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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 (37 wt% formaldehyde in water) using an enzymatic process. Formaldehyde, methanol, and hydrogen peroxide are considered carcinogenic and/or hazardous materials. In light of this, a process design was made that minimizes the waste and emissions generated. Currently, many hollow fiber membrane (HFM) technologies are emerging into existing markets, allowing for more cost-effective separations and reactions. HFMs are becoming more useful in the chemical industry. With the recent growth in the areas of biochemical and environmental technologies, many potential future markets are available for the use of HFMs. The enzyme, methanol oxidase, catalyzes the reaction in the continuous-stirred tank fermentor. HFMs were used in an ultrafiltration unit off of the continuous-stirred tank fermentor to recover the enzyme for recycle. Process Description The BFD (Figure 1) and four PFDs (Figures 2-5) show a process to produce formaldehyde and hydrogen peroxide. Methanol (fresh and recycled) at 49.3°C and 11.49 bar mixes with water (fresh and recycled) at 203.4°C and 11.49 bar. Together they enter heat exchanger, E-101, at 139°C and 11.49 bar and leave at 50°C and 11.15 bar. Oxygen (fresh and recycled) is sparged through the liquid mixture of methanol and
It is then flashed to 0. no intercooling) to obtain a pressure of 8 bar. a cooling jacket was added to the reactor. The liquid R134a is sent through the cooling jacket and then is recycled back through the same process. The enzyme. Refrigerant-134a (R-134a) flows through the cooling jacket. The oxygen must first diffuse into the water before it can be reacted.5%. The reaction is a function of the enzyme concentration. which lowers the temperature of the liquid R-134a to -28°C.29 bar.2 oxygen. This tower removes mostly methanol with some water and small amounts of formaldehyde in Stream . composed of formaldehyde.15 bar in compressor C-101 and is recycled back to Stream 3. Stream 12 is pumped to 1.35 bar. Stream 10.6°C and 0. Stream 6 is flashed to remove most of the oxygen along with trace amounts of the other products. R-134a is sent through two compressors in series (C-201 A/B. The top. Stream 7. The top. The bottom. The reaction must proceed at -22°C! To reach this temperature. methanol. at 85°C and 0. R-134a condenses and subcools to 35°C in E-201. taken from the top of the reactor. this flash unit separates out the oxygen leaving a negligible amount of oxygen behind in Stream 12. The enzyme is sent back to the reactor for reuse. is sent to V-101 at -22°C and 11. is sent to V103 at 66. is sent to the incinerator.15 bar. Again. methanol oxidase. The reactor has a conversion of oxygen of 74. This refrigeration loop is illustrated in Figure 4. water. The ultrafiltration unit recovers excess enzyme from the outlet of the reactor. This vacuum distillation column separates almost pure hydrogen peroxide as the bottom product. is compressed from 8 bar to 11. hydrogen peroxide.22 bar in P-103 before it enters T-102.75 bar. catalyzes the reaction. and oxygen. Stream 8. is sent to T-101. The unreacted oxygen. Stream 9. Stream 6.
Stream 15. The bottom of this tower. water is separated from formaldehyde to produce a 37% by weight formaldehyde in water solution. consists mainly of formaldehyde and water at 112. is stable for up to 2 days (1). Unit 300 provides the steam used in the distillation columns and flash vessels. V-103. Necessary Information and Simulation Hints Formaldehyde and hydrogen peroxide is produced by the following reaction CH3OH + O2 → CH2O + H2O2 Methanol Oxidase The enzyme. Stream 16.4°C and 20. The condensate return from the process was pumped and then sent to H-301. the enzyme can last for as long as 50 days (2). is mostly water at 239.3 13. This stream is at 207. The kinetic expression is of the Michaelis-Menten form Vmax [CA] rA = Km + [CA] . The bottom. methanol oxidase. This stream is at 179. It is split and some of the water is mixed with Stream 10 to produce the desired 50% by weight hydrogen peroxide in water in Stream 19. when operating under cryogenic conditions. P-106 A/B pumps Stream 13 up to 11.36 bar. In T-103. P-105 pumps Stream 14 up to 20 bar before entering T-103.53 bar.36 bar. The steam is sent to E-103. E-105.7°C and 20. V-101.9°C and 1.15 bar where it is recycled back to the reactor.97 bar. and V-103 at 240°C and 20 bar. The steam produced in this unit is at 20 bar. Stream 14.4°C and 19. But.
Km. By using the following equation (4) Φ= k1 D AB (k C )2 where k1 is the reaction rate constant. However. kC is the mass transfer coefficient for a bubble in water. the oxygen must be dissolved into the liquid before it can react. Vmax was calculated to be 0. Therefore. Km = 0.4 mM Since. The turnover number is the maximum amount of products that can be produced per active site on the enzyme (3). is dependent on enzyme concentration. and Φ is the ratio of the rate of reaction to the rate of diffusion. Vmax. it was estimated that .4 The maximum rate of reaction. according to the following equation Vmax = TO [Eo] where TO is the turnover number. in this case. the enzyme is used to catalyze the reaction in the liquid phase. for this enzyme is a function of enzyme concentration.3137 mM/min. the enzyme is at such a high concentration that oxygen becomes rate-limiting (1). DAB is the diffusivity of oxygen in water. 220 mole per minute per mole of active sites (1). the relative rates of reaction and diffusion are important. [Eo]. The Michaelis-Menten constant.
2. Thermodynamic models in most simulators do not accurately predict the VLE involving water. P. Hattfield. Patent #5. Giguère. 474-475. Chemical Engineering Volume 3. Cussler. and formaldehyde.. hydrogen peroxide. Ch.. Vapor-Liquid Equilibrium Data Collection.. E. Chemistry Data Series (Aqueous-Organic Systems – Supplement 1). Arlt.827. and O. Vol. References: 1. DECHEMA. Pergamon Press. 3rd Edition. New York.. 1997. “Conversion of Alcohols to Aldehydes and Hydrogen Peroxide by Substrate and Product Tolerant Methanol Oxidases.G.5 Φ = 0.920. Diffusion. and W. Patent #4. G. and Peacock. Gmehling. 1990. 6. 3. Therefore.. Cambridge. 2nd Edition. “Vapor Pressures and Boiling Points of Binary Mixtures of Hydrogen Peroxide and Water. 1940.S. et al. 1. Onken.S. Maass.. Mass Transfer Fluid Systems.056 This means that the oxygen diffuses approximately 20 times faster than it reacts.” U. D. 4. 1993.F. U. .” Canadian Journal of Research.055.. 1981.” U. 18B. Richardson. New York. 5. Hoiberg. NY.W. J. Part 1a.234. we can assume that water in the reaction vessel is fully saturated with oxygen. A. “Enzymatic Process for Manufacturing Formaldehyde and Hydrogen Peroxide. 181-193. methanol. J. K-values were input based on data for the water-formaldehyde-methanol system (5) and the water-hydrogen peroxide system (6).L.16. D. 1994. pp.
6 Equipment Descriptions R-101 A/B UF-101 A/B E-101 C-101 CJ-101 V-101 T-101 E-102 V-102 P-101 A/B VU-101 E-103 P-102 A/B V-103 P-103 A/B T-102 E-104 V-104 P-104 A/B E-105 P-105 A/B P-106 A/B Continuously Stirred Fermentor Ultrafiltration Enzyme Recovery Reactor Feed Cooler Oxygen Recycle Compressor Reactor Cooling Jacket O2 Flash Unit H2O2 Vacuum Distillation H2O2 Condenser H2O2 Reflux Drum H2O2 Reflux Pumps Vacuum Unit H2O2 Reboiler H2O2 Bottoms Pump O2 Flash Unit Product Pumps Methanol Distillation Tower Methanol Condenser Methanol Reflux Drum Methanol Reflux Pumps Methanol Reboiler Methanol Bottoms Pump Methanol Recycle Pumps .
7 T-103 E-106 V-105 P-107 A/B C-201 A/B E-201 V-201 H-301 P-301 Formalin Distillation Tower Formalin Condenser Formalin Reflux Drum Formalin Reflux Pumps Refrigerant Compressor Refrigerant Cooler Refrigerant Flash Steam Package Boiler Steam Loop Pump .
037.2 2.Stream No.775.0 68.4 1.49 0 8.865.0 0 1 0 1 0 1 58.9 0.868.4 38.1 0.0 --124.15 11.6 1.6 0.0 2.9 140.4 1.962.3 1.262.8 2. 49.8 Temperature (oC) Pressure (bar) Vapor Mole Fraction Total Flow (kg/h) Total Flow (kmol/h) Component Flowrates (kmol/h) -234.0 68.539.9 2.540.9 50.5 11.300.1 ----91.15 11.1 0.35 0 3.3 44.8 2.8 --234.3 11.774.6 0.160.0 1 2 3 4 5 6 7 8 9 66.497.0 141.0 124.8 -- Formaldehyde Methanol Water Hydrogen Peroxide Oxygen .1 10 84.121.496.8 2.221.001.4 44.3 2.6 93.0 -----0.6 ---1.1 --31.2 2.0 0.15 0.6 56.9 31.35 0.0 90.15 11.0 3.540.9 ** 92.6 92.35 0 56.49 11.9 203.2 -22.8 2.993.1 91.1 2.6 53.29 0 53.539.9 140.4 278.3 2.3 92.2 93.3 0.
0 0.539.1 -- 1.4 62.9 2.6 11.0 173.600.7 179.8 112.079.1 2.7 37.6 1.36 20.3 44.8 Methanol 0.502.6 91.36 20.249.01 140.5 92.9 207.4 Hydrogen Peroxide ** -- -- 1.7 128.942.454.9 3.200.36 0 6.4 92.2 11 12 13 14 15 16 17 18 19 Temperature (oC) Pressure (bar) Vapor Mole Fraction Total Flow (kg/h) Total Flow (kmol/h) Component Flowrates (kmol/h) ** 92.198.774.97 20.465.29 1.036.5 48.7 241.1 2.22 1.29 1 1.080.452.4 2.36 0 21.4 173.53 19.0 68.6 0 0 0 0 0 0 0.7 239.1 0.609.7 239.03 2.Stream No.0 1.0 53.0 0.04 2.1 7.0 4.4 20.8 -- -- -- -- Water -1.199. 68.1 64.1 345.092.494.5 ----- Formaldehyde 0.8 Oxygen -- -- -- -- -- -- -- .9 0.4 239.2 265.6 3.9 11.6 1.
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