Millar 2017

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Review
Industrial Production of Formaldehyde using Polycrystalline Silver Catalyst
Graeme John Millar, and Mary Collins
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b02388 • Publication Date (Web): 26 Jul 2017
Downloaded from http://pubs.acs.org on August 3, 2017
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Page 1 of 53 Industrial & Engineering Chemistry Research
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3 Industrial Production of Formaldehyde using Polycrystalline Silver Catalyst
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5 *Graeme J. Millar and 1Mary Collins
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8 Institute for Future Environments, and 1School of Chemistry, Physics & Mechanical
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10 Engineering, Science and Engineering Faculty, Queensland University of Technology (QUT),
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12 Brisbane, Queensland 4000, Australia. Email: graeme.millar@qut.edu.au
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We report the first comprehensive review of the industrial process for the catalytic partial
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17 oxidation of methanol to formaldehyde using silver catalyst. Formaldehyde remains a key,
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19 large volume industrial chemical which is ubiquitous to household, commercial, aviation,
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21 pharmaceutical and automotive products due to its high reactivity and versatility. Critical
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analysis of the various technological approaches used to manufacture formaldehyde,
24 characteristics of silver catalysts employed, process conditions, and performance values has
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26 been presented. The three common plant types are: almost complete conversion (BASF
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28 type); incomplete conversion followed by distillation (ICI type); and the off-gas recycle
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30 process which dominates world production due to its extensive use in China. Polycrystalline
31 silver remains the most popular catalyst, with only minimal use of alternate supported
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33 catalysts or gauze materials. Catalyst physical properties such as bulk density, purity,
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35 mechanical strength, size fraction and shape are important in relation to overall
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37 formaldehyde synthesis performance. Process yields majorly range from ca. 82 to 92 % and
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catalyst lifetimes vary from 4 weeks to 12 months. There is a research need to not only
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40 raise overall yields consistently to in excess of 90 % but to also maximise catalyst life.
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42 Aspects which should be taken into account include: purification of feed components;
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44 development of a systematic means for catalyst bed design; improvement and
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46 standardization of process configuration; equipment optimization; investigation of the
47 benefits of feed or catalyst additives; protection of the catalyst bed from poisoning events
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49 and discovery of preferred process operating conditions. In the near term, focussing on
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51 optimization of the current formaldehyde synthesis industry is seen as more prospective
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53 from a commercial point of view, than longer term investigation of alternate pathways for
54 manufacturing formaldehyde from methane or carbon dioxide which may not be viable for
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56 at least a decade.
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Industrial & Engineering Chemistry Research Page 2 of 53
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3 Key Words: silver catalyst; methanol; oxidation; formaldehyde; engineering; chemistry
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5 1. Introduction
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7 Formaldehyde remains one of the most important chemicals produced in the world today
8 due to its unparalleled reactivity and versatility 1. Primarily, formaldehyde is employed in
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10 the production of resins for the wood panel industry, with urea formaldehyde (UF), phenol
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12 formaldehyde (PF) and melamine formaldehyde (MF) resins and their variants representing
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14 the major formulations 2-5. Formaldehyde is also used to make chemicals such as polyacetal
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or polyoxymethylene (POM) 6, pentaerythritol 7, 8, paraformaldehyde 9, acetylenic chemicals
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17 10 11 12-14
, hexamine and methylal (dimethoxymethane) . Consequently a wide range of
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19 industrial applications depend upon formaldehyde such as construction, automotive,
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21 aviation, pharmaceuticals and cosmetics 1.
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24 In the early twentieth century the manufacture of formaldehyde on a small scale was
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26 initiated in Europe and the USA 15. The development of high-pressure synthesis of methanol
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28 by BASF in 1923 allowed the production of formaldehyde on a true industrial scale .
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30 Initially, gauze made of silver wire was used as the catalyst element 17. However this type of
31 catalyst has almost entirely replaced by a shallow catalyst bed of silver crystals 18. Further
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33 19
development resulted in the mixed iron oxide-molybdenum oxide catalyst which now
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35 competes with the silver process, accounting for approximately forty-five percent of the
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37 world’s production of formaldehyde . Other processes that employ oxidation of
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hydrocarbons or hydrogenation of carbon monoxide are not industrially significant since
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40 they compare unfavourably with methanol conversion either in terms of cost or decreased
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42 yield 21, 22.
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46 A concentration of 37 wt % formaldehyde is used as a standard for pricing or production
47 data, although in reality industrial plants typically make formaldehyde solutions of up to 55
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49 wt % concentration 1. The silver catalyst based process for formaldehyde manufacture
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51 proceeds by two pathways, a partial oxidation reaction [Equation 1] and a dehydrogenation
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53 reaction [Equation 2].
54 Equation 1: + → +
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56 Equation 2: → +
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ACS Paragon Plus Environment
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3 Despite the considerable importance of formaldehyde to our daily lives until this point there
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5 has not been a comprehensive review of the industrial synthesis using polycrystalline silver
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7 catalyst. Despite lower yields of formaldehyde compared to the metal oxide process the
8 silver process continues to grow in popularity. This latter situation is at least in part due to
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10 inherently cheaper production plants as the ability to operate with excess methanol results
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12 in substantially smaller units than the metal oxide process which requires excess air. In
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14 addition, catalyst costs are normally less with silver compared to metal oxide and silver
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catalysts can be regenerated on site, which is not the case with the oxide materials. Utilities
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17 consumption is also less with silver based formaldehyde plants due primarily to the reduced
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19 need for electricity to drive the air blowers. Consequently, this study will present
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21 information regarding the industrial practices employed, silver catalyst properties, process
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engineering and operating principles. Ultimately, this review will provide an insight into the
24 challenges to optimise formaldehyde synthesis and produce the next generation of
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26 formaldehyde manufacturing technology.
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30 2. Process Definitions
31 The formaldehyde industry employs a variety of terms to describe the efficiency of the
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33 methanol oxidation process. These terms are quantifiable measurements of the process
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35 efficiency and include methanol conversion, selectivity, formaldehyde yield, production
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37 ratio and catalyst life.
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40 2.1 Selectivity
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42 When converting the methanol feed it is important to produce valuable formaldehyde and
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44 not by-products such as carbon dioxide, carbon monoxide, and formic acid. Formaldehyde
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46 selectivity is a measure of the amount of formaldehyde produced per unit of methanol
47 reacted and is defined as in Equation 3.
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50
! "#$%&'(& )#&*+& ×-..
51 Equation 3: % ℎ =
! /'%0 102 ! /'%0 3*/
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3 Also of interest is an understanding of the quantities of carbon dioxide and carbon
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5 monoxide as they give an indication of the extent of methanol combustion and
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7 formaldehyde decomposition during the formaldehyde synthesis process [Equations 4 & 5].
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9
! 8%#90 :;<;& )#&*+& ×-..
10 Equation 4: % 4 5 6 7 = ! /'%0 102 ! /'%0 3*/
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12
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14 Equation 5:
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! 8%#90 0<;& )#&*+& ×-..
16 % 4 5 = 5 7 =
17 ! /'%0 102 ! /'%0 3*/
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20 2.2 Methanol Conversion
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22 The cost of methanol is the most critical parameter with respect to formaldehyde
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24 production economics. Typically, ca. 70 % of the manufacturing cost is attributable to
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methanol feedstock. Therefore, it is crucial to convert as much methanol as possible into
27 formaldehyde during the industrial reaction. The percentage methanol conversion is
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29 defined as in Equation 6.
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($ ! $/'%0 ;0 – $ ! $/'%0 */) < -..
33 Equation 6: % =ℎ5 5> 5 = $ ! $/'%0 ;0
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35
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37 Alternatively, methanol conversion can be calculated from knowledge of the composition of
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39 the product in the absorber bottoms (most useful when dealing with plants equipped with
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distillation units) [Equation 7].
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44 Equation 7:
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46 % =ℎ5 5> 5 =
47 % !#$%&'(& +0+0/#%/;0 ;0 C#&*+/ < -..EF
48 B(% !#$%&'(& +0+0/#%/;0 ;0 C#&*+/ < -..EF)G% $/'%0 ;0 C#&*+/H 7100
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50
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52 As a worked example, consider an absorber bottoms composition of 44 wt% formaldehyde
53 and 15 wt% methanol [Equation 8].
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KK < -..EF
57 Equation 8: % =ℎ5 5> 5 = B(KK < -..EF)G-LH 7100 = 75.8%
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5 2.3 Formaldehyde Yield
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Formaldehyde yield can be defined as shown in Equation 9.
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8
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10 Equation 9:
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% "#$%&'(& Q+/;R;/( < % /'%0 80R# ;0
12 % = ℎ P =
-..
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16 Yield is the most often quoted parameter in formaldehyde plants and can range from 82 to
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92%, depending on the quality of the plant operation. Even a one per cent change in yield
19 can represent significant financial benefit to formaldehyde producers.
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23 Many formaldehyde plants use “production ratio” as the key performance indicator which is
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25 defined as “kg of methanol required to make 1 tonne of 37 wt% formaldehyde”. The
26 theoretical minimum value is 394.7 kg of methanol per tonne of 37 wt% formaldehyde. For
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28 formaldehyde plants which produce high concentration formaldehyde solutions, the
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30 production ratio is also defined as “kg of methanol required to make 1 tonne of 50 wt%
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32 formaldehyde”, which in turn means the theoretical minimum methanol consumption is
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533.3 kg of methanol per tonne of 50 wt% formaldehyde. Finally, the Indian formaldehyde
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35 marketplace favours calculation of the production ratio in terms of “tonnes of 37 wt%
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37 formaldehyde made from 1 tonne of methanol”, with theoretical limit of 2.53 tonnes of 37
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39 wt% formaldehyde. A summary of the relationship between the various yield definitions is
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41 illustrated in Table 1.
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44 Table 1: Demonstration of the relationship between formaldehyde yield and production
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46 ratios
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48 Formaldehyde Yield Production Ratio (kg Production Ratio (kg Production Ratio
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(%) of MeOH to make 1 of MeOH to make 1 (tonnes of 37 wt% FA
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51 tonne of 37 wt% FA) tonne of 50 wt% FA) made from 1000 kg
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53 of MeOH)
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55 82 481 650 2.08
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57 83 476 643 2.10
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2
3 84 470 635 2.13
4
5 85 464 627 2.15
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7 86 459 620 2.18
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9
87 454 613 2.20
10 88 449 606 2.23
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12 89 443 599 2.25
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14 90 439 593 2.28
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16 91 434 586 2.31
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18 92 429 580 2.33
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21 Table 2 displays an example of operating data from a formaldehyde plant using silver
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23 catalysts along with appropriate calculation of performance parameters.
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3 Table 2: Example of performance values from an operating formaldehyde plant
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5 Methanol Consumption 30,000 kg/day
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7 Formaldehyde Produced 50,824 kg/day
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9
Formaldehyde in Product 48 wt %
10 Methanol in Product 1.5 wt %
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12 Formaldehyde Produced 65,934 37 wt% basis/day
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14 Production Ratio 455 kg of methanol per tonne
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16 37wt% formaldehyde
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Formaldehyde Selectivity 89.24 %
19 Methanol Conversion 97.15 %
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21 Formaldehyde Yield 86.7 %
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25 2.4 Catalyst Life
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Silver catalysts typically operate in a formaldehyde plant for a period of between a few
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28 months and a year. Silver sinters at the high reaction temperatures, thus resulting in
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30 elevation of pressure drop over the bed and usually decreased performance. It is preferable
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32 for catalysts to last as long as possible, however, there is a point where the lower
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34 productivity, higher power costs and safety considerations outweigh the cost of replacing
35 the catalyst. The life of silver catalyst is highly dependent upon the operating conditions of
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37 the formaldehyde reactor. For example, the catalyst life is usually longer when the catalyst
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39 is operating at relatively low temperatures and comparatively small plant loads. The form of
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41 the silver catalyst used has also been observed to play a critical role in terms of provision of
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longer useful operating life as can be seen in Table 3.
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46 Table 3: Examples of catalyst life for two types of silver catalyst in a range of formaldehyde
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48 plants
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50 Silver Catalyst Type 1 Life (days) Silver Catalyst Type 2 Life (days)
51 Plant 1 180 100
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53 Plant 2 100 75
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55 Plant 3 43 23
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57 Plant 4 110 42
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5 It has been proposed that the water ballast process (BASF) promotes longer catalyst life as
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7 introduction of water with its associated high heat capacity promotes homogenous
8 distribution of heat over the catalyst bed and thus minimises sintering and coke formation
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10 23
. The consequences of catalyst poisoning cannot be ignored and may be a major factor in
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12 relation to catalyst life. A catalyst with a design life of six months can be significantly
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14 compromised due to the quality of methanol . If the methanol feedstock has a high
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permanganate reactivity the catalyst life was found to be reduced to only two months.
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19 At the end of its useful life, silver catalyst is normally returned to the catalyst supplier for
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21 reprocessing. Therefore, essentially the silver bullion component is loaned to the
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formaldehyde producer and fabrication costs are incurred for the conversion of the silver to
24 the catalyst form. Some formaldehyde producers have suggested that only the uppermost
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26 section of the silver bed should be removed and replaced with fresh silver catalyst .
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28 However, it has not been demonstrated that this latter approach is beneficial in terms of
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30 maintaining overall catalyst performance since the lower portion of the bed may have
31 sintered or been poisoned during the previous operational campaign.
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35 3. Industrial Process Designs for Methanol Oxidation to Formaldehyde using Silver
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37 Catalysts
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3.1 Almost Complete Conversion of Methanol
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40 Gerloff 26 described the single pass, almost complete conversion of methanol method which
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42 is often referred to as the “BASF process”. Sperber intimated that the operating
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44 temperature of the silver catalyst was in the range 600 to 700 oC, and that formaldehyde
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46 yields were as high as 87.5 %. A mixture of air, steam and methanol was supplied to the
47 silver catalyst in the gas phase, with the methanol/water mass ratio typically 60/40. Hence,
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49 why the BASF process is also termed the water ballast method . The process for the
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51 almost complete conversion of methanol to formaldehyde is shown in Figure 1. A mixture
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53 of methanol and water is typically fed into the evaporator vessel wherein air is sparged into
54 the solution. The gaseous feed mixture is subsequently superheated to ensure the presence
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56 of liquid is eliminated prior to being fed to the reactor where it flows through a 20-30 mm
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3 thick bed of silver crystals. A gas filter system may be present immediately prior to the
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5 reactor entrance as is usually a flame arrestor for safety reasons.
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33 Figure 1: Almost complete conversion process for methanol oxidation to formaldehyde
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36 The product formaldehyde gas is thermally unstable and thus rapid cooling of the gaseous
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38 mixture is achieved by passage through a waste heat boiler system containing pressurized
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40 water 28. The exit gas stream is normally in the range 120 to 200 oC and this is then passed
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42 into an absorption tower which contains appropriate packing material. The high
43 concentration formaldehyde solution is withdrawn from the bottom of the column and the
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45 non-condensable gases (off-gas) exit from the final stage which is usually a bubble-capped
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47 system . To aid the production of high concentration formaldehyde solutions the water
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49 quantity required for the feed is often initially added to the top of the absorber column and
50 29
then drained from the exit of the final stage . This process modification has two main
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52 benefits: (1) the volume of water added to the absorber is 200 to 500 % greater than in
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54 normal operation which means that the emissions of formaldehyde and methanol from the
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56 column are minimized; (2) the water contains recaptured methanol and formaldehyde
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58 which are recycled to the reactor and ultimately enhance process yield. An example of
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1
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3 operating parameters for an almost complete conversion formaldehyde unit is shown in
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5 Table 4.
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8 Table 4: Typical operating parameters for an almost complete conversion formaldehyde
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10 plant
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12 Air Flow Rate 6040 Nm3/h
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14 Air Flow Rate 6,040,000 L/h
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16 Molar Air Flow Rate 269643 mol/h
17 Methanol Flow Rate 4667 kg/h
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19 Methanol Purity 99 %
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21 Methanol Quantity 4620 kg/h
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23 Molar Methanol Flow Rate 144375 mol/h
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25 Molar Air/Methanol Ratio 1.87
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Water Flow Rate 2364 kg/h
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28 Water Purity 94 %
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30 Actual Water Flow 2222 kg/h
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32 Steam/Methanol Mass Ratio 0.48
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3.2 Incomplete Conversion of Methanol Followed by Distillation
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37 An alternative approach to formaldehyde synthesis is to operate the production unit with a
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39 large excess of methanol such that distillative recovery of methanol is required to meet
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41 product specifications [Figure 2]. This approach has the advantage that comparatively low
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43
reaction temperatures are often employed which may suppress undesirable secondary
44 reactions. For example, Eek-Vancells reacted a methanol/air/steam mix at 560 oC to obtain
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46 an effluent comprising of 1000 kg/h formaldehyde, 782.2 kg/h methanol and 470 kg/h water
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48 (in addition to non-condensable products) 30. Distillation facilitated production of a solution
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50 containing 55 wt% formaldehyde and <1 % methanol. Methanol recovered at the top of the
51 column was recycled to the evaporator. However, the main drawback of distillation is that it
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53 represents not only additional capital expenditure when constructing the formaldehyde
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55 plant but also it consumes a significant quantity of steam. Table 5 provides an example of
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57 typical operating parameters for an incomplete conversion followed by distillation process.
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30 Figure 2: Incomplete conversion followed by distillation process for methanol oxidation to
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32 formaldehyde
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3 Table 5: Typical operating parameters for an incomplete conversion followed by distillation
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5 formaldehyde plant
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Air Flow Rate 2130 Nm3/h
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10 Air Flow Rate 2,130,000 L/h
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12 Molar Air Flow Rate 95,089 mol/h
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Methanol Quantity 2459 kg/h
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19 Molar Methanol Flow Rate 76,844 mol/h
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21 Molar Air/Methanol Ratio 1.23
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23 Water Flow Rate 414 kg/h
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25 Water Purity 99 %
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Actual Water Flow 410 kg/h
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32 Actual Methanol Flow 2459 kg/h
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34 Steam/Methanol Mass Ratio 0.17
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37 3.3 Off-Gas Recycle
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39 The off-gas recycle process involves replacement of a portion of the water in the feed
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41 stream by off-gas from the absorber column [Figures 3 & 4]. In theory, this approach
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43 allows production of higher concentrations of formaldehyde as inherently dilution of the
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formaldehyde product has been mitigated. Off-gas from the absorber column normally
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46 contains a mixture of nitrogen, hydrogen, carbon dioxide, carbon monoxide, formaldehyde,
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48 methane, unreacted oxygen and methanol, in addition to lesser quantities of argon and
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50 other inert gases 30.
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31 Figure 3: Off-gas recycle process for methanol oxidation to formaldehyde
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47 (a) (b)
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50 Figure 4: Off-gas recycle formaldehyde plant (a) Absorber towers and off-gas burning facility
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52 (b) gas filter and reactor
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56 Halbritter et al. 31 demonstrated the use of a feed-stream comprising of 14.6 parts air, 6.28
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parts methanol, 1.57 parts steam and 10.05 parts off-gas, which resulted in a formaldehyde
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3 yield of 89.88 % and a product containing a formaldehyde concentration of 50.4 wt% and
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5 methanol content of 0.085 wt%. Qi and Li simulated an off-gas recycle process and
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7 determined that a further improvement in energy efficiency of 18.7 % and reduction in cold
8 utility requirements of 10.4 % was possible by modification of standard plant designs.
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12 4. General Process Parameters and Conditions
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14 4.1 Feed Materials
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4.1.1 Methanol
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17 Methanol is made using a two stage process: (1) natural gas (or coal) is steam reformed to
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19 produce a syngas mixture (CO, CO2 and H2) in the presence of a nickel based catalyst 33; (2) a
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21 copper/zinc oxide/alumina catalyst converts the syngas to methanol at ca. 250 oC and 50 to
22 34-37
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100 atm pressure . The resultant crude methanol also contains small quantities of by-
24 product hydrocarbons such as dimethyl ether, acetone and methyl formate. Consequently,
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26 a multi-stage distillation process is applied to the “crude methanol” to convert it to 99 %
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28 purity 38. Greene & Baber indicated that removal of the light end impurities was sufficient
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30 to facilitate good formaldehyde synthesis performance . Their solution was to use a
31 topping column consisting of any suitable packed tower or plate column of about four
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33 theoretical plates. Initially, the crude methanol was dosed with 5 M NaOH until pH 7-9 and
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35 then introduced to the column. The resultant liquid was withdrawn and then fed to a
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37 single-plate flash boiler to separate volatile components from the salt residue. This latter
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patent illustrated that catalyst efficiency of up to 94.4 % could be achieved using
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40 40
appropriate levels of water in the feed. Similarly, BASF also revealed that distillation to
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42 remove the lower-boiling fraction relative to methanol was sufficient to provide acceptable
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44 formaldehyde synthesis performance. Interestingly, they showed that conventional
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46 methanol purity tests such as boiling point range, permanganate solution discoloration, and
47 discoloration by sulfuric acid addition all failed when using the distilled crude methanol yet
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49 formaldehyde yield was apparently unaffected.
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53 A portion of the methanol required as the feed for formaldehyde production can also be
54 obtained from a co-located resin plant. Wolf et al. 41 advocated the use of condensate from
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56 urea formaldehyde synthesis which comprised of 0.4 to 5 % methanol and formaldehyde in
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3 aqueous solution. However, it was revealed that it was necessary to add substantial
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5 quantities of sodium hydroxide prior to distillative recovery of the methanol.
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8 Yuichi 42
recommended that methanol should be purified by a combination of Teflon
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10 cartridge filters to remove particulate matter and an ion exchange resin to remove dissolved
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12 cations such as sodium, iron, calcium and potassium.
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4.1.2 Water
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17 Water for the formaldehyde manufacturing process is often sourced from bores, local
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19 municipal supplies or surface water resources. As such there is usually a requirement to
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21 purify the water prior to introduction into the formaldehyde plant. Normally reverse
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osmosis units are employed as are ion exchange demineralization systems in combination
24 with sand filters, microfiltration and other common water purification strategies.
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28 4.1.3 Air
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30 Air is introduced into the formaldehyde plant via an air blower. Air inherently contains
31 impurities such as particulate matter, volatile organic chemicals, acidic gases, salts and
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33 various other substances dependent upon the plant location. As a minimum, air is usually
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35 passed through a dust filter and other options employed to purify the air include washing
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37 with either water or a sodium hydroxide solution 43.
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40 4.2 Evaporation of Water & Methanol
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42 Prior to entry to the reactor unit, both water and methanol must be vaporized and mixed
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44 with the incoming air stream. Practically, three common approaches are used to achieve
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46 this latter goal: absorber column, vaporizer (evaporator) and methanol reboiler with steam.
47 The overarching issue is to produce a gas mixture which is not flammable [Figure 5] and
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49 great care must be taken to ensure safety considerations are always met . These
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51 approaches are described below.
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3 Water
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5 0
100
6 10
90
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8 20
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9 30 Flammable
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11 40
60 Region at 100 oC
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20 0
0 10 20 30 40 50 60 70 80 90 100 Methanol
21 Air
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23 Figure 5: Phase diagram for methanol/air/water mixtures showing explosive region
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27 4.2.1 Absorber Column
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BASF have advocated the use of an absorber column to achieve complete saturation of air
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30 45
with methanol [Figure 6]. For example, Aicher et al. described a column which
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32 incorporated a multitude of angled bubble-cap sieve plates. When compared with a column
33
34 containing only non-inclined sieves the formaldehyde yield was increased from 86.3 to 88 %
35
36
and catalyst life extended from 70 to 100 days. The underlying reason for the enhanced
37 performance was the proposition that the column design more effectively removed
38
39 particulate matter, fine liquid droplets (mist) and catalyst poisons compared to alternate
40
41 designs.
42
43
44 4.2.2 Vaporizer Vessel
45
46 Mixtures of methanol and water are fed to an evaporator wherein the liquid is heated by
47
48 means of a steam bundle and the air is flowed through a sparger system [Figure 7]. The
49
50 concentration of methanol in the vaporizer is often calculated using an empirical
51
relationship between liquid density and methanol content. Heat is supplied by means of a
52
53 tube bundle wherein steam generated in the waste heat boiler section of the plant is used.
54
55 The liquid level is maintained such that it fills approximately 50 % of the vessel. Operating
56
57 temperatures for the evaporator depend upon the precise composition of the liquid in the
58
59
60
1
2
3 vessel and relate to vapour liquid equilibrium diagrams of the methanol-water-
4
5 formaldehyde mixture 46-48. As mentioned in Section 3.1, formaldehyde may be found in the
6
7 vaporizer unit due to passage of the feed water though the absorber column prior to
8 entering the evaporator. To prevent the passage of liquid droplets a demister pad is usually
9
10 placed at the exit of the evaporation unit.
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Figure 6: Absorber column for saturation of air with methanol
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57 Figure 7: Vaporizer configuration in a formaldehyde plant
58
59
60
1
2
3 Once the gas mixture leaves the demister pad a superheater is present to raise the
4
5 temperature to ca. 120 oC. With the evaporator design illustrated in Figure 7, several
6
7 problems can occur. For example, the development of foams in the evaporator vessel is
8 known and this phenomenon results in increased pressure and potential carryover of foam
9
10 to the silver catalyst which can cause a decrease in performance 49. One solution proposed
11
12 was the addition of “thick oil” (comprised of various long chain alcohols and ethers) to the
13
14 vaporizer section which was apparently successful in eliminating foam accumulation. The
15
presence of material deposits in evaporation units is also found during most shutdown
16
17 periods when the vessels are usually cleaned prior to plant re-start.
18
19
20
21 4.2.3 Methanol Reboiler and Steam
22
23
Off-gas recycle formaldehyde plants commonly vaporize the feed components in separate
24 streams and then combine all four components together in a mixing chamber [Figure 8].
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49 Figure 8: Separate feed streams in an off-gas recycle formaldehyde plant
50
51
52 The outlined approach has the advantage of allowing precise control of the feed mixture
53
54 composition due to each individual component being present in separate streams.
55
56
57
58
59
60
1
2
3 4.3 Feed Additives
4
5 Several studies have suggested that small concentrations of specific chemicals can be added
6
7 to the gaseous feed-stream in order to promote the formaldehyde synthesis process.
8
9
10 4.3.1 Amines
11
12 Diem et al. 50 indicated that the addition of amines such as dimethylamine, diisobutylamine
13
14 and piperidine could be added to the gaseous feed mixture at small concentrations (0.00007
15
to 0.0001 moles amine to every mole of methanol). Depending upon reaction conditions
16
17 evidence was provided that up to 1 % increase in formaldehyde yield could be achieved by
18
19 the presence of the amine. Notably, the most significant impact appeared to be a reduction
20
21 in the quantity of formic acid in the final product. A reduction in formic acid content can
22 51
23
promote storage stability of the formaldehyde solution. Zhou et al. studied the
24 interaction of dimethylamine, oxygen and formaldehyde on a silver single crystal. These
25
26 authors found that the dimethylamine readily adsorbed on silver surfaces modified by the
27
28 presence of atomic oxygen and could react with formaldehyde to make N,N-
29
30 dimethyformamide with high selectivity.
31
32
33 4.3.2 Halides
34
35 Similarly to addition of amines, improvements in the synthesis of formaldehyde have been
36
37 claimed through the introduction of halogen-containing compounds into the mixture 52. Up
38
to 500 ppm of either CH2Br2, HBr, C3F8, CH3CH2I, BF3 and CH2Cl2 were introduced by
39
40 Branecky and Harris 52 to a methanol/air stream fed to a silver catalyst of 25.4 mm depth. In
41
42 general, the addition of the halide containing compound appeared to promote methanol
43
44 conversion (0.82 to 4.31 %) and increase formaldehyde selectivity (0.67 to 2.79 %).
45
46
47 The fundamental reason for the promotional effect of iodide species in silver oxidation
48
49 catalysts has been examined by Dai et al. 53 who used in situ Raman spectroscopy to probe
50
51 the reaction of methanol and oxygen on an iodide modified silver surface. These authors
52
53 concluded that exposure of silver catalyst to methyl iodide inhibited the coverage of oxygen
54 species responsible for combustion and promoted the sorption of methanol on the silver
55
56 surface. Wang et al. 54 applied density functional theory (DFT) to understand the influence
57
58 of iodide upon oxygen sorption to a Ag (100) surface. It was discovered that both iodide
59
60
1
2
3 and atomic oxygen species competed for the same fourfold hollow sites on the silver. As a
4
5 consequence, iodide modification of the surface could minimise the coverage of surface
6
7 atomic oxygen species thought to be responsible for non-selective oxidation of methanol.
8 In addition, iodide changed the electronic properties of the silver substrate and enhanced
9
10 the binding strength of atomic oxygen adsorbed on the silver surface, which again was
11
12 proposed to increase formaldehyde selectivity. In relation to subsurface oxygen (Oγ) which
13
14 is widely reported to be the active species responsible for dehydrogenation of methanol to
15
formaldehyde, iodide was suggested to shorten the distance between the subsurface
16
17 oxygen species and the silver surface.
18
19
20 55
21 Qian et al. performed microreactor tests of methanol oxidation on polycrystalline silver
22
23
catalyst wherein 100 ppm of methyl iodide was introduced to the feed-stream. Introduction
24 of CH3I was found to limit methanol conversion but enhance formaldehyde selectivity. The
25
26 overall effect of the halogen addition was a decrease in formaldehyde yield but a positive
27
28 aspect was the suppression of formic acid production.
29
30
31 4.3.4 Nitrous Oxide
32
33 56
Diercks et al. considered the possibility of adding nitrous oxide to the feed-stream in a
34
35 formaldehyde synthesis facility. It was suggested that from 1 to 50 % N2O could be added
36
37 and an example was provided which indicated the yield of formaldehyde was 93.3 % with
38
methanol conversion of 99.1 % and formaldehyde selectivity of 94.1 %. In comparison,
39
40 without the presence of nitrous oxide the formaldehyde yield was 90.2 % with a methanol
41
42 conversion of 97.9 % and formaldehyde selectivity of 92.2 %. The latter results appeared
43
44 impressive but the obvious drawback relates to the substantial increase in cost of nitrous
45
46 oxide compared to air which is essentially free apart from the power to operate the blower.
47
48
49 4.4 Gas Mixing & Filtration
50
51 Yu et al. outlined the need for a quaternary mixer which blends the four components of an
52 57
53 off-gas recycle plant . There also exists the possibility of contamination of the silver
54 catalyst from foreign material in the feed gas stream and as such filters are often present
55
56 prior to the methanol oxidation reactor. BASF patented a baffle system for the removal of
57
58 impurities such as liquid droplets and particulate matter present in a vaporized crude
59
60
1
2
58
3 methanol stream . In practice, the baffle arrangement was found to be effective in that
4
5 both formaldehyde yield (81.6 to 82.5 %) and catalyst life (25 to 80 days) was improved.
6
7 Solid deposits collected from the baffle plates were found to comprise of a mixture of
8 sodium formate, sodium carbonate, and compounds of iron, calcium, magnesium, sulfur and
9
10 silicon.
11
12
13
14 4.5 Formaldehyde Reactor Designs
15
Generically, there are two basic formaldehyde reactor designs which can be classed as
16
17 “side” or “top” entry. There is no consensus as to which design has any advantages albeit it
18
19 should be pointed out that a major consideration is to ensure even flow distribution over
20
21 the catalyst bed surface. As such the feed mixture is not usually directed to the catalyst bed
22
23
without a means to distribute the gas stream evenly over the silver surface. For example, Ye
24 et al. 59
illustrated the use of a side entry reactor wherein the influent gas was forced to
25
26 traverse around a conical structure with an entry port at the uppermost apex. Regardless of
27
28 which location the feed enters the reactor vessel the catalyst bed is circular and ranges from
29
30 0.9 to 3 m in diameter [Figure 9].
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47 (a) Silver catalyst bed prior to use (b) Operating silver catalyst bed
48
49
50
51 Figure 9: Images of silver catalyst bed as (a) prepared and (b) during operation
52
53
54 Immediately above the catalyst bed may be a baffle system to aid the aforementioned gas
55
56 distribution, thermocouples and pressure gauges and a means to initiate the catalytic
57
58 reaction during plant start-up (see section 4.12). The metallurgy of the reactor vessel has
59
60
1
2
60
3 been raised as a pertinent issue in optimizing formaldehyde synthesis. Dubois et al.
4
5 advised that the reactor material chosen should be able to form a protective oxide layer
6
7 during reaction conditions.
8
9
10 Within the reactor unit is placed silver catalyst which is usually applied in several layers with
11
12 specified mesh sizes (see Section 5.4). In turn the silver catalyst is supported on a series of
13
14 meshes which can either be located on top of the underlying boiler tube sheet or on a base
15
plate with holes cut out to allow gas flow to the gas cooling system (see Section 4.6) [Figure
16
17 10].
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44 Figure 10: Representation of silver catalyst bed configuration
45
46
47 It is important to lay the silver catalyst in the reactor in the correct manner. It is logical that
48
49 the silver bed depth should be kept as uniform as possible. As such Chen 61 described the
50
51 use of a specially constructed tool which was designed to press the silver catalyst bed in
52
such a manner as to make the bed height even.
53
54
55
56 The majority of formaldehyde plants simply use a one stage reactor process to convert
57 62
58 methanol, however McMillan et al. advocated the use of two reactors in series which
59
60
1
2
3 both contained silver catalyst. The first stage was operated at comparatively low
4
5 temperature to ensure that the methanol was not completely reacted and ideally had
6
7 formaldehyde to methanol molar ratio in the reactor effluent of 1.7:1 to 2.5:1. Air was
8 typically introduced between the two stages and the second stage reactor was operated at a
9
10 higher temperature than the first stage. A key difference in operation of the reactor stages
11
12 was the use of a gas hourly space velocity in the range 90,000 to 180,000 h-1 in stage 1 and a
13
14 corresponding range of 130,000 to 270,000 h-1 in stage 2.
15
16
17 4.6 Support Gauze and Base Plate
18
19 4.6.1 Support Gauze
20
21 Gauze is typically placed either on top of a base plate or directly on the top of the waste
22
23
heat boiler tube sheet [Figure 10 & 11] 63, 64. The selection of gauze material for which the
24 silver catalyst is arranged is important in terms of maximising performance. BASF have
25
26 proposed that the use of a stainless steel support gauze is more beneficial, in that not only
27
28 does it minimise sintering of the silver catalyst but also if 1.5-2.5 % molybdenum is
29 65
30 incorporated in the steel, carbon deposition on the catalyst surface is also reduced .
31 Mitsubishi Gas Chemicals also indicated that a copper carrier containing 0.1 to 0.6 % arsenic
32
33 inhibits catalyst deterioration 66.
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53 Figure 11: Images of fresh (left) and used (right) copper support gauze
54
55
56
57
58
59
60
1
2
3 Another support plate consists of quartz sand, wherein the pressure drop is preferably 1.5
4
5 to 5 times that of the catalyst bed 67. Claimed benefits include more uniform gas flow and
6
7 suppression of side reactions.
8
9
10 The sizes and numbers of support gauzes to employ is not standardized throughout the
11
12 formaldehyde industry. The basic premise is to prevent the finest silver grains passing
13
14 through the gauze structure; hence it is common to encounter mesh of a similar spacing as
15
the smallest silver catalyst mesh fraction employed. In many plants, more than one gauze is
16
17 applied to support the silver but no scientific rationale has been published to elucidate
18
19 which is the optimal approach.
20
21
22
23
4.6.2 Support Plate
24 The support plate (or base plate) may perform several functions, such as supporting the
25
26 catalyst and promoting uniform gas flow without adding too much pressure drop or reacting
27
28 with the catalyst. Copper support plates have the advantage of a thermal expansion
29
30 coefficient similar to that of the silver catalyst bed, so that thermal stresses don’t cause
31 cracks that would lead to bypassing. However, copper plates tend to react with silver to
32
33 form alloys, or cause sintering and are also prone to becoming brittle in the presence of
34
35 hydrogen formed in the reaction 65.
36
37
38
4.6.3 Configuration of Catalyst in Relation to Waste Heat Boiler Tube Sheet
39
40 The residence period which the product formaldehyde spends in the reaction “hot zone”, is
41
42 very important with regards to the obtained formaldehyde yield (due to the gas phase
43
44 decomposition of formaldehyde to carbon monoxide and hydrogen). BASF indicated that if
45
46 the distance from the baseplate to the tube sheet of the downstream heat exchanger was 4
47 cm, then the concentration of carbon monoxide was 0.6 % 68
. Alternatively, the catalyst
48
49 could simply be directly placed on top of gauze supports which are laid on top to the tube
50
51 sheet. The benefit of placement of flow directing supports on top of the tube sheet of a
52
53 tubular heat exchanger system has been described 69. The outlined concept design in Figure
54 12 was targeted at reducing the residence time of the product gases at high temperature
55
56 conditions, thus avoiding side reactions such as the gaseous decomposition of
57
58 formaldehyde.
59
60
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22 Figure 12: Illustration of the use of flow directing supports underneath silver catalyst beds
23
24
25
26 4.7 Waste Heat Boiler
27
28 It is essential to cool the product formaldehyde mixture as rapidly as possible to avoid
29 70
decomposition of gaseous formaldehyde to produce carbon monoxide and hydrogen .
30
31 The reaction product leaves the catalyst layer at ~600 to 700 °C and is required to be cooled
32
33 to less than 350°C as rapidly as possible to avoid formation of by-products 71. Vitvitskii and
34 72
35 Averbukh determined that the decomposition of formaldehyde was not only dependent
36
upon temperature but also residence time, with reaction times of 0.01 s or less
37
38 71
recommended. Maux proposed that reinjection of a portion of the off-gas emitted from
39
40 the absorber columns should be conducted immediately underneath the silver catalyst bed.
41
42 The objective was to enhance the rate of cooling of the product gases and ultimately
43
44 increase process yield. A serpentine arrangement of cooling coils located close the exit of
45 the catalyst bed has also been suggested as being an efficient means of removing heat
46
47 effectively in order to minimise side reactions 73. Linzer et al. 74 described a novel design of
48
49 waste heat boiler which could reduce the exit gas temperature to < 300 oC in 60 ms. A
50
51 horizontal tube heat exchanger was employed and the presence of a spray unit also allowed
52
for the gas temperature to be further reduced to 80 oC. The use of ceramic inserts in the
53
54 boiler tubes is also claimed to aid the rate of heat transfer 62.
55
56
57
58
59
60
1
2
3 4.8 Absorber Design and Operation
4
5 The object of the absorber stage is to condense formaldehyde, unreacted methanol, and
6
7 water to produce concentrated solutions ranging from 37 to 55 wt% formaldehyde. A
8 typical design is shown in Figure 13 for the absorber unit. In practice, 3 or 4 recirculation
9
10 stages are employed wherein heat is removed from the solution by normally plate heat
11
12 exchangers 75.
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37 Figure 13: Schematic representation of a formaldehyde absorber unit
38
39
40
41 The inlet temperature of the gaseous mixture which comprises mainly of nitrogen,
42
43 formaldehyde, hydrogen, unreacted methanol and water vapour is typically in the range of
44
45 120 to 160 oC depending upon formaldehyde plant configuration 29
. Winkelman et al. 76
46 presented a computational study which modelled commercial absorbers used in the

47
48 production of formaldehyde. The model which was able to accurately simulate industrial
49
50 data from operating formaldehyde plants and the main factors identified which promoted
51
52 the absorption process were: relatively large volumes of make-up water; recycling of liquid
53
in the column stages at high ratios; and reduced temperatures for the recycled liquid.
54
55
56
57
58
59
60
1
2
3 Yoshikawa et al. 29 described a means to produce high strength formaldehyde solutions (up
4
5 to 60 wt%) by adding a volume of make-up water equal to the amount of steam required in
6
7 the feedstream and then taking a side cut from an upper section of the absorber column
8 (often a tray type structure such as a bubble-cap) which was then added to the feed
9
10 mixture. The fundamental idea was to enhance the recovery of methanol while not
11
12 significantly diluting the formaldehyde product, which was in harmony with the calculations
13
14 of Winkelman et al. 76 which indicated that increasing the make-up water volume enhanced
15
the column efficiency. The resultant process water contained small percentage amounts of
16
17 methanol and formaldehyde.
18
19
20
21 4.9 Off-Gas Composition
22
23
Ideally, the off-gas which exits the absorber column should comprise of carbon dioxide,
24 carbon monoxide, nitrogen, hydrogen and perhaps some oxygen. Normally, some methanol
25
71
26 and formaldehyde may also be present due to absorber inefficiencies . Methylal
27
28 (dimethoxymethane) and methyl formate are also often present in amounts less than 1 v/v
29
30 %. BASF reported that the percentage of gases in the off-gas stream from an almost
31 complete methanol conversion formaldehyde plant was 3.5 % for carbon dioxide, 0.11 to
32
33 0.18 % for carbon monoxide, 17.3 to 18.2 % for hydrogen and 0.3 to 0.6 % oxygen with the
34
35 balance being nitrogen 77.
36
37
38
4.10 Distillation
39
40 Formaldehyde plants equipped with distillation units typically aim to produce consistent
41
42 product compositions such as 50/1 or 54/0.5 (wt % formaldehyde/wt % methanol). To
43
44 achieve this standard of product requires control of the solution composition made in the
45
46 initial conversion step over the catalyst bed. In relation to the catalytic reaction it is also
47 desirable to increase the formaldehyde yield and as such optimization of the formaldehyde
48
49 plant requires an understanding of the relationship between the absorber bottoms
50
51 composition and the expected distillation product composition in order to determine the
52 78
53 boundaries within which the formaldehyde plant can be operated. Ott et al. not only
54 simulated the distillation of formaldehyde solutions but also compared the postulated
55
56 performance with laboratory data. An important aspect of the latter study was the
57
58 inclusion of the complex solution behaviour of formaldehyde wherein it forms a range of
59
60
1
2
3 species such as methylene glycol, poly(oxymethylene) glycols, hemiformal and
4
5 poly(oxymethylene) hemiformals. Although the correlations were in some instances in
6
7 accord with experimental data it was concluded that equilibrium stage models were not
8 optimal and that the impact of reaction kinetics should also be considered. Terelak et al. 79
9
10 scaled up distillation tests with formaldehyde solutions to pilot plant level and discovered
11
12 that their physicochemical fluid property model simulated the pilot plant data to a high
13
14 degree of accuracy. Žilnik et al. 80 used ASPEN software to model the distillation process for
15
formaldehyde solutions and found that the predictions were not accurate due to the
16
17 influence of chemical kinetics and mass transfer.
18
19
20
21 4.11 Off Gas Burning
22 81
23
Baumann et al. detailed the generation of electricity from the off-gas produced during
24 formaldehyde synthesis which made use of the inherent fuel value of the hydrogen and
25
26 methanol present. Combustion of the off gas also had the benefits of reducing
27
28 environmental emissions, potentially attracting carbon capture credits due to the reduced
29
30 demand for fossil fuel based energy, in addition to supplying a portion of the formaldehyde
31 plant electricity needs. The question arises to the economic viability of the latter approach
32
33 as it would require significant capital investment, and is also dependent on the percentage
34
35 of hydrogen present in the off-gas which can vary significantly between different
36
37 formaldehyde units.
38
39
40 4.12 Reaction Light-Off
41
42 It is desirable for silver catalysts to produce formaldehyde solutions within specification as
43
44 soon as possible after being introduced to the industrial reactor in order to minimise
45
46 product which does not meet customer requirements. In the best instance, suitable product
47 is made within several hours but examples of 24 hours or more are not uncommon.
48
49
50
51 4.12.1 Hot Nitrogen Gas
52
53 Catalyst activation involving the use of hot nitrogen gas which is flowed over the catalyst
54 bed has been described. The nitrogen gas is externally heated by any type of suitable heat
55
56 exchanger and the aim is to preheat the catalyst bed to a temperature between 280 and
57
58 350 oC before introduction of the methanol/steam/air mixture 31
. This latter method has
59
60
1
2
3 the advantage of being relatively clean as minimal possibility of contamination of the
4
5 catalyst with carbon, copper oxide or rust during the catalyst activation process can occur.
6
7 In addition the entire volume of the reactor head is heated to high temperature, therefore
8 there is practically zero chance of methanol or water condensation during start-up which
9
10 can impact catalyst performance. No overheating of the parts of the catalyst surface
11
12 happens in contrast to methods involving the use of flames (as outlined below).
13
14
15
4.12.2 Heating with a Flame
16
17 Some formaldehyde plants have the methanol oxidation reaction initiated by exposing the
18
19 silver catalyst surface to a flame [Figure 14]. Compressed air is typically introduced to an
20
21 ignition system located immediately above the catalyst bed which in turn makes the
22
23
air/methanol ratio enter a region where combustion occurs. This method has not only the
24 disadvantages of uneven heat distribution across the bed surface, potential health and
25
26 safety issues as a flame is present but also it is typically not a fast process in terms of
27
28 achieving light-off in the reactor vessel.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
(a) (b)
46
47
48
49
Figure 14: Examples of start-up procedures involving (a) flame (b) electrical means to
50
51 generate heat
52
53
54
55
56
57
58
59
60
1
2
3 4.12.3 Electrical Heating
4
5 Electrical heating is commonly used in Chinese designed formaldehyde plants and is a rapid
6
7 means of heating the catalyst with typical light off of the bed occurring within 2 minutes
8 [Figure 14]. An electrical coil is placed upon an insulating support framework as close to the
9
10 catalyst surface as possible to aid rapid light-off.
11
12
13
14 4.12.4 Acceleration of Bed Light-Off
15
In situations where difficulty in achieving reaction “light-off” is encountered, doping of the
16
17 catalyst bed with a fine layer of silver oxide (Ag2O) has been reported to exhibit beneficial
18
82
19 effects . Sprinkling of very fine silver powder (0.1-1 micron) on top of the silver bed,
20
21 permitted the reaction to start at 205-230 oC 83
. Millar et al. 84
employed both
22
23
Environmental Scanning Electron Microscopy (ESEM) and Raman microscopy to characterise
24 the interaction of methanol/air mixtures with silver (I) oxide. The silver oxide was
25
26 discovered to decompose to form very finely divided silver grains which were noted to be
27
28 exceptionally active due to a combination of the crystal faces exposed and the number of
29
30 intergrain boundaries created. Alternate approaches to alleviating the problem of slow
31 reaction light-off include construction of multilayered beds of silver catalyst with different
32
33 particle sizes 24. Using this latter invention it was claimed that light-off can be achieved at
34
35 temperatures of 553-573 K. In general, smaller silver grains were found to exhibit greater
36 85
37 activity , however due to sintering and plugging effects a bed cannot be entirely
38
constructed of these relatively small particles.
39
40
41
42 4.13 Process Conditions
43
44 4.13.1 Space Velocity & Methanol Loading
45
46 Space velocity is considered an important factor in improving the yield of formaldehyde.
47 The highest yields are obtained at relatively high space velocities, which is probably due to
48
49 the shortened contact time inhibiting side reactions. Gas Hourly Space Velocity (GHSV) is
50
51 defined as the number of times bed volume is swept out with reactant gas per hour (h-1).
52
53 Consequently, the residence time is defined as time the reactant/product stays within the
54 catalyst bed [Equation 10].
55
56
57
58
59
60
1
2
-
3 Equation 10: S>5 = × 3600
4 TUQV
5
6
7 The useful operating region for space velocity is typically 100,000 to 250,000 h-1. The
8
9 precise space velocity which provides optimum process benefits depends upon the plant
10
11 configuration. When the space velocity is less than the minimum recommended value then
12
13 problems can occur due to side reactions which typically produce carbon deposits.
14 Formaldehyde is not stable under normal reaction conditions and will decompose to form
15
16 carbon monoxide in the gas phase. Carbon monoxide can undergo further changes via the
17
18 Boudouart Reaction to make carbon and carbon dioxide.
19
20
21
Methanol loading on the catalyst bed is another useful measure when operating the
22
23 formaldehyde plant. A typical value for catalyst loading is 2.0 metric tons of methanol per
24
25 hour per m2 of catalyst bed area which equates to 25 kg/min/m2 86. Table 6 provides an
26
27 illustration of the variation of methanol loads encountered in industrial formaldehyde
28
29
plants.
30
31
32 Table 6: Examples of process conditions in a range of formaldehyde plants
33
34 MeOH flow Area of Bed Surface Methanol Load
35
36 (kg/min) (m2) (kg/min/m2)
37
Plant 1 15.625 0.697 22.4
38
39 Plant 2 23.6 0.697 34
40
41 Plant 3 36.11 1.33 27.2
42
43 Plant 4 33.33 1.21 27.5
44
45 Plant 5 64.17 2.27 28
46
47
Plant 6 43.05 1.17 36.8
48 Plant 7 31.25 1.13 27.7
49
50
51
52 4.13.2 Feed Ratios
53
54 Szustakowski 85 examined the importance of oxygen/methanol molar ratio during methanol
55
oxidation on a silver catalyst. He found that both methanol conversion and formaldehyde
56
57 yield were promoted when the O2/CH3OH ratio was increased from 0.25 to 0.40.
58
59
60
1
2
3 Waterhouse et al. 87 found that a molar ratio of methanol to oxygen of 2.25 was optimal in
4
5 terms of degree of methanol conversion and formaldehyde selectivity of polycrystalline
6
7 silver catalyst. These latter authors ascribed the relationship between feed stoichiometry
8 and catalyst performance in terms of the presence of various oxygen species on the silver
9
10 catalyst. For example, at low CH3OH/O2 ratios the dominance of the non-selective Oα
11
12 species was postulated. Lefferts et al. 88 noted that increasing oxygen concentration in the
13
14 feed generally enhanced formaldehyde production while also promoting carbon monoxide
15
and carbon dioxide formation. Use of higher reaction temperatures appeared to diminish
16
17 the amount of carbon dioxide formed.
18
19
20
21 It has been recognised for some time that addition of water to the reactor feed improves
22
23
conversion and yield. The oxygen concentration in the feed can be raised without causing
24 overheating, because some of the reaction heat is absorbed by water. The higher oxygen
25
26 concentration uses a larger proportion of hydrogen formed in the endothermic
27
28 formaldehyde synthesis reaction, and thus favourably shifts the equilibrium. The addition of
29
30 water can also activate the catalyst and extend the catalyst life. Lightly bound catalyst
31 poisons are often stripped off at high water addition rate. The optimal yield usually occurs
32
33 at a 60/40-weight ratio of methanol/water 86. Water fed to the reactor can be supplied as
34
35 moisture in the air, as water in the methanol feed, or as a separate stream. Water to be
36
37 added to the reactor feed can also be supplied be recycling dilute formaldehyde solution
38
from the top section of the absorber.
39
40
41
42 4.13.3 Dehydrogenation/Oxidation ratio
43
44 An insight to the formaldehyde plant operating conditions can be determined by calculation
45
46 of the dehydrogenation/oxidation ratio which can be estimated as shown in Equation 11.
47 Equation 11:
48
49 6ℎ Y5 5/ 7 5
50 = > [ =ℎ5 6ℎ Y5 ℎ
51 =
52 = > [ =ℎ5 7> ℎ
53
54 Nagy and Mestl 89 proposed that surface embedded atomic oxygen (Oγ) was responsible for
55
the direct dehydrogenation of methanol reaction to produce formaldehyde and hydrogen,
56
57 and that surface adsorbed atomic oxygen (Oα) was responsible for the non-selective
58
59
60
1
2
3 oxidation of formaldehyde. Examination of the hydrogen content of the product gas
4
5 revealed that at elevated temperatures the direct dehydrogenation reaction dominates and
6
7 this result was in accord with the discovery that surface atomic oxygen species were largely
8 desorbed by this point.
9
10
11
12 4.13.4 Effect of Reaction Temperature
13
14 As the reaction temperature is raised from 200-700 °C the conversion of methanol increases
15 88
along with the production of formaldehyde . An increasing rate of the side reaction to
16
17 form carbon monoxide is also observed due to gaseous decomposition of formaldehyde.
18
19 Carbon dioxide is also formed, with relatively more at temperatures less than 350 oC
20
21 compared to when temperatures typical of industrial formaldehyde synthesis are employed
22 88
23
. The maximum yield of formaldehyde lies at the temperature at which the sum of the
24 losses due to unreacted methanol and from the formation of side products is at minimum.
25
26 Temperature is normally controlled by adjusting the amount of air that is supplied.
27
28
29
30 5. Polycrystalline Silver Catalyst
31 5.1 Pure Silver Catalyst
32
33 Polycrystalline silver catalyst is typically made by metal refiners. Examination of various
34
35 commercially available silver catalysts has revealed that they are not the same in terms of
36
37 physical properties [Figure 15]. This latter observation is at least partially due to the fact
38
that formaldehyde producers usually only request that the silver is at least 99.99 % pure and
39
40 of specified mesh fractions, hence there is often insufficient quality control in terms of silver
41
42 catalyst synthesis as desirable properties for formaldehyde synthesis are not explicitly part
43
44 of the customer specification.
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
2
3
4
5
6
7
8
9
10
11
12
13
14 High Bulk Density Medium Density
15
16 Figure 15: SEM images of two types of polycrystalline silver catalyst
17
18
19
20 The basic properties of importance when considering metallic catalysts include: (1) purity;
21
22 (2) surface area; (3) packing density; (4) porosity; (5) shape; (6) mechanical strength and (7)
23
thermal conductivity. In China, two types of silver catalyst are used, the first is a high
24
25 density product termed “crystal silver” which is similar to the high bulk density material
26
27 illustrated in Figure 14. The second material is termed “foam silver” and this has an almost
28
29 wire like appearance and is characterized by a low bulk density (ca. 1 g/mL). Although the
30
31
“foam silver” has the highest surface area its performance is hindered by the exceptionally
32 low mechanical stability which leads to limited lifetimes in the order of only a few weeks.
33
34
35
36 Silver gauze was one of the original catalysts used for formaldehyde synthesis, but it is rarely
37 90
38 if ever used today. Nevertheless, recently Baltes et al. described a silver gauze catalyst
39 which exhibited improved formaldehyde yields which correlated with decreasing wire
40
41 diameter. Importantly the formaldehyde selectivity was said to increase from 87 to 90 %
42
43 when changing from a polycrystalline silver catalyst to a wire mesh silver material.
44
45 Methanol conversion in each instance was 99 %. It was noted however that no catalyst
46
lifetime information was provided and as such it is not known if the mechanical stability of
47
48 the silver mesh was sufficient for industrial implementation.
49
50
51
52 5.2 Modified Silver Catalyst
53 Several efforts to promote the catalytic performance of silver catalyst for formaldehyde
54
55 91
synthesis have been described. Claus et al. proposed that silver catalyst could be doped
56
57 with Pd, Pt, Rh, Ru and Ir in addition to oxides such as alumina which were stable at
58
59
60
1
2
3 elevated reaction temperatures of up to 720 oC. An example of a 2 wt% doped silver
4
5 catalyst was presented wherein the formaldehyde yield was claimed to be 90.4 %. Esumi 92
6
7 suggested that silver alloyed with either platinum, palladium or rhodium may be suitable
8 methanol oxidation catalysts. Silver-lead catalyst has also been revealed by Gerberich 93
9
10 and under conditions where incomplete methanol conversion was achieved the
11
12 formaldehyde selectivity was reported as 91.8 %. Silver catalysts modified by the addition
13 94
14 of barium, strontium, calcium, and/or indium may be beneficial for oxidation reactions .
15
BASF promoted the idea of doping the surface of silver catalyst with phosphate species 95-97.
16
17 Diercks et al. 96 described the application of Na2P2O7 species on silver catalyst and proposed
18
19 that the activation time was shortened during catalyst light-off conditions.
20
21 Supported catalysts have also been proposed with silver supported on pumice stone widely
22 98 99
23
reported to have been used in the Russian formaldehyde industry . Chen et al.
24 proposed that silver coated on ceramic microspheres was an effective catalyst for methanol
25
26 oxidation to formaldehyde with methanol conversion stated to be in the range 90 to 98 %.
27 100
28 Diem et al. similarly indicated that silver deposited on porcelain spheres could be
29 101
30 employed in formaldehyde synthesis reactions. In another patent, Diem et al.
31 demonstrated that silver particles on an alumina support could also be considered for
32
33 methanol oxidation purposes.
34
35
36
37 5.3 Electrochemical Synthesis of Polycrystalline Silver
38
Two electrochemical cell configurations are employed to manufacture polycrystalline silver
39
40 catalyst [Figure 16]. A Balbach-Thum cell consists of horizontal cast silver anodes, which are
41
42 located in a top basket lined with cloth that is designed to collect anode slime and thus
43
44 prevent contamination of produced silver crystals. In the cell bottom is usually either a
45
46 carbon or more routinely a stainless steel cathode plate onto which the silver dendrites are
47 deposited. The electrolyte is typically prepared by dissolution of silver in concentrated nitric
48
49 acid and ultimately may contain from 10 to 200 g/L of silver following dilution with RO
50
51 water. Other metal ions are present in the electrolyte as a result of migration from the
52
53 anode material and species may include copper, lead, bismuth, and cadmium. Removal of
54 the product silver crystals is achieved by manual scraping of the cathode plate.
55
56
57
58
59
60
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 Balbach-Thum Cell
16
17 Moebius Cell
18
19
20 Figure 16: Balbach-Thum and Moebius cells for electrocrystallization
21
22 Moebius first patented a process in 1884 using silver nitrate as a conducting media for the
23
24 electrolytic production of silver crystals. In the Moebius system, the anodes are cast, drilled
25
and bolted to hanger bars before being immersed in the electrolyte. A woven cloth bag of
26
27 controlled porosity is carefully placed about the anodes to catch any anode slime produced.
28
29 Normally, mechanically operated scrapers move back and forth over the cathode surface
30
31 and thus dislodge silver crystals which then fall to the bottom of the cell and can
32
33
subsequently be periodically removed.
34
35
36 In general, polycrystalline silver can be obtained by operation of an electrochemical cell, for
37
38 example the conventional Moebius or Balbach-Thum cells [Figure 16], using a silver nitrate
39
40 electrolyte in the pH range 1-4 containing between 5 and 100 g/L dissolved silver, a cell
41 temperature of 10-80 oC, a current density between 100 and 3000 A/m2 and a cell voltage
42
43 102
between 0.2 and 9 volts . In particular, preparation methods specifically related to
44
45 polycrystalline silver catalysts include the continuous electrolytic refining of silver in an
46
47 aqueous solution of silver nitrate and nitric acid at 24 oC, 3.1 volts and a current density of
48
1.2 amp/dm2 103
wherein silver grains of 0.2 to 2.5 mm in size are stripped from a slowly
49
50 rotating polypropylene anode. Also known is the addition of organic inhibitors to the
51
52 electrochemical cell to modify the structure of the silver crystals deposited. For example,
53
54 the addition of thiourea at the solubility limit produces crystals of the unorientated
55
56
dispersion type 104.
57
58
59
60
1
2
3 5.4 Silver Catalyst Bed Design
4
5 Silver catalyst beds are typically composed of a range of mesh fractions with the general
6
7 rule being that the largest granules are placed on the bottom of the bed, medium grains in
8 the middle section and fine silver on the top of the bed. Bed depths range from 1.5 to 3 cm
9
10 for the majority of catalyst beds in operation today. It is claimed that greater yields can be
11
70
12 achieved through use of several layers of catalyst, characterised by differing grain size .
13
14 For example, a double layer catalyst comprising both coarse and fine grains has been
15 105 24
recommended . Aicher et al. explored the concept of grain size distribution and bed
16
17 layer thickness and suggested three or more layers should be employed and specified an
18
19 overall total layer thickness of 15 to 25 mm. Laying of silver grains only at the outer edge of
20
21 the silver bed has also been described, presumably to minimize the possibility of the a
22
23
portion of the feed bypassing the catalyst due to inefficient sealing against the reactor wall
24 24
. Szustakowski 85 determined that smaller silver catalyst particles enhanced the degree of
25
26 methanol conversion and formaldehyde yield, an observation which may relate to the
27
28 increased silver surface area available for reaction to occur. However, it has also been
29
30 shown that beds with predominantly large crystals (80 to 90 % from 0.75 to 3 mm crystals)
31 relative to beds containing smaller silver granules (0.2 to 1 mm) gave a significantly higher
32
33 yield (90.8 % compared to 86.8 %) 77.
34
35
36
37 Dual bed designs incorporating two different catalysts have also been claimed to be
38 106
advantageous. Anita suggested that placing a metal oxide catalyst (iron molybdenum
39
40 107
oxide) on top of a silver catalyst can promote formaldehyde synthesis. Zhang et al.
41
42 proposed that the upper layer of the bed should be silver catalyst and that the lower portion
43
44 should be comprised of copper granules. The preferred ratio of copper to silver ranged
45 108
46 from 5:1 to 1:1. Wachs and Wang also suggested a similar arrangement wherein the
47 upper layer was silver and the lower layer was copper.
48
49
50
51 6. Mechanism for Formaldehyde Synthesis
52
53 It is beyond the scope of this article to review the fundamental catalytic science studies in
54 fine detail, however, a brief summation of the main features will be presented here.
55
56
57
58
59
60
1
2
3 6.1 Oxygen Chemistry
4
5 The oxygen chemistry with silver catalysts is critical in terms of the industrial partial
6 109
7 oxidation of methanol to form formaldehyde. Rocha et al. used in situ XPS to examine
8 the interaction of oxygen with either silver foil, silver powder or single crystals. Five distinct
9
10 oxygen species were detected and denoted Oα1, Oα2, Oα3, Oβ and Oϒ: Oα1 is ascribed to the
11
12 formation of oxygen induced reconstruction of crystal faces on silver; Oα2 is weaker in oxidic
13
14 character than Oα1 and is proposed to be an oxide located at steps and edges on the silver
15
surface; Oα3 is an “electrophilic oxygen” as described by Buhktyiarov and co-workers; Oβ is
16
17 assigned to oxygen atoms located in the bulk silver structure; Oϒ is stable at high
18
19 temperatures similar to those encountered during industrial methanol oxidation processes,
20 110
21 and is assumed to be the active site for formaldehyde synthesis . A range of surface
22
23
science investigations have been completed using various silver single crystals to determine
24 how oxygen interacts under different conditions. Ertl and co-workers [116, 117]
25
26 demonstrated that the dominant oxygen species present at industrial conditions were those
27
28 located in subsurface locations. Incorporation of oxygen species in the silver catalyst
29
30 promoted the formation of a distinct terrace and facets along with a series of small pits in
31 the surface 111. Scanning Tunnelling Microscopy (STM) images revealed that the Oϒ species
32
33 was located in the uppermost silver surface layer and this was due to the similar radius of
34
112
35 atomic oxygen and metallic silver . Raman spectroscopy has also been used to identify
36 84, 113, 114
37 the molecular and atomic oxygen species present on silver catalyst . The surface
38
embedded Oϒ species was characterized by a vibration at ca. 810 cm-1 and dissolved atomic
39
40 oxygen by a band at ca. 610 to 640 cm-1 115. Temperature Programmed Desorption (TPD) of
41
42 oxygen species present on polycrystalline silver as a function of various heat treatments has
43
44 shown that Oϒ was stable until at least 600 oC, whereas dissolved atomic oxygen (Oβ)
45
46 desorbed at ca. 380 oC 116.
47
48
49 6.2 Methanol Oxidation
50
51 Contact of only gaseous methanol with silver catalyst does not result in discernible interaction
52
53 with the surface, but the presence of adsorbed atomic oxygen was demonstrated by Wachs
54 and Madix 117
to promote chemisorption and subsequent reaction to create methoxy,
55
56 formaldehyde and formate species. Isotopic labelling revealed that the initial step was the
57
58 interaction of methanol with atomically adsorbed oxygen to produce a methoxy species.
59
60
1
2
3 Subsequent loss of hydrogen produced formaldehyde and also potentially formate species
4
5 which were thought to be an intermediate in the combustion process to make carbon dioxide
6
7 and water. The basic steps in the catalytic reaction are shown below which agree with the
8 work of Wachs & Madix 117.
9
10
11
12 The Partial Oxidation of Methanol to Formaldehyde
13
14 Equation 12: (Y) + () → () + ()
15
Equation 13: (Y) + () → () + ()
16
17 Equation 14: () → (Y)
18
19 Equation 15: () → () + ()
20
21 Equation 16: () → (Y)
22
23
24
25
26 Carbon Dioxide Production
27
28 Equation 17: () + () → () + ()
29
30 Equation 18: () → (Y) + ()
31 Equation 19: 2 () + () → (Y)
32
33
34
35 Methyl Formate
36
37 Equation 20: () + () → ()
() → () + ()
38
Equation 21:
39
40 Equation 22: H () → (Y )
41
42
43
44 Formic acid is normally produced at ppm levels in the silver catalyst process [Equation 22]
45
46 and excessive amounts can cause problems relating to storage of product formaldehyde.
47
48
49 Equation 23: + →
50
51
52
53 Other undesirable reactions, which must be avoided by proper control of temperature and
54
other factors if high yield are to be obtained, include the previously mentioned thermal
55
56 decomposition of formaldehyde to form carbon monoxide and hydrogen. The microkinetic
57
118, 119
58 modelling of Andreasen and co-workers supported the findings of Wachs and Madix
59
60
1
2
117
3 . Practically, the operating temperatures for methanol oxidation are commonly in the range
4
5 550 to 700 oC and thus the coverage of atomically adsorbed oxygen under these conditions has
6
7 been suggested to be relatively small 89. Hence, it has been argued that embedded atomic
8 oxygen (Oϒ) is the active species for direct dehydrogenation of methanol to formaldehyde 87, 89.
9
10 Sun et al. 120 applied density functional theory and found that the OH bond formed by reaction
11
12 of embedded atomic oxygen (Oϒ) with methanol was weaker than the corresponding OH bond
13
14 created by interaction of methanol with surface atomic oxygen. As a result, the propensity to
15
form hydrogen was enhanced and thus promoted the dehydrogenation pathway for
16
17 121
formaldehyde synthesis. Temporal-Analysis-of-Products research by van Veen et al.
18
19 regarding methanol oxidation on polycrystalline silver also supported the idea that embedded
20
21 atomic oxygen (Oϒ) was indeed highly selective to formaldehyde and hydrogen, whereas
22
23
surface atomic oxygen was able to oxidise methanol to form carbon dioxide and water.
24 Schubert et al. 112, 122 reported that the reaction with surface oxygen was of limited selectivity,
25
26 a point also emphasised by Lefferts et al. 123 who indicated that weakly bound oxygen was the
27
28 cause of methanol combustion. As such the following reactions may apply [Equations 23 to
29
30 27].
31
32
33 Equation 24: (>) + (>]4) → (>) + (>]4)
34
35 Equation 25: (>) → (>) + (>)
36
37 Equation 26: (>]4 ) + (>]4) → (>]4) + (>]4)
38
39 Equation 27: (>) + (>]4) → (>]4)
40
41 Equation 28: (>]4) → (Y ) + "_5 ℎ "
42
43
44
45 However, Andreasen et al. 118 argued that their microkinetic model for formaldehyde synthesis
46
47 did not require the assumption of more than one active oxygen species. Instead they indicated
48
49 that selectivity was related to kinetics and not thermodynamics. At higher temperatures such
50 as those encountered for industrial formaldehyde synthesis it was proposed that consumption
51
52 of oxygen for formaldehyde production resulted in unavailability of oxygen to cause unwanted
53
54 side reactions.
55
56
57
58
59
60
1
2
3 Regardless of the debate regarding the fundamental mechanism for formaldehyde synthesis,
4
5 “pin hole” defects have been widely reported to be apparent on the silver surface during
6
7 methanol oxidation conditions in accord with Equation 27 110, 124. For example, Millar et al. 18
8 used Environmental Scanning Electron Microscopy (ESEM) to observe the formation of “hill-
9
10 like” structures as the reaction temperature was elevated to ca. 450 oC before widespread
11
12 production of “pin-holes” at temperatures above ca. 600 oC. Closer inspection of the pin-hole
13
14 defects using Field Emission Scanning Electron Microscopy revealed the presence of debris
15
comprised of small silver particles in the immediate vicinity of each pin-hole thus confirming an
16
17 “explosion” of water vapour from the subsurface region of the catalyst occurred 114.
18
19
20
21 7. Catalyst Poisons
22
23
Industrially, one of the most critical issues with relation to catalyst performance is poisoning
24 of the silver surface which can result in diminished methanol conversion, reduction in
25
26 selectivity to formaldehyde, enhanced sintering of silver crystals and blockage of the
27
28 catalyst bed. Inherently, polycrystalline silver catalyst is of low surface area and thus it is
29
30 particularly susceptible to the effects of even low concentrations of impurities in the feed
31 stream.
32
33
34
35 7.1 Rust
36
37 Catalytic performance of silver can be compromised when iron is present on the surface 125,
38 126
. Iron (rust) contamination can arise from degradation of plant components and also be
39
40 125
present in feed materials. Deng et al. deposited iron nitrate on a polycrystalline silver
41
42 surface and investigated the impact by a variety of surface science techniques. As the
43
44 extent of iron present on the silver surface was raised, the formaldehyde selectivity
45
46 decreased and the methanol conversion increased. Consequently it was inferred that the
47 iron species promoted the combustion of methanol. X-ray photoelectron spectroscopy
48
49 revealed that the oxidation state of the iron species increased as the amount of iron present
50
51 was enhanced and this behaviour corresponded with increasing production of carbon
52 127
53 monoxide and subsequently carbon dioxide during reaction conditions. Jede et al.
54 further illuminated the situation with regards to iron poisoning of silver catalyst by
55
56 determining that even a 2 % monolayer coverage of the catalyst surface with iron species
57
58 was sufficient to promote combustion of methanol.
59
60
1
2
3
4
5 7.2 Silica
6
7 Silica is usually introduced as a catalyst poison through the feed water supply. Without a
8 water purification process the silver catalyst can become spoiled by the deposition of silica
9
10 on the silver surface. As a result the formaldehyde yield can decrease due primarily to a
11
12 reduction in methanol conversion. Figure 17 shows a Scanning Electron Microscope (SEM)
13
14 image of silica deposits on a silver catalyst as confirmed by energy dispersive spectroscopy.
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
(a) (b)
32
33
34 Figure 17: Example of silica deposition on a silver catalyst surface (a) SEM image of silver
35
36 catalyst grain (b) EDS trace for observed impurities
37
38
39 7.3 Carbon
40
41 Carbon is almost always found either in the used catalyst bed or in the area immediately
42
43 below the catalyst bed [Figure 18]. One pathway to carbon formation is via the
44
45 decomposition of formaldehyde gas.
46
Equation 29: (Y) ↔ (Y) + (Y)
47
48
The decomposition of formaldehyde is favoured at the high reaction temperatures normally
49
50 encountered and the extent of this reaction depends upon the residence time of the hot
51
52 formaldehyde gas in the bed. The Boudouard reaction can then occur to produce
53
54 carbonaceous deposits.
55
56
Equation 30: 2 ↔ +
57
58
59
60
1
2
3 In some instances, carbon is observed as a distinct layer in the silver catalyst bed cross
4
5 section [Figure 18] directly below an uppermost “white layer” of silver. This behaviour may
6
7 be due to issues with the feed ratios employed which may accelerate carbon deposition.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38 Figure 18: Examples of carbon decomposition in a silver catalyst bed
39
40
41
42 8. Future Directions
43
44
It is clear from this review that the formaldehyde synthesis process using silver catalyst
45 represents a fascinating challenge to improve performance. Key issues which should be
46
47 addressed include: (1) process optimization to maximise formaldehyde yield and further
48
49 reduce utilities consumption; (2) development of improved silver catalysts which are
50
51 tailored specifically for reaction conditions; (3) elimination of poisoning of silver catalysts;
52 (4) creation of a detailed economic model for formaldehyde production with silver catalysts
53
54 and comparison to the alternate metal oxide process.
55
56
57
58
59
60
1
2
3 Efforts will still be directed towards development of synthesising formaldehyde directly
4 128 129
5 from methane or carbon dioxide , but it should be remembered that a substantial
6
7 amount of capital has been invested in formaldehyde infrastructure hence any substantial
8 changes in the formaldehyde synthesis industry may take many years to appear. As such it
9
10 is more prospective to optimise current techniques such that the payback to industry could
11
12 be obtained immediately.
13
14
15
There exists a threat to the formaldehyde industry in terms of the development of non-
16
17 formaldehyde based resins 130. As this latter market is the major consumer of formaldehyde
18
19 in many global locations, it would be prudent for the formaldehyde industry to attempt to
20
21 diversify the uses for formaldehyde. One such example is the oxidation of formaldehyde to
22
23
formic acid which is a catalytic process which can be added to existing formaldehyde
24 production facilities 131.
25
26
27
28 9. Conclusions
29
30 Formaldehyde synthesis from methanol using a silver catalyst is a well-established
31 technology that continues to be widely employed industrially, with its continual growth in
32
33 popularity greatly attributed to the dominance of this process in the Chinese market. There
34
35 are three commonly employed process variations with the off-gas recycle process variant
36
37 considered state of the art technology due to reported higher formaldehyde yields and
38
production of high strength formaldehyde concentrations. However, there is no consensus
39
40 as to the best design of formaldehyde plants with considerable differences in equipment
41
42 specifications apparent.
43
44
45
46 Operating conditions are somewhat varied and there is a distinct need to understand the
47 fundamentals of formaldehyde synthesis to a greater degree if enhancement of
48
49 formaldehyde yields to levels which are comparable with the metal oxide catalysed
50
51 methanol oxidation process is to be gained. Academic literature has focussed on
52
53 fundamental studies of catalyst mechanisms on silver catalyst but only rarely addressed
54 problems which are industrially important such as catalyst bed design, design of improved
55
56 catalysts which are industrially viable, impact of catalyst poisoning and how to mitigate
57
58 these effects, and optimization of process design. It is generally agreed that high space
59
60
1
2
3 velocities are required to minimise side reactions and that reaction temperature should be
4
5 maintained as low as possible.
6
7
8 Polycrystalline silver catalyst made electrochemically dominates the formaldehyde industry
9
10 but it is evident that the quality is not consistent and that physical parameters such as high
11
12 surface area, good porosity, excellent mechanical strength, acceptable thermal conductivity,
13
14 and a medium bulk density are not always adhered to. The major drawback of
15
polycrystalline silver catalysts is their extreme sensitivity to catalyst poisons due to the
16
17 inherently low surface area present in metallic catalysts. A means to protect the silver
18
19 catalyst surface from contamination is desirable.
20
21
22
23
All too often, poor formaldehyde yields or unsatisfactory catalyst lifetimes have been
24 ascribed to undesirable catalyst properties despite the fact no catalyst autopsy was
25
26 performed or investigation of plant operation completed. Consequently, there exists
27
28 considerable scope to introduce and apply state of the art catalyst science and standardised
29
30 engineering methods to the formaldehyde industry.
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
2
3 10. Acknowledgements
4
5 We would like to thank all the formaldehyde producers, formaldehyde equipment suppliers,
6
7 and personnel who have shared their knowledge with us and allowed us to gain an insight
8 into the fascinating world of industrial methanol oxidation over silver catalyst.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
2
3 11. References
4
5 1. Kowatsch, S., Formaldehyde. In Phenolic Resins: A Century of Progress, 2010; pp 25-40.
6 2. Silva, D. A. L.; Lahr, F. A. R.; Varanda, L. D.; Christoforo, A. L.; Ometto, A. R., Environmental
7 performance assessment of the melamine-urea-formaldehyde (MUF) resin manufacture: a case
8 study in Brazil. J. Cleaner Prod. 2014, 96, 299-307.
9 3. Ayrilmis, N.; Lee, Y. K.; Kwon, J. H.; Han, T. H.; Kim, H. J., Formaldehyde emission and VOCs
10 from LVLs produced with three grades of urea-formaldehyde resin modified with nanocellulose.
11 Building and Environment 2016, 97, 82-87.
12 4. Li, C.; Zhang, J.; Yi, Z.; Yang, H.; Zhao, B.; Zhang, W.; Li, J., Preparation and characterization of
13 a novel environmentally friendly phenol-formaldehyde adhesive modified with tannin and urea. Int.
14
J. Adhes. Adhes. 2016, 66, 26-32.
15
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