MOVING BED BIOFILM REACTOR (MBBR) SYSTEM FOR CONVERSION OF SYNGAS COMPONENTS TO LIQUID PRODUCTS

RELATED APPLICATIONS

This application claims the benefit of and priority to United States Patent Application 11/833,864 filed August 3, 2007, the entirety of which is hereby incorporated by reference.

FIELD OF THE INVENTION

This invention relates to the biological conversion of CO and mixtures of CO ₂ and H ₂ to liquid products.

DETAILED DESCRIPTION

BACKGROUND

Biofuels production for use as liquid motor fuels or for blending with conventional gasoline or diesel motor fuels is increasing worldwide. Such biofuels include, for example, ethanol and n-butanol. One of the major drivers for biofuels is their derivation from renewable resources by fermentation and bioprocess technology. Conventionally, biofuels are made from readily fermentable carbohydrates such as sugars and starches. For example, the two primary agricultural crops that are used for conventional bioethanol production are sugarcane (Brazil and other tropical countries) and corn or maize (U.S. and other temperate countries). The availability of agricultural feedstocks that provide readily fermentable carbohydrates is limited because of competition with food and feed production, arable land usage, water availability, and

other factors. Consequently, lignocellulosic feedstocks such as forest residues, trees from plantations, straws, grasses and other agricultural residues may become viable feedstocks for bio fuel production. However, the very heterogeneous nature of lignocellulosic materials that enables them to provide the mechanical support structure of the plants and trees makes them inherently recalcitrant to bioconversion. Also, these materials predominantly contain three separate classes of components as building blocks: cellulose (C ₆ sugar polymers), hemicellulose (various C5 and C ₆ sugar polymers), and lignin (aromatic and ether linked hetero polymers).

For example, breaking down these recalcitrant structures to provide fermentable sugars for bioconversion to ethanol typically requires pretreatment steps together with chemical/enzymatic hydrolysis. Furthermore, conventional yeasts are unable to ferment the C5 sugars to ethanol and lignin components are completely unfermentable by such organisms. Often lignin accounts for 25 to 30% of the mass content and 35 to 45% of the chemical energy content of lignocellulosic biomass. For all of these reasons, processes based on a pretreatment / hydrolysis / fermentation path for conversion of lignocellulose biomass to ethanol, for example, are inherently difficult and often uneconomical multi- step and multi conversion processes.

An alternative technology path is to convert lignocellulosic biomass to syngas (also known as synthesis gas, primarily a mix of CO, H ₂ and CO ₂ with other components such as CH ₄ , N ₂ , NH3, H ₂ S and other trace gases) and then ferment this gas with anaerobic microorganisms to produce biofuels such as ethanol, n-butanol or chemicals such as acetic acid, butyric acid and the like. This path can be inherently more efficient than the pretreatment / hydrolysis / fermentation path because the gasification step can

convert all of the components to syngas with good efficiency (e.g., greater than 75%), and some strains of anaerobic microorganisms can convert syngas to ethanol, n-butanol or other chemicals with high (e.g., greater than 90% of theoretical) efficiency. Moreover, syngas can be made from many other carbonaceous feedstocks such as natural gas, reformed gas, peat, petroleum coke, coal, solid waste and land fill gas, making this a more universal technology path.

However, this technology path requires that the syngas components CO and H ₂ be efficiently and economically dissolved in the aqueous medium and transferred to anaerobic microorganisms that convert them to the desired products. And very large quantities of these gases are required. For example, the theoretical equations for CO or H ₂ to ethanol are:

6 CO + 3 H ₂ O -> C ₂ H ₅ OH + 4 CO ₂ 6 H ₂ + 2 CO ₂ -> C ₂ H ₅ OH + 3 H ₂ O Thus 6 moles of relatively insoluble gases such as CO or H ₂ have to transfer to an aqueous medium for each mole of ethanol. Other products such as acetic acid and n- butanol have similar large stochiometric requirements for the gases.

Furthermore, the anaerobic microorganisms that bring about these bioconversions generate very little metabolic energy from these bioconversions. Consequently they grow very slowly and often continue the conversions during the non-growth phase of their life cycle to gain metabolic energy for their maintenance.

Many devices and equipment are used for gas transfer to micro organisms in fermentation and waste treatment applications. These numerous bioreactors all suffer from various drawbacks. In most of these conventional bioreactors and systems, agitators with specialized blades or configurations are used. In some others such as gas lift or fluidized beds, liquids or gases are circulated via contacting devices. The agitated vessels require a lot of mechanical power often in the range of 4 to 10 KW per 4000 liters - uneconomical and unwieldy for large scale fermentations that will be required for such syngas bioconversions. The fluidized or fluid circulating systems cannot economically provide the required gas dissolution rates. Furthermore, most of these reactors or systems are configured for use with micro organisms in planktonic or suspended form i.e. they exist as individual cells in liquid medium.

Furthermore, for the suspended cultures to get high yields and production rates the cell concentrations in the bioreactor need to be high and this requires some form of cell recycle or retention. Conventionally, this is achieved by filtration of the fermentation broth through microporous or nonporous membranes, returning the cells and purging the excess. These systems are expensive and require extensive maintenance and cleaning of the membranes to maintain the fluxes and other performance parameters.

Cell retention by formation of bio films is a very good and often inexpensive way to increase the density of micro organisms in bioreactors. This requires a solid matrix with large surface area for the cells to colonize and form a biofilm that contains the metabolizing cells in a matrix of biopolymers that the cells generate. Trickle bed and

some fluidized bed bioreactors make use of biofϊlms to retain microbial cells on solid surfaces while providing dissolved gases in the liquid by flow past the solid matrix. They suffer from either being very large or unable to provide sufficient gas dissolution rates.

Moving Bed Biofilm Reactors (MBBR) have been shown to be high-rate, compact systems for wastewater treatment, particularly where slow growing organisms are involved. Hallvard Odegaard describes the use of MBBR systems for the treatement of wasterwater in Innovations in wastewater treatment: the moving bed biofilm process - Water and Science & Technology VoI 53 No 9 pp 17-32. These biofilm type rectors are especially compatible with highly efficient (in terms of both gas transfer efficiency [power per mass of gas transferred] and dissolution efficiency) such as jet and/or slot aerators/gas transfer devices. The combination of the MBBR process and these gas transfer devices overcomes the problems associate with alternate approaches described above.

SUMMARY OF THE INVENTION

The instant invention involves using a buoyant or suspended carrier as a media for supported the biomass in what is termed a MBBR. In this system the fermenting biomass adheres to and grows on the surfaces of an inert biomass carrier media as biofilm. The gaseous substrates CO and/or CO2/H2 are delivered via any device that will promote high gas dissolution and utilization. Such devices include gas spargers and preferably a high efficiency gas transfer system such as jet or slot aerator/gas transfer devices. The gas injection device will normally serve the additional function of creating eddy currents in

the surrounding liquid for thoroughly mixing the contents of the fermentation vessel. Gas bubbles from the gas delivery device will rise to the liquid surface and provide additional mixing and gas dissolution. Desirably the fermentation vessel has sufficient depth to ensure high gas dissolution and utilization. Typically the fermentation vessel has a minimum depth of 9 meters that is wetted by the fermentation broth and achieves at least 80% gas dissolution. The wetted depth of the fermentation broth provides the working volume where the motion of gas and liquid keeps the biomass carrier moving. The biomass carrier is typically maintained in the reactor via an outlet sieve or other suitable screening device. The turbulence created by any flow of gas and/or liquid through the vessel can also provides sufficient shear so as to maintain the bio film thickness on the biomass carrier in the desirable range.

It has been observed that the presence of oxygenates such as ethanol in the fermentation media at as low as 1% (weight/volume) has a profound effect on gas transfer efficiency. The change in surface tension results in smaller bubbles being generated and therefore a significantly greater surface area of gas bubbles exposed to the liquid. The result is transfer rates of up to 3 times that observed for clean water.

The result of combining a MBBR system having a gaseous feed with a highly efficient gas transfer system, preferably such as a jet or slot aerators/gas transfer devices, results in an economical and high product volumetric production rate system for production of liquid products. One additional advantage of the slot and jet gas transfer devices is that they are relatively clog free and treatment of the syngas components for small particulates is not necessarily required.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a schematic drawing showing two different types of media for the MBBR biomass carrier.

Fig. 2 shows the carrier media of Figs. l(a) and (b) with attached bio film Fig. 3 is a schematic drawing shows combination of a typical MBBR reactor and conventional gas sparging aerator for gas transfer

Fig. 4 is a schematic drawing shows combination of a typical MBBR reactor and slot aerator for gas transfer.

DETAILED DESCRIPTION OF THE INVENTION

Bioconversions of CO and H2/CO2 to acetic acid, ethanol and other products are well known. For example, in a recent book concise description of biochemical pathways and energetics of such bioconversions have been summarized by Das, A. and L. G. Ljungdahl, Electron Transport System in Acetogens and by Drake, H. L. and K. Kusel, Diverse Physiologic Potential of Acetogens, appearing respectively as Chapters 14 and 13 of Biochemistry and Physiology of Anaerobic Bacteria, L. G. Ljungdahl eds,. Springer (2003). Any suitable microorganisms that have the ability to convert the syngas components: CO, H ₂ , CO ₂ individually or in combination with each other or with other components that are typically present in syngas may be utilized. Suitable microorganisms and/or growth conditions may include those disclosed in U.S. Patent Application Serial No. 11/441,392, filed May 25, 2006, entitled "Indirect Or Direct Fermentation of Biomass to Fuel Alcohol," which discloses a biologically pure culture of the microorganism Clostridium carboxidivorans having all of the identifying

characteristics of ATCC no. BAA-624; and U.S. Patent Application Serial No. 11/514,385 filed August 31, 2006 entitled "Isolation and Characterization of Novel Clostridial Species," which discloses a biologically pure culture of the microorganism Clostridium ragsdalei having all of the identifying characteristics of ATCC No. BAA- 622; both of which are incorporated herein by reference in their entirety. Clostridium carboxidivorans may be used, for example, to ferment syngas to ethanol and/or n- butanol. Clostridium ragsdalei may be used, for example, to ferment syngas to ethanol.

Suitable microorganisms and growth conditions include the anaerobic bacteria Butyribacterium methylotrophicum, having the identifying characteristics of ATCC 33266 which can be adapted to CO and used and this will enable the production of n- butanol as well as butyric acid as taught in the references: "Evidence for Production of n- Butanol from Carbon Monoxide by Butyribacterium methylotrophicum," Journal of Fermentation and Bioengineering, vol. 72, 1991, p. 58-60; "Production of butanol and ethanol from synthesis gas via fermentation," FUEL, vol. 70, May 1991, p. 615-619. Other suitable microorganisms include Clostridium Ljungdahli, with strains having the identifying characteristics of ATCC 49587 (US-A- 5,173,429) and ATCC 55988 and 55989 (US-A- 6,136,577) and this will enable the production of ethanol as well as acetic acid. All of these references are incorporated herein in their entirety.

The instant invention uses MBBR in concert with highly efficient gas transfer devices, such as jet or slot aerators/gas transfer devices, to dissolve gases into the liquid phase for delivering CO and/or a mixture Of H ₂ and CO ₂ to the anaerobic microorganism

maintained as a biofϊlm on inert biomass carrier media. The microorganisms in the biofilm use the CO and/or H2/CO2 in the gas and transform them into ethanol and other liquid products. The biomass support media allows the slow growing anaerobic microorganisms to be maintained in the fermentation vessel at concentrations well above what is possible with suspended culture. The result is a highly efficient and economical conversion of the CO and/or CO ₂ ZH ₂ Io liquid products.

This invention can be used with any stream that contains a suitable concentration of syngas components. Suitable streams will preferably contain a minimum of 10 wt.% CO and/or H ₂ . The system will normally operate under anaerobic conditions.

Suitable media for the MBBR biomass carrier made from polymers have been recently developed and commercialized for wastewater treatment and purification applications. Typically these media are made from hydrophobic polymers such as polyethylene or polypropylene which are processed to create a highly protected external or internal surface area for biofϊlm attachment and accumulation of high biomass concentrations. Several commercial organizations supply such media primarily as extruded cylindrical media.

Suitable media is commercially available from a number of companies including

AnoxKaldnes, Siemens/ Aqwise and Hydroxyl. Some characteristics of the different media from the two largest supplies, AnoxKaldnes and Hydroxyl, are given in the Table 1 below.

Table 1. Partial List of Commercially available MBBR media

I Dia P rote Total

Compa ength meter cted surface surface

Model ny ( (m (m ² /m (m ² / mm) m) ³ ) m ³ )

AnoxK aldnes K1 I 9 500 800

K3 2 25 500 600

Natrix

C2 0 36 220 265

Natrix

M2 0 64 200 230

Biofil m-Chip M .2 48 1200 1400

Biofil m-Chip P 45 900 990

Hydrox Active yi Cell 5 22 448 588

The media employed are generally extruded cylindrical type media made from polypropylene, polyethylene or recycled plastics. These materials typically provide the media with a relative density of .9 to .98 with respect to the fermentation broth and a ratio of protected surface/ total surface of at least 60%. The design of the media is such to maximize the overall surface area for attachment of a bio film. Accordingly the internal or protected surface area will generally be at least 60% of the total surface area of the media. The media volume shall comprise between 30% and 70% of the wetted volume of the fermentation vessel.

Figs. l(a) - l(d) illustrate two examples of the many suitable structures that can supply the moving media for support of biofilms. Fig. l(a) depicts the transverse view of a spoke and hub type media. Fig l(a) shows a cylinder 2 intersecting eight parallel vanes 4 that emanate from the center point of cylinder 2 and protrude outside its circumference. The internal sectors defined by the vanes and inner cylinder wall provide the interior surface for retention of a bio film. Figs. l(c) and l(d) illustrate another geometry for a support media 6 wherein an outer cylinder supports a rectangular grid work 10 of internal surfaces for the supporting a bio film. Fig l(b) and l(d) depicts side views of the medial of Fig l(a) and l(c) respectively which typically have a nominal diameter of from 5 to 50 mm and a width between 2 and 50 mm.

Fig 2 shows a biofilm growing on the support media 1 of Figs. l(a) & l(b). The support media grows on the interior surfaces of the media. The internal vane structure blocks entry of surrounding carrier media to protect the biofilm while also providing additional surface for support of the biofilm.

Fig. 3 schematically shows a support media 3 suspended in a fermentation broth held by a fermentation vessel 16 of an MBBR system 14. A conventional gas sparger 17, of the type typically used for aeration, injects a feed gas 19 containing at least one of CO or a mixture of CO ₂ and H ₂ into the fermentation broth. The dispersed feed gas at least partially dissolves into the fermentation broth as it travels upwardly towards its liquid surface 18. Gas recovery chamber 13 collects any residual feed gas and gaseous

fermentation outputs for recovery as stream 11. Stream 11 can undergo separation of gas components for recovery and/or recycle to stream 19 as desired.

The fermentation vessel maintains the fermentation broth and media at optimal metabolic conditions for the expression of the desired liquid products by the microorganisms. These conditions typically include a pressure of 1 to 5 bar and temperature of from 20 to 50 ⁰ C within the fermentation vessel.

The dissolved feed gas feeds a biofϊlm that grows on support media 3 to produce the liquid products of this invention. A sieve device 5 screens the support media from flowing into an outlet 9 that recovers the liquid products from the vessel 16. Preferably the sieve and outlet withdraw liquid from the upper section of the vessel but may withdraw liquid from any location at or below liquid level 18.

The distance between the liquid level 18 and the bottom of vessel 16 defines the wetted depth of the MBBR system. Most applications will require a minimum wetted depth of at least 9 meters and wetted depths greater than 15 meters are preferred.

Liquid recovered via outlet 9 typically undergoes separation in a product recovery section (not shown) to recover liquid products. The product recovery section that removes the desirable product from liquid taken by outlet 9, while leaving substantial amounts of water and residual nutrients in the treated stream, part of which is returned to the vessel 16 via line 7. A nutrient feed may be added via to the broth as needed to compensate for the amount of water removed and to replenish nutrients. The nutrient feed may enter vessel 16 directly or via line 7.

Fig. 4 depicts a generalized view of a flow arrangement similar to that of Fig. 3 except for the substitution of the conventional sparger 17 with a jet aerator 20. The jet aerator 20 provides a high velocity "throat" or contact chamber that educts the feed gas 19' comprising CO and/or CO ₂ /H ₂ into intimate contact with fermentation broth withdrawn from outlet 9. A line 22 transfer the broth from outlet 9 to a pump 17 that raises the pressure of the liquid to a range of about 3 to 5 bar. Pump 17 to provides the desired liquid velocity for to subject the educted gas to high shear forces that dissolve some of the gas and generates relatively fine microbubbles (0.1 to 1.0 mm in diameter) with the remainder of the gas. Ejection of this mixture from the contact chamber into the fermentation vessel creates a plume 21 that typically enters the fermentation vessel horizontally or at a slight downward angle. The force of the plume creates eddy currents in the surrounding liquid thoroughly mixing the contents of the fermentation vessel. As the plume dissipates, the gas bubbles rise to the liquid surface providing additional mixing and gas dissolution.

Example

A ;H\ m fermentor in the form of a fermentation vessel having a 1.5 meter diameter and a 20 meter wetted depth is used as a MBBR for the conversion of carbon monoxide and hydrogen into ethanol. The fermentor is filled approximately 50% of the liquid working volume with AnoxKaldnes Kl media. A gas of about 40% CO, 30% H ₂ , and 30% CO ₂ is fed to the vessel at 3.5 m ^' -pei minute and ^• < bm absolute inlet pressure and the residual gas exits the module at less than 0.1 bar outlet pressure. This gas flow is

added to a slot aeration/gas transfer device operated at a liquid recycle flow rate of 400 liters per minute. The fermentation medium having the composition given in Table 2 is used to fill the fermentor and maintained at about 37 °c. The fermentor is maintained under anaerobic conditions.

The fresh fermentation medium contains the components listed in Tables 2 & 3(a)-(d). Initially, the bioreactor system is operated in the batch mode and inoculated with 2000 liters of an active culture of Clostridium ragsdalei ATCC No. BAA-622. The fermentation pH is controlled at pH 5.9 in the first 24 hours by addition of 1 N NaHCO ₃ to favor cell growth and then allowed to drop without control until it reaches pH 4.5 to favor ethanol production. The system remains in the batch mode for 1 day to establish the attachment of the microbial cells on the media surface. Then, the system is switched to continuous operation, with continuous withdrawal of the fermentation broth for product recovery and replenish of fresh medium. With the continuous operation, suspended cells in the fermentation broth are gradually removed from the bioreactor system and decrease in concentration, while the biofilm attached on the media continues to grow until the biofilm reaches a thickness equilibrated with the operating conditions. The ethanol concentration at the end of the 10-day batch operation is 5 g/L. At the beginning of the continuous operation, a low broth withdrawal rate is selected so that the ethanol concentration in the broth does not decrease but increases with time. The broth withdrawal rate is then gradually increased. After 30 days of continuous operation, the ethanol concentration increases to 30 g/L with the broth withdrawal rate at 22 liters per

minute. The attached cell concentration is approximately 5 g/L dry weight at this point in time.

Table 2. Fermentation Medium Com ositions

Table 3 c . Vitamin Solution