Enzymatic Production of Formaldehyde and Hydrogen Peroxide from Methanol

Background The process uses the enzyme, methanol oxidase, to convert alcohol and oxygen to formaldehyde and hydrogen peroxide. The goal is to produce 50,000 tonne/y of 50 wt% hydrogen peroxide and 60,000 tonne/y of formalin !" wt% formaldehyde in water# using an enzymatic process. $ormaldehyde, methanol, and hydrogen peroxide are considered carcinogenic and/or hazardous materials. %n light of this, a process design was made that minimizes the waste and emissions generated. &urrently, many hollow fi'er mem'rane ($)# technologies are emerging into existing mar*ets, allowing for more cost+effective separations and reactions. ($)s are 'ecoming more useful in the chemical industry. ,ith the recent growth in the areas of 'iochemical and environmental technologies, many potential future mar*ets are availa'le for the use of ($)s. The enzyme, methanol oxidase, catalyzes the reaction in the continuous+stirred tan* fermentor. ($)s were used in an ultrafiltration unit off of the continuous+stirred tan* fermentor to recover the enzyme for recycle. Process Description The -$. $igure /# and four 0$.s $igures 1+5# show a process to produce formaldehyde and hydrogen peroxide. )ethanol fresh and recycled# at 23.!4& and //.23 'ar mixes with water fresh and recycled# at 10!.24& and //.23 'ar. Together they enter heat exchanger, 5+/0/, at /!34& and //.23 'ar and leave at 504& and //./5 'ar.

6xygen fresh and recycled# is sparged through the li7uid mixture of methanol and oxygen. The oxygen must first diffuse into the water 'efore it can 'e reacted. The enzyme, methanol oxidase, catalyzes the reaction. The reaction is a function of the enzyme concentration. The reactor has a conversion of oxygen of "2.5%. The reaction must proceed at +114&8 To reach this temperature, a cooling 9ac*et was added to the reactor. :efrigerant+/!2a :+/!2a# flows through the cooling 9ac*et. :+/!2a is sent through two compressors in series &+10/ ;/-, no intercooling# to o'tain a pressure of < 'ar. :+/!2a condenses and su'cools to !54& in 5+10/. %t is then flashed to 0."5 'ar, which lowers the temperature of the li7uid :+/!2a to +1<4&. The li7uid :+ /!2a is sent through the cooling 9ac*et and then is recycled 'ac* through the same process. This refrigeration loop is illustrated in $igure 2. The unreacted oxygen, ta*en from the top of the reactor, is compressed from < 'ar to //./5 'ar in compressor &+/0/ and is recycled 'ac* to =tream !. The ultrafiltration unit recovers excess enzyme from the outlet of the reactor. The enzyme is sent 'ac* to the reactor for reuse. =tream 6, composed of formaldehyde, methanol, water, hydrogen peroxide, and oxygen, is sent to >+/0/ at +114& and //./5 'ar. =tream 6 is flashed to remove most of the oxygen along with trace amounts of the other products. The top, =tream ", is sent to the incinerator. The 'ottom, =tream <, is sent to T+/0/. This vacuum distillation column separates almost pure hydrogen peroxide as the 'ottom product, =tream /0, at <54& and 0.!5 'ar. The top, =tream 3, is sent to >+ /0! at 66.64& and 0.13 'ar. ;gain, this flash unit separates out the oxygen leaving a negligi'le amount of oxygen 'ehind in =tream /1.

=tream /1 is pumped to /.11 'ar in 0+/0! 'efore it enters T+/01. This tower removes mostly methanol with some water and small amounts of formaldehyde in =tream /!. 0+/06 ;/- pumps =tream /! up to //./5 'ar where it is recycled 'ac* to the reactor. The 'ottom, =tream /2, consists mainly of formaldehyde and water at //1.34& and /.5! 'ar. 0+/05 pumps =tream /2 up to 10 'ar 'efore entering T+/0!. %n T+/0!, water is separated from formaldehyde to produce a !"% 'y weight formaldehyde in water solution, =tream /5. This stream is at 10".24& and /3.3" 'ar. The 'ottom of this tower, =tream /6, is mostly water at 1!3."4& and 10.!6 'ar. %t is split and some of the water is mixed with =tream /0 to produce the desired 50% 'y weight hydrogen peroxide in water in =tream /3. This stream is at /"3.24& and 10.!6 'ar. ?nit !00 provides the steam used in the distillation columns and flash vessels. The steam produced in this unit is at 10 'ar. The condensate return from the process was pumped and then sent to (+!0/. The steam is sent to 5+/0!, 5+/05, >+/0/, >+/0!, and >+/0! at 1204& and 10 'ar. Necessary Information and imulation Hints $ormaldehyde and hydrogen peroxide is produced 'y the following reaction

Methanol Oxidase

CH!OH + O1 CH1O + H1O1

The enzyme, methanol oxidase, is sta'le for up to 1 days /#.

-ut, when

operating under cryogenic conditions, the enzyme can last for as long as 50 days 1#. The *inetic expression is of the )ichaelis+)enten form Vmax @CAA

rA = Km + @CAA

The maximum rate of reaction, Vmax, for this enzyme is a function of enzyme concentration, @EoA, according to the following e7uation

Vmax = TO @EoA

where TO is the turnover num'er, 110 mole per minute per mole of active sites /#. The turnover num'er is the maximum amount of products that can 'e produced per active site on the enzyme !#. Vmax was calculated to 'e 0.!/!" m)/min. The )ichaelis+)enten constant, Km, is dependent on enzyme concentration. (owever, in this case, the enzyme is at such a high concentration that oxygen 'ecomes rate+limiting /#,

Km = 0.2 m)

=ince, the enzyme is used to catalyze the reaction in the li7uid phase, the oxygen must 'e dissolved into the li7uid 'efore it can react. Therefore, the relative rates of reaction and diffusion are important. -y using the following e7uation 2#

k/ D AB

( kC ) 1

where k/ is the reaction rate constant, DAB is the diffusivity of oxygen in water, kC is the mass transfer coefficient for a 'u''le in water, and is the ratio of the rate of reaction to the rate of diffusion, it was estimated that

B 0.056

This means that the oxygen diffuses approximately 10 times faster than it reacts. Therefore, we can assume that water in the reaction vessel is fully saturated with oxygen. Thermodynamic models in most simulators do not accurately predict the >C5 involving water, methanol, hydrogen peroxide, and formaldehyde. D+values were input 'ased on data for the water+formaldehyde+methanol system 5# and the water+hydrogen peroxide system 6#.

!eferences" /. (oi'erg, .., et al., E&onversion of ;lcohols to ;ldehydes and (ydrogen 0eroxide 'y =u'strate and 0roduct Tolerant )ethanol 6xidases,F ?.=. 0atent G2,310,055, /330. 1. (attfield, H.,., E5nzymatic 0rocess for )anufacturing $ormaldehyde and (ydrogen 0eroxide,F ?.=. 0atent G5,1!2,<1", /33!. !. :ichardson, I.$., and 0eacoc*, ..H., Chemical Engineering Volume ! 0ergamon 0ress, Jew Kor*, JK, /332.
rd

Edition,

2. &ussler, 5.C., Di""usion! Mass Trans"er #luid $%stems! &nd Edition, &am'ridge, Jew Kor*, /33", &h./6. 5. Hmehling, I., ?. 6n*en, and ,. ;rlt, Va'or()i*uid E*uili+rium Data Collection, &hemistry .ata =eries ;7ueous+6rganic =ystems L =upplement /#, >ol. /, 0art /a, .5&(5);, /3</, pp. 2"2+2"5. 6. HiguMre, 0. ;. and 6. )aass, E>apor 0ressures and -oiling 0oints of -inary )ixtures of (ydrogen 0eroxide and ,ater,F Canadian ,ournal o" -esearch, #$B, /</+/3!, /320.

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E%uipment Descriptions :+/0/ ;/?$+/0/ ;/5+/0/ &+/0/ &I+/0/ >+/0/ T+/0/ 5+/01 >+/01 0+/0/ ;/>?+/0/ 5+/0! 0+/01 ;/>+/0! 0+/0! ;/T+/01 5+/02 >+/02 0+/02 ;/5+/05 0+/05 ;/0+/06 ;/&ontinuously =tirred $ermentor ?ltrafiltration 5nzyme :ecovery :eactor $eed &ooler 6xygen :ecycle &ompressor :eactor &ooling Iac*et 61 $lash ?nit (161 >acuum .istillation (161 &ondenser (161 :eflux .rum (161 :eflux 0umps >acuum ?nit (161 :e'oiler (161 -ottoms 0ump 61 $lash ?nit 0roduct 0umps )ethanol .istillation Tower )ethanol &ondenser )ethanol :eflux .rum )ethanol :eflux 0umps )ethanol :e'oiler )ethanol -ottoms 0ump )ethanol :ecycle 0umps

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T+/0! 5+/06 >+/05 0+/0" ;/&+10/ ;/5+10/ >+10/ (+!0/ 0+!0/

$ormalin .istillation Tower $ormalin &ondenser $ormalin :eflux .rum $ormalin :eflux 0umps :efrigerant &ompressor :efrigerant &ooler :efrigerant $lash =team 0ac*age -oiler =team Coop 0ump

tream &a'le for Formaldehyde and Hydrogen Peroxide Production

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++

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++ 1!2.! 1,520.6 /.0 ++

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=tream Jo. Temperature o&# 0ressure 'ar# >apor )ole $raction Total $low *g/h# Total $low *mol/h#

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