 oC
MeOH: 5440 kg/h p = 1 bar
T = 15 oC
water
p = 1,4 bar
A
air
B V H R C
p = 1,4 bar T = 54 oC T = 85 oC o T = 15 oC
T = 150 C

O2: 3580 kg/h Φ = 1879 kW Φ = 203 kW Φ= − 6128 kW Φ= − 3564 kW

N2: 11790 kg/h formaldehyde: 4807 kg/h
T = 15 C o water: 8351 kg/h
p = 1 bar MeOH: 310 kg/h
T = 16 oC
p = 4 bar

Fig. 11. Simple oxide process modification.

temperature of about 300  C. The mathematical approximation Eq.
(3) of temperature in the reactor (Tr) for hybrid was:
Tr ¼ 300Xoxide þ 600
The oxide process had the higher available heat (Fig. 8). The
available heat can be estimated approximately by using the graph’s
8. An almost exact estimation can be established by using the Aspen
Plus simulator. The mathematical approximation Eq. (4) of total
available heat (Fav) for hybrid was:
Fav ¼ 7238Xoxide þ 2149
4.4. Choosing the best hybrid catalyst process
The best one needs to be chosen from among the hybrid
processes as criteria for the energy analysis was used and for
maximal additional product production. The energy criteria used
was the thermodynamic method, better known as “pinch analysis”.
Pinch analysis helps us to better analyse heat integration, the
available heat during a process using graphical representation as
a grand composite curve (Figs. 9 and 10). This is a powerful tech-
(3) nique for the synthesis of a utility system and the results from this
method can be used to postulate a superstructure [11]. Pinch
analysis is guiding heat and power integration using an extended
grand-composite curve [12]. Thermodynamic analysis does not
guarantee a global optimum solution because it cannot be used
simultaneously with the material balance, but it quickly proposes
good ideas for the heat and power integration of complex
(4) processes [13].
Comparisons between the grand composite curves of the oxide
and silver hybrid processes were decisive for choosing the kind of
hybrid. Fig. 9 presents comparisons between the pure oxide process
and hybrids with 80% oxide and 20% silver catalysts, and 60% oxide
and 40% silver catalysts. The hybrid with 80% oxide and 20% silver
catalysts can therefore choose the higher temperature profile and
thus a higher quality of available heat.

formaldehyde: 20 kg/h
+ non-reacted gases
fresh methanol T = 61 oC
H2O: 3150 kg/h MeOH: 1539 kg/h
p = 1.4 bar
T = 21 oC T = 48 oC
MeOH: 5440 kg/h p = 1 bar p = 1.4 bar
M
T = 15 oC
p = 1,4 bar
water Φcon = − 2354 kW
A
air
B V H R C D
p = 1,4 bar T = 54 oC T = 85 oC o T = 70 oC
T = 150 C

O2: 1435 kg/h Φ = 1882 kW Φ = 122 kW Φ= − 2587 kW Φ= − 1853 kW Φreb = 2389 kW

N2: 4721 kg/h formaldehyde: 3634 kg/h
T = 15 oC water: 4747 kg/h formaldehyde: 3634 kg/h
p = 1 bar MeOH: 1539 kg/h water: 4747 kg/h
T = 66 oC T = 82 oC
p = 1.4 bar p = 1.4 bar

Fig. 12. Simple silver process modification.

2534 A.K. Kralj / Energy 35 (2010) 2528e2534
Fig. 10 presents comparisons between the pure silver process
and hybrids with 80% silver and 20% oxide catalysts, and 90% silver
and 10% oxide catalysts. The hybrid with 90% silver and 10% oxide
catalysts can, therefore, provide enough quantity of additional
available process heat, and product increase.
4.5. Simulation of the best hybrid catalyst process
The proposed hybrid processes were tested and simulated by
using an Aspen Plus simulator. Both the 100% oxide and 100% silver
formaldehyde production processes can be modified during hybrid
processes, therefore, the two best studies were presented:
1 Oxide process modification with 80% oxide and 20% silver
catalysts
2 Silver process modification with 90% silver and 10% oxide
catalysts.
The oxide process modification with 80% oxide (mixture of an
iron oxide with molybdenum and vanadium) and 20% silver cata-
lysts - the oxide hybrid process (Fig. 11) was very close to the oxide
process, having little difference. The inlet stream of air can be
decreased by 14% (from 4189 kg/h of oxygen to 3580; Fig. 4). The
temperature in the reactor was higher by about 60  C (Fig. 7),
therefore, it would produce the highest pressure steam for elec-
tricity cogeneration. The available heat in the reactor was a little
lower (from 6411 kW to 6000 kW) during the oxide hybrid process.
The oxide hybrid process has the lower catalytic costs, but the silver
catalyst is cheaper [8]. The production of formaldehyde was lower
by 3.8% as a pure catalyst process.
The silver process modification with 90% silver and 10% oxide
catalysts e the silver hybrid process (Fig. 12) was very close to the
silver process, having little difference. The inlet stream of air
decreased by 27% (from 1130 kg/h of oxygen to 1435; Fig. 4). The
temperature in the reactor was lower by about 30  C (Fig. 7) but
with an additional reactor heat enthalpy of 1370 kW. This heat can
be used for heating the column reboiler, so during this process
steam is not needed for heating. The silver hybrid process had the
highest catalytic costs [8]. The production of formaldehyde was
higher by 1.9% compared to the pure catalyst process.
5. Conclusion
Hybrid catalysts are used more frequently in enzyme catalysis
than in chemical catalysis. The nature of a hybrid catalyst can be
changed with additional positive characteristics. Opportunities for
positively increasing these characteristics depend very much on
used the hybrid catalysts. An important characteristic of a hybrid
catalyst is its effect on process efficiency.
The limited hybrid catalysts can have an additional effect on the
quality and/or quantity of available heat and product production by
using limited hybrid catalysts. The hybrid silver and oxide
processes can have an effect on the quality and/or quantity of
available heat and product production. The criteria as to which
hybrid can be used, is the quality and/or quantity of available heat
and maximal additional product production.
The results and methodology for possible theoretically identi-
fiable hybrid catalytic themes can be analysed graphically, by using
Aspen Plus. The most important parameters: such as inlet oxygen’s
mass flows, inlet methanol mass flows, conversion in the reactor,
temperature in the reactor, and available heat, can be defined
between hybrid oxide and silver processes.
Both the 100% oxide and 100% silver formaldehyde production
processes can be modified during hybrids’ processes, therefore, two
studies were presented:
1 oxide process modification with 80% oxide and 20% silver
catalysts;
2 silver process modification with 90% silver and 10% oxide
catalysts.
The oxide process modification was based on 80% oxide catalyst
material and the addition of 20% silver catalyst. The oxide process
modification can synthesize formaldehyde with additional energy
efficiency, therefore, it would produce the highest pressure steam
for electricity cogeneration. The overall methanol conversion is
3.8% lower in an oxide hybrid plant than in a 100% oxide process.
The silver process modification was based on 90% silver catalyst
material and the addition 10% oxide catalysts. The 10% changing
catalyst can enlarge the available heat and product production by
1.9%.
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