Reactor, CO2 sorbent system, and process of making H2 with simultaneous CO2 sorption

Abstract

A reactor and process for production of hydrogen gas from a carbon-containing fuel in a reaction that generates carbon dioxide is described. The carbon-containing fuel can be, for example, carbon monoxide, alcohols, oxygenates bio-oil, oil and hydrocarbons. In preferred embodiments, the reactor includes a monolithic structure form with an array of parallel flow channels. Methods of using the reactor are also described. In the reactor apparatus of the present invention, the catalytic reaction for hydrogen formation is conducted in conjunction with a carbonation reaction that removes carbon dioxide that is produced by the reactor. The carbonation reaction involves reaction of the carbon dioxide produced from the hydrogen formation reaction with metal oxide-based sorbents. The reactor apparatus can be periodically regenerated by regeneration of the sorbent. A carbon dioxide sorbent system comprising a solid sorbent and a eutectic, mixed alkali metal molten phase is also described.

Claims

1. A reactor for producing hydrogen, comprising: a plurality of reaction channels comprising a steam reforming catalyst or water gas shift catalyst, each reaction channel comprising one or more channel walls; wherein at least one reaction channel wall is porous to carbon dioxide; at least one sorbent chamber adjacent the reaction channel, separated from the reaction channel by one or more channel walls and comprising a CO2 sorbent; and wherein the reaction channel comprising the steam reforming catalyst has an average diameter of between 0.1 mm and 10 mm, wherein the reactor channels each have an inlet and an outlet, and wherein the sorbent chamber(s) have no ports or closed ports configured such that gaseous flow into and out of a sorbent chamber is only through the porous reaction channel wall(s).

2. The reactor of claim 1 wherein the reactor comprises at least 10 parallel reaction channels.

3. The reactor of claim 1 wherein the catalyst is a steam reforming catalyst and wherein the steam reforming catalyst is a wall coating and wherein an open bulk flow path is present in reaction channel.

4. The reactor of claim 3 wherein the steam reforming catalyst comprises Ni, Cu, Mg, Ce, and Al.

5. The reactor of claim 1 wherein the reactor comprises a honeycomb monolith.

6. The reactor of claim 5 comprising a plurality of parallel reaction channels alternating with plurality of parallel sorbent chambers; preferably at least 10 parallel reaction channels alternating with at least 10 parallel sorbent chambers.

7. The reactor of claim 1 wherein sorbent fills a cross-section of the sorbent chamber.

8. The reactor of claim 1 wherein the reactor comprises a honeycomb monolith; and wherein the monolith comprises: a macro- and meso-porous material; a metal oxide; titania, alumina, silica; or a dense material such as metal with apertures for gas flow.

9. The reactor of claim 1 wherein the sorbent surrounds at least one reaction channel.

10. The reactor of claim 1 wherein a single sorbent chamber surrounds the plurality of reaction channels.

11. The reactor of claim 1 wherein the porous channel wall has a volume average pore size that in the range of about 1 nm to 100 m.

12. A method of steam reforming, comprising passing hydrocarbon and steam into the reactor of claim 1.

13. A method of converting hydrocarbons to H2, comprising passing a carbon fuel and water into the reactor of claim 1; wherein the water is in the form of steam or wherein the water is converted to steam within the reactor; wherein the reaction channel is at a temperature of at least 350 C.; wherein the steam and carbon fuel react in the reaction channel at a temperature of at least 350 C. to produce at least H.sub.2 and CO.sub.2; wherein at least a portion of the CO.sub.2 flows into the sorbent chamber where it is sorbed by the CO.sub.2 sorbent; and regenerating the CO.sub.2 sorbent.

14. The method of claim 13 wherein the carbon fuel is a hydrocarbon and wherein the reactor comprises a steam reforming catalyst.

15. The method of claim 14 wherein the reforming and sorption are performed at a temperature less than or equal to about 700 C., in some embodiments less than or equal to about 550 C. in a time of less than about 10 minutes.

16. The method of claim 14 wherein the reforming and sorption are performed iteratively in a plurality of cycles with a delay between any subsequent cycle of less than or equal to about 10 minutes.

17. The method of claim 14 wherein the hydrocarbon feedstock is a bio-oil.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

(2) FIGS. 1A-1C. Process flow diagrams comparing conventional hydrogen production processes (FIGS. 1A-1B) with a simplified flow diagram enabled by present invention (FIG. 1C).

(3) FIG. 2 schematically illustrates a swing reactor configuration for production of a H2-rich stream.

(4) FIG. 3 schematically illustrates a catalytic system for combined cracking and steam reforming reaction in the same catalyst structure.

(5) FIG. 4 schematically illustrates a catalytic system with catalyst adjacent the CO2 sorbent.

(6) FIG. 5 Thermodynamic equilibrium curves of MgO carbonation and CaO carbonation.

(7) FIG. 6A schematically illustrates a monolithic bed structure with a porous, inert reaction channel wall.

(8) FIG. 6B schematically illustrates a monolithic bed structure with a porous, catalytically active reaction channel wall.

(9) FIG. 7 is a schematic illustration of a CO2 sorbent material system according to the present invention.

(10) FIGS. 8A-8B show CO.sub.2 sorption performances of CaO sorbents (comparative base: as-prepared CaO, CaO+10 wt % LiNaK-carbonate); (8A). At 500 C. constant sorption temperature but different regeneration temperature; (8B). At 700 C. constant regeneration temperature but different sorption temperature.

(11) FIG. 9 TGA testing results of dolomite sorbent under two sets of sorption and regeneration conditions (comparative base); Green lines denoted as [1]=sorption: 400 C., CO.sub.2, 99 min; regeneration: 500 C., air, 51 min; Red lines denoted as [2]=sorption: 500 C., CO.sub.2, 90 min; regeneration: 600-750 C., air, 90 min.

(12) FIG. 10 TGA testing results of dolomite+10 wt % LiNaKCO3 composite sorbent under two sets of sorption and regeneration conditions; Red lines denoted as [7]=sorption: 400 C., CO.sub.2, 99 min; regeneration: 500 C., air, 51 min; Blue lines denoted as [6]=sorption: 500 C., CO.sub.2, 90 min; regeneration: 600-750 C., air, 90 min.

(13) FIG. 11 Synergistic effects of the proposed composite sorbent design (sorption in 10% CO.sub.2, regeneration at 700 C. in N.sub.2 for all the runs).

(14) FIG. 12 TGA testing results of dolomite+10 wt % LiNaKCO3 composite sorbent at lower working temperatures; Green line denoted as [1]=sorption: 360 C., CO.sub.2; regeneration: 400 C., N.sub.2 Red line denoted as [2]=sorption: 360 C., CO.sub.2; regeneration: 450 C., N.sub.2; Blue line denoted as [3]=sorption: 400 C., CO.sub.2; regeneration: 550 C., air.

(15) FIG. 13 TGA testing results of a composite sorbent comprising MgO+Na2CO3+LiNaKCO3 (sorption: 400 C., CO.sub.2, 99 min; regeneration: 500 C., air, 51 min) Red line=Temperature profile, Green line=weight change.

(16) FIG. 14 Multiple cycling tests of dolomite-based composite sorbents with two different promoter loading levels (sorption at 550 C. in 10% CO.sub.2; dashed line=temperature profile; red line denoted as [2]=sorbent #1 1-8 cycles; blue line denoted as [3]=sorbent #1 9-16 cycles; green line denoted as [1]=sorbent #2 1-8 cycles).

(17) FIGS. 15A-15D show CO.sub.2 sorption breakthrough curves with different H.sub.2O/steam ratio in the feed gas (GHSV=5,800 v/v/h on dry gas basis @ standard gas conditions) a). Breakthrough curve (H.sub.2O/dry gas=0); (b). CO.sub.2 loading (H.sub.2O/dry gas=0); (c). CO.sub.2 loading (H.sub.2O/dry gas=0.25); (d). CO.sub.2 loading (H.sub.2O/dry gas=1.0).

(18) FIGS. 16A-16B show stability of sorbent beds with repeated sorption/regeneration cycling (sorption conditions: 500 C., H.sub.2O/dry gas=1) FIG. 16A shows various conditions on various days; FIG. 16B shows H.sub.2O/dry gas=1:1, P=2.0 bar, 17.sup.th day.

(19) FIGS. 17A-17D show micro-structures of fresh and used composite sorbents (A). as-prepared with 350 C. pre-calcination; (B). as-prepared with 725 C. pre-calcination; (C). Spent sorbent from run 6-12; (D). Spent sorbent from run 7-31.

(20) FIG. 18 Elemental mapping of as-prepared composite sorbent with 350 C. pre-calcination.

(21) FIG. 19 Elemental mapping of spent composite sorbent from run 6-12.

(22) FIG. 20 Elemental mapping of spent composite sorbent from run 7-31.

(23) FIG. 21 XRD patterns of dolomite composite sorbent containing 5 wt % eutectic LiNaK-carbonate (pre-calcined at 350 C.) before testing. Red filled square=CaCO3 phase, Blue filled diamond=Ca(OH)2 phase, pink filled triangle=MgO phase.

(24) FIG. 22 XRD patterns of the dolomite composite sorbent after parametric CO2 sorption tests (activated state). Red filled square=Ca(OH)2 phase, Blue filled diamond=MgO phase, green filled diamond=CaO phase.

(25) FIG. 23 XRD patterns of the dolomite composite deactivated after CO2 sorption tests (sorbent exposed to liquid water). Black line=Dolomite, pink filled triangle (up)=Ca(OH)2, orange filled triangle (down)=Mg(OH)2, green filled circle=CaCO3 phase

(26) FIGS. 24A-24B show TiO.sub.2 monolith used to load the sorbent of present invention.

(27) FIGS. 25A-25D show microstructures of the NiCuMgCeAl oxide composite catalyst particle.

(28) FIGS. 26A-26B show Gas production profiles of bio-oil reforming in four monolith catalyst channels after periodic regeneration in air (reforming conditions: bed temperature=560 C., pressure=5 psig, 0.2 cc/min bio-oil, 0.2 cc/min de-ionized water, 200 sccm Argon purge gas; regeneration conditions: 200 sccm air at the same temperature and pressure). (A) 7 reforming/regeneration cycles in 1.sup.st day (B) 5 reforming/regeneration cycles in 2.sup.nd day.

DETAILED DESCRIPTION OF THE INVENTION

(29) One of the advantages of the present invention is that it can reduce the size and complexity of hydrogen production processes and devices. Compared to the conventional hydrogen production processes (FIGS. 1A-1B), the inventive process (FIG. 1C) produces a hydrogen-rich stream from one reactor vessel without using large external furnace to heat the reactor, without requiring any oxygen, and without requiring a separate water-gas-shift reactor. A down-stream hydrogen purification unit can be dramatically downsized by producing a H.sub.2-rich stream.

(30) FIG. 2 schematically illustrates a swing reactor configuration for production of a H2-rich stream. In a preliminary step, bio-oil liquid can be converted to an aerosol with steam and introduced into the catalyst bed. The droplet size is preferrably smaller than the channel opening (and, preferably, is 1 mm or less). There are several techniques to obtain uniform distribution at this scale. The steam laden with the dispersed oil droplets flows through the monolith channel. Upon exposure to the hot catalyst, the majority fraction of the bio-oil may be vaporized for gas-phase SR and residual liquid is spread onto the channel wall as a thin film for liquid-phase SR.

(31) The following are the likely reactions occurring in the bed.
C.sub.nH.sub.m+nH.sub.2O=(n+m/2)H.sub.2+nCO steam reforming
CO+H.sub.2O=H.sub.2+CO.sub.2 water gas shift
C.sub.nH.sub.mO.sub.k.fwdarw.C.sub.xH.sub.y+kH2O Coking & de-oxygenation reaction
CO.sub.2+MO=MCO.sub.3 CO2 capture
CO.sub.2 produced by the reforming reactions is captured with a metal oxide sorbent (MO). The exothermic carbonation reaction supplies heat to the endothermic SR reaction. The coking reactions are also exothermic. In the short term, aromatic-type coke containing some H element is typically formed which is reactive to oxidation. Graphite-type coke (nearly free of H), which tends to occur in the long term, can be avoided by frequent regeneration.

(32) When the CO.sub.2 sorbent is saturated and H.sub.2 yield becomes low due to decreased temperature and catalyst deactivation, the reactor is switched to regeneration mode. Hot air or O2-containing gas is introduced into the catalyst bed to burn off the coke. As the catalyst bed is heated up, the metal carbonate decomposes to release CO.sub.2, thus regenerating the CO.sub.2 sorbent. The heat of carbonate decomposition may be partially or completely supplied by the combustion reaction. Residual fuel gas, which is rejected from the downstream PSA purification process, can be fed into the reactor undergoing regeneration and burned to supply additional heat. After regeneration, the reactor is switched back to the SR mode. In this way, the catalyst is maintained in an active state so that the SR reaction can be run at high space velocity.

(33) The compositions and structures of a preferred catalyst system of present invention are illustrated in FIG. 3. In this model, a working catalyst provides two kinds of active catalysis sitesacidic and redox. The acidic site enables cracking of larger bio-oil molecules (or polymers) into smaller molecules, while the redox site catalyzes steam reforming reactions to convert the bio-oil molecule or its fragments into CO.sub.2 and H.sub.2. These two sites are made adjacent each other so that concerted effects can be realized. The new catalyst system will preferably be active after air calcination. The materials providing redox catalytic sites are preferably metal oxide nano-composites consisting of transition metal (Ni, Cu, Fe) oxides and metal oxides of oxygen mobility (CeO.sub.2, ZrO.sub.2CeO.sub.2, TiO.sub.2). The catalyst is activated by air calcination. The materials providing acidic sites can be -alumina, ultra-stable zeolite Y, beta-zeolite, or HZSM-5.

(34) FIG. 4 illustrates a new sorbent design model. The MgO-based sorbent system is targeted by this work for low-temperature sorption (<400 C.) and CaO-based sorbent system is targeted for high-temperature sorption (>350 C.), based on thermodynamic calculation. In addition to chemical and physical properties, cost is an important factor to select raw materials for preparation of new sorbents.

(35) FIG. 5 shows that the pure MgO sorbent has a working temperature at lower end of the temperature range of present interest. The working temperature of CaO is at the upper end. Thus, thermodynamic equilibrium constant can be modified by introducing dopants into MgO lattice structures or by making MgCO.sub.3 form a compound with other metal carbonates. The preferred dopant is CaO or CaCO.sub.3. Vice verse, sorption properties of CaO may be modified by introduction of MgO. Sorption and regeneration kinetics is another important performance factor for a working catalyst. Two approaches have been explored to develop a stable sorbent of rapid kinetics. One approach is to stabilize the pore structures of the reactive material by use of some stabilizers so that the pore structures would be stable during constant conversion between MO and MCO3. The preferred stabilizing materials include Na.sub.2CO.sub.3, K.sub.2CO.sub.3, MgO, CaCO.sub.3, Al.sub.2O.sub.3, and TiO.sub.2. The stabilizers are the material that maintains a stable structure under sorption/regeneration conditions. Another approach is to catalyze reaction kinetics of CO.sub.2 gas with MO solid by incorporation of some catalytic materials at gas/MO interfaces. The possible catalytic materials are molten carbonates and/or nitrates of alkaline elements (Li, Na, K), which are alternatively called promoters in the descriptions herein. The preferred catalytic materials are molten carbonates of alkaline elements (Li, Na, K), because of its chemical and thermal stability.

(36) The reforming catalyst and CO.sub.2 sorbent materials are made into monolithic bed structures in the reactor. FIG. 6 shows two possible ways to construct such a monolith bed. One way (FIG. 6a) is to use an inert monolith substrate of porous walls, fill the alternate channels with the CO.sub.2 sorbent powder, and coat the reforming catalyst on the wall of open channels. As the bio-oil and steam flows through the channel, the reforming reaction takes place on the channel wall, produced CO.sub.2 diffuses across the channel wall and reacts with the CO.sub.2 sorbent. Another way is to use an active monolith substrate of channel walls comprising an active reforming catalyst. The CO.sub.2 sorbent is used to fill alternate channels. In such a configuration, CO.sub.2 mass transfer distance and heat transfer distance between the reforming site and CO.sub.2 capture site are minimized.

(37) In the monolith bed design, the SR catalyst, WGS catalyst (optional), and CO2 sorbent can be integrated in the same reactor thereby minimizing mass and heat transfer resistance between the SR reaction and carbonation reaction. Essentially, all these sequential reactions can occur at the same spot.

(38) Compared to the packed bed, the monolith bed includes the following advantages:

(39) Straight flow channels minimizes the dead space in the bed, avoids accumulation of residuals and particulates in the bed, and enables rapid changeover of reacting fluids;

(40) Straight flow channels provide a low pressure drop and minimize parasitic power consumption during regeneration;

(41) the reactions are confined inside individual channels and temperature run-away due to auto-thermal reactions can be mitigated; and

(42) adsorbent and catalyst materials are integrated into a fixed structure, and particle attrition and bed upset can be avoided during rapid swing operation.

(43) The monolithic reactor also provides unique performance attributes compared to fluidized beds. Fluidized beds have been studied for both bio-oil SR and biomass gasification. It is a commercially-proven technology for coupling of endothermic and exothermic reactions, and one successful example is the fluid catalytic cracking (FCC) process in refineries. However, the circulating fluidized bed (CFB) system involves complex designs and requires highly specialized technical resources to operate and maintain. For a stand-alone H2 production plant with a capacity that is orders of magnitude smaller than the FCC process, it will be difficult to make such a unit economical. The proposed monolith reactor is compared to CFB as follows:

(44) there is no loss of catalyst and sorbent in the monolith reactor, while significant catalyst loss could occur in the fluidized bed due to severe particle attrition and entrainment in reactor effluents;

(45) the monolith reactor enables the CO2 sorbent coupled with the reforming catalyst in a layer-by-layer structure, while sorbent and catalyst particles can be segregated in CFB; and

(46) the monolith reactor has a simple, modular-type structure that can be scaled up by numbering up of reaction channels. Automotive catalytic converters and diesel particulate filters are examples of how compact a monolith reactor can be made. In contrast, CFB designs are significantly affected by their processing capacity scale and the unit must be large to obtain high productivity.

(47) The monolith reactor makes it possible to develop a compact H2 production plant with a simple process flow diagram (FIG. 2). High (>90%) energy efficiency may be realized through effective thermal management at plant scale. The reactors are insulated to prevent heat loss. Thermal energy from reactor effluents is recovered through heat exchange with feed streams. Though two reactors are used to conduct respective reforming and regeneration reactions, the overall reactor size will be reduced by conducting the reforming reaction at a higher space velocity than the conventional SR reactor. >90% H.sub.2 gas stream can be produced from the reactor with in situ CO.sub.2 capture, which will reduce the PSA size compared to the conventional process. The high-temperature furnace and WGS reactor can be eliminated.

(48) As illustrated in FIG. 7, a composite sorbent comprises an inert phase, an active phase, and a promoting phase. The active phase reacts with CO.sub.2 under sorption conditions and releases CO.sub.2 under regeneration conditions. The preferred materials for the active phase are MgO, CaO, Mg(OH).sub.2, Ca(OH).sub.2, or mixture thereof. The inert phase maintains its crystalline structures during carbonation under the sorption conditions and de-carbonation of the active phase under the regeneration conditions, and thus, serves as a structural stabilizer. The preferred inert materials are MgO, CaCO.sub.3, alkaline carbonates, ceramic oxides (Al.sub.2O.sub.3, CeO.sub.2, ZrO.sub.2), and mixture thereof. The same material may function as an active phase or inert phase for different application conditions. For example, MgO is an active phase at working temperatures below 450 C. but can be an inert phase for working temperatures above 400 C. The particle or grain sizes of these two phases should be kept as small as possible to maximize the specific reaction surface area. The promoter is dispersed in the composite matrix to catalyze reaction of CO.sub.2 gas with the active phase and/or subsequent decomposition of the carbonate. The preferred promoters are eutectic alkaline carbonates that become liquid at the sorption and regeneration temperatures. For example, LiNaK-carbonate has a melting point around 400 C. and serves as an effective promoter at working temperatures around and above 400 C. The promoter is uniformly distributed in the composite sorbent and the liquid-phase promoter may be retained inside the composite pores by capillary force.

(49) After the sorbent was tested through tens of sorption/regeneration cycles, a fully-activated working sorbent containing the three major crystal phases, MgO, CaO, and Ca(OH).sub.2, was formed, as evidenced by XRD analysis. As expected, MgO crystal phase was intact during the sorption and regeneration as a structural stabilizer. The CaCO.sub.3 crystal phase was not present in an activated sorbent or its presence is minor. CaO can be converted into Ca(OH).sub.2 in the presence of water vapor. The LiNaK-carbonate phase remained dispersed and was not detectable by the XRD. The following are possible chemical reactions involved in the sorbent preparation and sorption/regeneration processes.

(50) Partial decomposition of dolomite at temperatures lower than 500 C.:
CaMg(CO.sub.3).sub.2(s).fwdarw.MgO.sub.(s)+CaCO.sub.3(s)+CO.sub.2(g)(1)

(51) Fully-decomposed dolomite at temperatures higher than 700 C.:
CaMg(CO.sub.3).sub.2(s).fwdarw.MgO.sub.(s)+CaO.sub.(s)+2CO.sub.2(g)(2)

(52) In the presence of H.sub.2O
CaO.sub.(s)+H.sub.2O.sub.(g).fwdarw.Ca(OH).sub.2(s)(3)

(53) CO.sub.2 sorption/regeneration:
CaO.sub.(s)/MgO.sub.(s)+CO.sub.2(g)CaCO.sub.3(s)/MgO.sub.(s)(4)
Ca(OH).sub.2(s)/MgO.sub.(s)+CO.sub.2(g)H.sub.2O.sub.(g)+CaCO.sub.3(s)/MgO.sub.(s)(5)

(54) As illustrated by SEM images, the as-prepared and activated sorbent have similar micro-structures. Ca, Mg, and alkaline metals are all well mixed at micrometer scale in both fresh and activate sorbents as a composite rather than as segregated particles. The molten carbonate works as a phase transfer catalyst to facilitate the sorption and regeneration reaction process.

EXAMPLES

Example I CO2 Sorbent Preparation

(55) The dolomite-based composite sorbent was prepared in the following way. The Li.sub.2CO.sub.3Na.sub.2CO.sub.3K2CO3 eutectics (LiNaKCO.sub.3) has a melting point about 397 C. It was prepared by mixing 32.2 wt. % Li2CO3 (99%, Sigma Aldrich), 33.3 wt. % Na2CO3 (99%, Sigma Aldrich) and 34.5 wt. % K.sub.2CO.sub.3 (99%, Sigma Aldrich). The powder mixture was ground together and then heated to 410 C. for 1 hr. The resulting eutectic was crushed and ground to a fine powder. Dolomite from City Chemical was used as received of after calcination at 850 C. for 4 hours in air. The dolomite was mixed with LiNaKCO.sub.3 at desired weight ratio by ball milling. The solid mixture was added into a Nalgene plastic bottle and mixed with 2-propanol (EMD Chemicals, Canada) and zirconia beads (diameter: 0.3-1.0 cm). The bottle was rotated at a speed of 150-200 rpm for 48-72 hours. The resulting slurry was dried at room temperature (RT) to allow evaporation of 2-propanol. Following drying, the cake was calcined at 350 C. or 725 C. in air in an alumina crucible for 3 hours. The comparative CaO sorbent was prepared by calcining Ca acetate (Alfa Aesar, 97%) at 800 C. for 3 hrs. The comparative MgO sorbent was obtained by calcining Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.xH.sub.2O power (99%, Sigma Aldrich) at 450 C. in air for 3 hours.

(56) Dolomite alone sorbent was prepared by heating an as-received dolomite mineral (City Chemical) was at 850 C. for 3 hours in a furnace to obtain complete decomposition.

(57) MgO was obtained by calcining Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.xH.sub.2O power (99%, Sigma Aldrich) at 450 C. for 3 hours in air. MgO was mixed with Na.sub.2CO.sub.3 (99%, Sigma Aldrich), Li.sub.2CO.sub.3 (99%, Sigma Aldrich), and K.sub.2CO.sub.3 (99%, Sigma Aldrich). The mixture contained 44 wt % MgO, 48 wt % Na.sub.2CO.sub.3, 3.9 wt % Li.sub.2CO.sub.3 and 4.2 wt % K.sub.2CO.sub.3. Typically, 33.5 g of the solid mixture was mixed with 60-100 g of 2-propanol (EMD Chemicals, Canada) and 120 g-200 g of zirconia beads (diameter: 0.3-1 cm). The bottle was rotated for 48-72 hours at a speed of 150-200 rpm. The obtained slurry was dried at RT C. in plates to evaporate 2-propanol and form thin cake (0.2-0.5 mm). Following the dry, the cake was calcined at 450 C. for 3 hrs. The calcined cake was crushed and sieved to 40-100 mesh particles for fixed-bed tests.

Example II CO2 Sorption Performances by TGA Tests

(58) Performance characteristics of sorbents for CO.sub.2 capture under steam-reforming conditions were tested on a thermo gravimetric analyzer (TGA, Netzsch Thermal Analysis, STA 409 cell) at ambient pressure. The sample weight for each test was approximately 20 mg. CO.sub.2 absorption was evaluated by heating sample in 10-100% CO.sub.2 to 500-600 C. Cyclic CO.sub.2 absorption and desorption were evaluated by exposing the sample to the CO.sub.2 gas for 50 minutes at 550 C. and then, raising the temperature in N2 flow and holding at 700 C. for 60 minutes. The gas flow rates for the sorption and regeneration processes were maintained at 70 ml/min and 90 ml/min, respectively. The heat of absorption was measured along with the TG tests through differential scanning calorimetry (DSC). The TGA tests help to identify CO.sub.2 sorption and regeneration temperatures, measure CO.sub.2 sorption capacity, and assess sorption and regeneration kinetics.

(59) For comparison, performances of CaO sorbents are shown in FIG. 8. FIG. 8a shows that the CaO sorbent weight increased with CO.sub.2 capture, and weight loss occurred only when the regeneration temperature was increased to 680 C. More regeneration occurred as the temperature was raised to 750 C. The regeneration temperature was not lowered by adding about 10 wt % promoters into CaO. The working capacity at higher regeneration temperatures diminished due to addition of this promoter. The results indicate sensitivity of CaO sorbent performances to the kind of promoters added.

(60) Furthermore, sorption/regeneration performances of the CaO sorbents with and without the promoter are compared at different sorption temperatures but under constant regeneration temperature at 700 C. in FIG. 8b. The CaO sorbent shows a little CO.sub.2 uptake at 500 C. sorption temperature. The CO.sub.2 sorption increases as the sorption temperature is raised to 550 C. and 600 C. By contrast, the promoter-added CaO provides less CO.sub.2 uptake than the CaO alone. The results indicate that the promoter works more effectively for the proposed composite sorbent structure in which a structural stabilizer is present. The CaO material alone may not be able to hold the molten carbonate promoter during the sorption/regeneration cycle.

(61) Because Mg and Ca are cheap alkaline earth metals, their compounds are attractive materials for CO.sub.2 capture application. Dolomite is a natural mineral of Mg and Ca carbonate compounds. At lower temperature, MgCO.sub.3 in dolomite is decomposed, whereas CaCO.sub.3 would decompose at a higher temperature.
MgCa(CO.sub.3).sub.2.fwdarw.MgO+CaCO.sub.3+CO.sub.2 at 400-450 C.
MgCa(CO.sub.3).sub.2.fwdarw.MgO+CaO+CO.sub.2 at 700-850 C.
To investigate feasibility of using this raw material for present application, the pre-calcined dolomite powder was tested under two sets of sorption/regeneration conditions (FIG. 9). At 500 C. regeneration temperature, no significant weight change was observed as the conditions were switched between sorption and regeneration. The sorbent was likely saturated by CO.sub.2 and the resulting carbonate did not decompose at the regeneration temperature. The weight gain/loss cycles appeared only when the regeneration was conducted at 700 C. and above. The results indicate that 700 C. is required to regenerate this sorbent.

(62) FIG. 10 shows the TGA testing results of the dolomite composite sorbent of present invention, which was prepared by adding 10 wt % LiNaK-carbonate into the above dolomite as promoter. The sorbent was tested under two sets of conditions. In first set of conditions, the sorption and regeneration temperatures were kept constant at 400 C. and 500 C., respectively. No apparent CO2 sorption working capacity was obtained in sorption/regeneration cycles, because the regeneration temperature was too low. In another set of testing conditions, the sorption temperature was kept constant at 500 C. while the regeneration temperature was varied from 600 to 750 C. Little CO2 working capability was shown at regeneration temperature below 700. The working capacity becomes significant at and above 700 C. regeneration temperature. The sorption equation is expressed as follows:
CaO.sub.(s)/MgO.sub.(s)+CO.sub.2(g)CaCO.sub.3(s)/MgO.sub.(s)
In FIG. 11, testing results for MgO, dolomite, and dolomite composite sorbents are compared under the identical sorption/regeneration conditions. The dolomite composite was prepared by dispersing 10 wt % LiNaKCO3 in dolomite. Synergistic effects of the composite sorbent design are clearly demonstrated. While the regeneration conditions (700 C. in air) were kept constant, CO.sub.2 sorption in was conducted at 500 C. for first two cycles, 550 C. for next two cycles and at 600 C. for last two cycles. There was little weight change for the MgO sorbent during these cycles, which confirms that MgO is an inert phase under these working conditions. Compared to the dolomite alone, the promoted dolomite shows much rapid sorption and desorption, and a large CO.sub.2 sorption working capacity.

(63) The above dolomite composite sorbent can be used at lower working temperatures, in which MgO becomes an active phase while CaCO.sub.3 functions as an inert phase. FIG. 12 shows performances of the dolomite composite sorbent at lower sorption and regeneration temperatures.
MgO.sub.(s)/CaCO.sub.3(s)+CO.sub.2(g)MgCO.sub.3(s)/CaCO.sub.3(s)
The sorbent was tested under three sets of sorption/regeneration conditions. The solid green and red lines in FIG. 12 represent the weight changes in two runs with respective 400 and 450 C. regeneration temperatures at the same sorption temperature (360 C.). The CO.sub.2 working capacity was stabilize around 5.6 wt. % after several cycles with 400 C. regeneration. The working capacity was about 5.75 wt. % with 450 C. regeneration temperature. The results indicate that CO.sub.2 captured at 360 C. can be efficiently regenerated at 400 C. The tests with 400 C.-sorption and 550 C.-regeneration temperature (dashed blue line) showed no significant weight change (solid blue line) during the sorption/regeneration cycles. The results suggest that working sorption temperature and regeneration temperatures for this composite sorbent are less than 400 C. and above 400 C. -450 C., respectively.

(64) Performance characteristics of a different composite sorbent are shown in FIG. 13. This sorbent comprises 44 wt % MgO as an active phase, 44 wt % Na.sub.2CO.sub.3 as an inert phase, and 12 wt % LiNaKCO.sub.3 as the promoting phase. Since MgCO.sub.3 decomposes at much lower temperature than CaCO3, this sorbent can be quickly regenerated at 500 C. or below. A stable 18.9 wt % working capacity was shown through 8 sorption/regeneration cycles.

(65) The experimental results conducted this quarter for CO.sub.2 sorbents are summarized in table 4. The sorbents that work at sorption temperatures 400 C. with regeneration temperature<600 C. are identified. More experiments are being conducted to find the sorbents with sorption temperatures from 400 to 550 C.

(66) TABLE-US-00004 TABLE 4 CO.sub.2 working capacity of sorbents with and without the eutectic LiNaK-carbonate promoter Initial sorption capacity (wt. %) Cyclic sorption capacity of the sorbent containing (sorption/regeneration temperature) promoter (sorption/regeneration temperature) Sorbent Without With some 500 C./ material promoter promoter 360 C./450 C. 400 C./500 C. 750 C. MgO <2% (330-385 C.) ~50% (330-385 C.) 60% in first T too high for sorption cycle, <1% in 2-8 cycle MgONa.sub.2CO.sub.3 7-8% (350-400 C./ 18-20% (350-400 C./ Stabilized at 15% Stabilized at T too high for 400-500 C.) 400-500 C. C.) 15% adsorption CaO 25% (500-600 C./ 25% (300-450 C./ T too low for regeneration unstable >680 C.), slow >680 C.), fast kinetics kinetics Decomposed 12% (500-600 C./ 25% (350-400 C./ Stable 5-8% 20% in first 25% dolomite >680 C.), slow, 400 C.-680 C.), cycle, <1% in kinetics fast kinetics 2-8 cycle

(67) To confirm performances of the composite sorbent design, a larger number of sorption/regeneration cycling tests were performed with two dolomite sorbents of different promoter loading levels. The sorption was conducted at 550 C. in 100% CO.sub.2 and regeneration was performed at 700 C. in N.sub.2. Sorbent #1 loaded with 5 wt. % promoter was tested for 16 cycles. Sorbent #2 loaded with 10 wt. % promoter was tested for 8 cycles. The results are plotted in FIG. 14. For the sorbent #1, the weight change due to CO.sub.2 sorption is low initially, but increases to 14.8 wt. % after 8.sup.th cycle and is stabilized at this level in the subsequent cycling tests. The sorbent #2 provides 19.9 wt. % initial CO.sub.2 uptake but its CO.sub.2 sorption weight gain declines to 11.8% after 8 cycles. Thus, 5 wt. % addition of the promoter looks sufficient and excessive addition may not have any benefit.

(68) TGA screening tests revealed strong synergism of the promoted dolomite sorbent. Impacts of the sorbent preparation on its cyclic performances were studied. The results are summarized in table 5. The dolomite can be used as received or pre-calcined at 850 C. in air for hours. The 850 C.-calcination converts the carbonate into Mg and Ca oxides. Addition of the promoter into the dolomite was evaluated at two different loading levels (5 wt. %, 10 wt. %). The resulting dry mixtures were calcined at two different temperatures (350, 725 C.) prior to TGA tests. Comparative pairs of sorbents #1 vs. 2, 3 vs. 4, and 5 vs. 6 show the impact of dolomite starting materials on the CO.sub.2 working capacity at the same promoter loading level and at the same calcination temperature. The CO.sub.2 sorption capacity as-measured with the as-received dolomite is normalized on the basis of MgO+CaO content, i.e., on the same basis as the sorbent derived from the calcined dolomite. No obvious advantage can be seen by using the pre-calcined dolomite. Comparative pairs, sorbent 1 vs. 3, 2 vs. 4, and 7 vs. 6, show no obvious advantage by increasing the promoter loading from 5 to 10 wt. % with the same starting material and same calcination temperature. Comparative pairs of sorbents 3 vs. 5, 4 vs. 6, and 2 vs. 7 reveal the impact of the composite sorbent calcination temperature with the same dolomite precursor and same promoter loading level. 725 C.-calcination does not show any significant difference from 350 C.-calcination. This group of experiments indicates that the composite sorbent preparation is not so sensitive to the starting material, calcination temperature, and promoter loading. A working sorbent structure is formed through repeated sorption/regeneration test cycles. The promoter is used as an additive to decorate the solid surface and intended not to exist as a separate phase. Thus, its excessive loading is not necessary or may become a negative factor by blocking accessibility of CO.sub.2 into the sorbent pores.

(69) TABLE-US-00005 TABLE 5 Effects of composite sorbent preparation on CO.sub.2 sorption performances (TGA test conditions: Sorption 550 C. 10% CO.sub.2/regeneration condition 700 C. N.sub.2) Sorbent Promoter addition Calcination Sorption/regeneration CO.sub.2 working capacity No Starting material level temp cycle # normalized, wt. % Effect of starting dolomite materials 1 As-received 5 wt % 725 C. 1st.fwdarw.8.sup.th.fwdarw.16.sup.th 19.4.fwdarw.28.3.fwdarw.28.3 2 850 C.-calcined 1st.fwdarw.8.sup.th 37.5.fwdarw.17.7 3 As-received 10 wt % 725 C. 1st.fwdarw.8.sup.th 38.0.fwdarw.22.7 4 850 C.-calcined 1st.fwdarw.8.sup.th 34.6.fwdarw.18.0 5 As-received 10 wt % 350 C. 1st.fwdarw.8.sup.th 23.3.fwdarw.20.5 6 850 C.-calcined 1st.fwdarw.8.sup.th 27.2.fwdarw.21.5 Effect of promoter addition level 1 As-received 5 wt % 725 C. 1st.fwdarw.8.sup.th.fwdarw.16.sup.th 19.4.fwdarw.28.3.fwdarw.28.3 3 10 wt % 1st.fwdarw.8.sup.th 38.0.fwdarw.22.7 2 850 C.-calcined 5 wt % 725 C. 1st.fwdarw.8.sup.th 37.5.fwdarw.17.7 4 10 wt % 1st.fwdarw.8.sup.th 34.6.fwdarw.18.0 7 850 C.-calcined 5 wt % 350 C. 1st.fwdarw.8.sup.th 29.7.fwdarw.17.0 6 10 wt % 1st.fwdarw.8.sup.th 27.2.fwdarw.21.5 Effect of composite calcination temperature 3 As-received 10 wt % 725 C. 1st.fwdarw.8.sup.th 38.0.fwdarw.22.7 5 350 C. 1st.fwdarw.8.sup.th 23.3.fwdarw.20.5 4 850 C.-calcined 10 wt % 725 C. 1st.fwdarw.8.sup.th 34.6.fwdarw.18.0 6 350 C. 1st.fwdarw.8.sup.th 27.2.fwdarw.21.5 2 850 C.-calcined 5 wt % 725 C. 1st.fwdarw.8.sup.th 37.5.fwdarw.17.7 7 350 C. 1st.fwdarw.8.sup.th 29.7.fwdarw.17.0

Example III. Packed Bed CO2 Sorption/Regeneration Tests of Composite Sorbents

(70) A packed bed sorption test was conducted on a tube tubular reactor (316 stainless steel, 0.5 OD, 0.049 wall thickness). The sorbent particles of 40-100 mesh were loaded into the reactor tube by tapping the reactor wall. The resulting packing density was about 0.6 g/cc. The sorbent bed was held by quartz wool on the top and bottom. The gas flow was directed downward through the sorbent bed. Individual gas flow rates were controlled by mass flow controllers (MKS Instruments model 1179A and 1479A), while water flow rate was controlled by HPLC pump (Cole Parmer model DigiSense 89000). The bed temperature was controlled by the furnace heating. The sorbent bed was heated to 700 C. in 0.5 liter/min air to activate prior to lowering to designated sorption temperatures. The water was preheated to vaporize at 150 C. prior to entering the reactor. The reactor effluent was cooled down to 4 C. to condense the majority of the entrained water vapor. The residual gas was analyzed by a quadruple mass spectrometer (Kurt J. Lesker model Quad 200). Typically, 0.5 liter/min dry gas consisting of 33% CO.sub.2 and 67% H.sub.2 was used to simulate the reforming gas.

(71) To elucidate effects of sorption conditions on the sorbent performances, we conducted packed bed tests with the sorbent #1. FIG. 15a shows CO.sub.2 breakthrough curves with dry gas of H.sub.2/CO.sub.2=2/1. CO.sub.2 loading is calculated by integrating the sorption breakthrough curves (FIG. 15b). The sorption capacity tends to decrease in three consecutive cycling. The sorbent cycling stability is substantially enhanced by addition of H.sub.2O into the feed gas. The four sorption curves with H.sub.2O/dry gas=0.25 converge quickly (FIG. 15c). With H.sub.2O/dry gas=1.0, the CO.sub.2 sorption curves for 4 cycles completely overlap (FIG. 15d). The positive effect of steam on the sorbent stability is clearly demonstrated. The sorbent appears to be more stable in the presence of steam. Such performance characteristics are highly desirable for CO.sub.2 capture under reforming conditions and for most practical applications, since the presence of steam is ubiquitous.
The present composite sorbent exhibits very rapid sorption kinetics. The CO.sub.2 sorption on the packed bed is nearly completed within 2 min for all the runs. It is estimated from the sorption breakthrough curve that the first order CO.sub.2 sorption rate constant is about 9.4 l/s for the un-saturated sorbent and about 4.0 l/s for the 95% saturated. The rapid sorption is necessary to reduce the reactor size and to combine the CO.sub.2 sorption with steam reforming reactions in situ. The CO.sub.2 sorption rate obtained in this work is comparable to CO.sub.2 adsorption into porous adsorbents. The former is a gas/solid carbonation reaction process, while the latter is mostly a physical adsorption process. The rapid sorption kinetics is attributed to catalyzing functions of the promoter. CaO has a higher density than CaCO.sub.3. It is known that solid diffusion often is a rate-limiting step for carbonation reactions. The liquid-phase promoter and presence of H.sub.2O may help breakup of CaO crystals into highly-porous structures for rapid CO.sub.2 diffusion and reaction.

(72) The same sorbent bed was tested under various conditions over a period of 17 days, while the regeneration conditions were kept the same (700 C. in air). It was noticed that the CO.sub.2 sorption capacity increased with the time as shown in FIG. 16a. During a 17-day testing period, the sorbent was tested at different sorption temperatures (400 to 650 C.), different H.sub.2O/dry gas ratios (0 to 1), and different reactor pressures (1 to 3 bars). Under these testing conditions, CO.sub.2 sorption for the CaO material is not limited by thermodynamic equilibrium. The CO.sub.2 sorption capacity is mainly determined by the active phase available for reversible carbonation reaction. This is evidenced by the CO.sub.2 sorption capacities measured at different temperatures (FIG. 16b). These results indicate that it may take a long time for a sorbent to establish a fully-activated working state. Rather than having a durable, permanent porous sorbent structure, the present composite sorbent realizes long-term, dynamic stability through reversible conversion of the sorbent between the carbonated and de-carbonated states. Such a conversion process is facilitated by the presence of promoter and steam. This synergistic sorbent design concept may be applied to other materials.

Example IV. Micro-Structures of the Composite Sorbent of Present Invention

(73) The dolomite sorbents prepared and tested in the previous examples were analyzed by electron scanning electromicroscopy (SEM) to check the micro-structures and compositions. As shown by SEM pictures in FIG. 17, all the four samples have a porous structures with grains or dense crystals less than 1.0 m. Table 6 lists the sorbent compositions of two fresh sorbents and two spent sorbents. It is noted that the sorbent was made by ball-milling of decomposed dolomite and eutectic LiNaK-carbonate. Li could not be measured by SEM probe. As expected, Mg, Ca, Na, and K are the dominating metal elements in these sorbents. Ca/Mg atomic ratio is close to stoichiometric Ca/Mg ratio (1:1) in the dolomite. Ratios of Na and K to Mg are all less than 0.20, because they are minor constituents as a promoting element.

(74) TABLE-US-00006 TABLE 6 Atomic compositions of dolomite composite sorbents of present invention Atomic ratio As-prepared (fresh) of metal Calcined Calcined at Tested in the packed bed element to Mg at 350 C. 725 C. Run 6-12 Run 7-31 Mg 1.00 1.00 1.00 1.00 Ca 0.87 1.04 1.11 1.11 Na 0.11 0.17 0.09 0.09 K 0.06 0.12 0.06 0.06
In addition to atomic compositions, the elemental distribution is very important to obtain the synergistic effects of the composite sorbent. Elemental mapping was conducted during SEM analysis. Maps of Mg, Ca, Na and K elements for one fresh and two spent sorbents are presented in FIGS. 18-20, respectively. Uniform distribution of Mg, Ca, Na, and K is shown by the three samples. The spent sorbent from run 6-12 was unloaded from the reactor after 18 cycles of repeated sorption/regeneration tests, sorption at 500 C. and regeneration at 700 C. The spent sorbent from run 7-31 was tested over a temperature range of 300 to 700 C. in a 17-day testing period of time. Those two sorbents did not show any apparent deactivation during testing. The SEM elemental mapping confirms that an active sorbent is associated with uniform elemental distribution.

(75) The crystal phases of the composite sorbent were measured by X-ray diffraction (XRD). FIGS. 21-23 show XRD peaks for the fresh, activated, and deactivated dolomite composite sorbents, respectively. The sorbent was prepared by incorporating 5 wt % eutectic LiNaK-carbonate into the decomposed dolomite. The major crystal phases in the as-prepared sorbent (FIG. 21) are MgO, CaCO3, and Ca(OH)2. MgCO3 in the dolomite was completely decomposed into MgO, while CaCO3 was partially decomposed into CaO. Ca(OH).sub.2 could be formed from hydration of CaO by moisture in ambient air. LiNaK-carbonate could not be detected by XRD because it presents in small quantities and is well dispersed in the composite.

(76) After the sorbent was tested under various conditions and unloaded from a fully-activated state, MgO crystal phase was intact (FIG. 22) because MgO served as a structural stabilizer of the composite sorbent under the present testing conditions. Ca(OH)2 and CaO in the activated sorbent are the active phase for CO2 sorption, which is expected. By contrast, metal oxide phases disappeared while the dolomite crystal phase emerged in a deactivated sorbent (FIG. 23). The composite sorbent was accidently deactivated due to condensation of liquid water in during CO2 sorption in the packed bed tests. The liquid water leached out all the eutectic carbonate from the composite sorbent so that the deactivated sorbent could not be regenerated at 700 C., which was the regeneration temperature during parametric and cyclic tests.

Example V. Comparative Example of Dolomite-Based Sorbent

(77) This example shows that sorbents without a sufficient amount of eutectic carbonate promoter is not active for CO2 sorption. Dolomite from City Chemical was calcined at 850 C. for 4 hours in air. 90 g of 850 C. calcined dolomite (MgOCaO) was mixed with 3.22 g of Li2CO3 (99%, Sigma Aldrich), 3.33 g of Na2CO3 (99%, Sigma Aldrich) and 3.45 g of K2CO3 (99%). The solid mixtures were added into a 500 ml Nalgene plastic bottle and mixed with 250 g of 2-propanol (EMD Chemicals, Canada) and 500 g of zirconia beads (diameter: 0.3-1 cm). The bottle was rotated for 18-96 hours at a speed of 150-200 rpm. The obtained slurry was dried at RT C. in plates to evaporate 2-propanol and form 0.2-0.5 mm thick cake. The cake was crushed and dried at 120 C. Then the sieved particles (<100 mesh) were calcined 725 C. for 3 hours in air.

(78) Both dried and pre-calcined sorbent particles were tested for CO2 sorption in the packed bed at 500 C. sorption temperature in CO2 and 725 C. regeneration in air. The sorbents showed initial CO2 sorption activity but quickly de-activated in the subsequent test cycles. The samples were analyzed to understand the problem. The atomic compositions of as-prepared and tested sorbents are listed in the Table 7 below.

(79) TABLE-US-00007 TABLE 7 Dolomite-based composite sorbents containing in-sufficient promoter Atomic ratio of metal As-prepared Tested in the packed element to Mg Dried at 120 C. Pre-calcined bed 500 C./725 C. Mg 1.00 1.00 1.00 Ca 1.04 0.73 0.38 Na 0.07 0.03 0.02 K 0.05 0.02 0.02
Small grains and porous structures (FIG. 17) are shown by the samples after drying, pre-calcination, and testing. However, Na and K content were drastically reduced after the sample was pre-calcined and tested. It is noted that Li could not be analyzed by SEM. Compared to the active, stable sorbent shown in the previous example, the sorbent prepared in this example has low Na and K content after testing. Elemental maps of Mg, Ca, K, and Na are shown in FIG. 18 indicating that even though the dried sample has certain amounts of Na and K, there is segregation of Na and K. To form a eutectic phase, Na and K carbonates need to exist together. The Na and K content in the pre-calcined and tested samples are too low to be clearly mapped in FIGS. 19 and 20.

(80) This example confirms the necessity to have an eutectic carbonate phase be uniformly distributed in an active composite sorbent with adequate amounts, such as, K and Na ratios to Mg greater than 0.020.

Example VI. Loading of Active Sorbents into Monolith Structures

(81) A TiO2 monolith (Cormetech, NC) was used to make the monolith-structured sorption bed. As shown in FIG. 24a, a monolith block with about 1 mm square channels and 0.36 mm wall thickness was core-drilled into pieces of 20 mm diameter for experimental purposes. This monolith has meso-porous wall structures to hold the sorbent particle and allow gases diffuse across. The monolith surface area decreased with increasing calcination temperature (FIG. 24b). The monolith maintains mechanical integrity and porous structures after various hydrothermal treatment. Several techniques were evaluated to load the sorbent particles into the monolith channels, which includes filtration of sorbent slurry through the channel wall, precipitation of the sorbent particles from into the channel from slurry, and dry powder packing. The dry powder packing was found to be a simple, effective method. The procedures are described in the following.

(82) First, alternative rows of channels on the bottom monolith were plugged by cement to hold the sorbent powder. Then, adjacent rows of the channels on the bottom monolith were plugged by cement to prevent the sorbent powder from filling all the channels. The dolomite sorbent was crushed and sieved to the sizes well below the channel opening (1.0 mm), such as 300 m. The pugged cement was held inside a tube that was mounted onto a vibrator or shaker in vertical orientation. The sorbent powder was poured onto top of the monolith, while the tube was shaken or vibrated. The powder may be added gradually as the channels were being filled. Filling was stopped after the channel was full.

(83) Nine pieces of the monoliths were filled with the composite sorbent powder and associated weight gains are listed in the Table 8 below. The average packing density of the sorbent powder inside the channel is 0.68 g/cc with standard deviation of 0.105 g/cc by assuming 1.0 mm channel width and 0.5 cm plugged channel length.

(84) TABLE-US-00008 TABLE 8 Loading of CO2 sorbent powder into TiO2 monolith by dry powder packing Monolith ID Length # of channels Wt. % Packing 60195 cm filled Monolith sample weight, g change density, g/cc 129-1 6.0 48 8.360 21.2 0.67 129-2 5.7 57 8.550 24.2 0.70 129-3 5.5 53 7.680 16.3 0.48 129-4 5.3 53 7.850 22.1 0.68 129-5 5.3 53 8.100 17.5 0.56 129-6 5.2 60 7.690 28.5 0.78 129-7 5.2 54 7.351 23.1 0.67 129-8 5.0 54 7.063 25.8 0.75 129-9 4.9 54 6.693 28.9 0.81

Example VII. Composite Catalyst Preparation

(85) The NiCuMgCeCeAlO metal oxide composite catalysts were first prepared as particles to characterize their properties. The nitrate salts used in the preparation were Ni(NO3)2.6H2O 100.0%, Cu(NO3)2.2.5H2O 98%, Mg(NO3)2.6H2O 99%, Ce(NO3)3.6H2O 99%, and Al(NO3)3.9H2O 98%. The nitrate salts were weighed according to required stoichiometric ratios and mixed. De-ionized water was added to obtain a clear solution. Then, a mixture of NaOH (0.88 mmol/g) and Na2CO3 (0.88 mol/g) solution was prepared. The mixed metal nitrates solution was heated in a water bath on a hot plate to 75-80 C., the NaOH/Na2CO3 solution was added drop-wise with stirring to pH=9-10. The temperature was controlled at 75-79 C. For sample 61880-49, about 89 g of NaOH (0.88 mmol/g)/Na2CO3 (0.88 mol/g) solution was added to 85.5 g of metal nitrates solution in 20 min. The mixture was stirred for 1 hr at 75-78 C for 1 hr. The solution compositions used for preparation of the composite catalysts are summarized in table 9. The precipitate was aged for 10 h at RT, centrifuged and washed with DI water for 4 times until pH=7. The precipitate was dried overnight at 40-50 C. and then 120 C for 28 hr. The dried precipitates was heated at 1 C./min to 500 C. and held at 500 C. for 6 h in air.

(86) The BET surface areas and pore sizes of four composite catalysts are listed in Table 10. The first four samples were prepared in the same batch at about 10 g scale. BET surface area and pore volume decreased with increasing Al content in the composite, while the pore size increased. The Ni:Cu:Mg:Ce:Al=1:0.2:0.1:1:2 formulation was chosen for parametric studies of the preparation process. A larger batch of the particle (100 g scale) was prepared using this formulation with quick precipitation and 2 times of water washing. With the sample calcination condition, the resulting catalyst has BET surface area of 140 m2/g, slightly less than the small-scale trial. The catalyst was further calcined at 725 C. for 6 hours.

(87) TABLE-US-00009 TABLE 9 Solution concentrations used for preparation of NiCuMgCeCeAlO composite catalyst particle Atomic ratio of metal Catalyst elements in solution Metal-NO3 solution conc. mmol/g # Ni Cu Mg Ce Al Ni Cu Mg Ce Al 61880-35 1 0.2 0.35 0.2 1.8 0.341 0.068 0.119 0.068 0.613 61880-49 1 0.2 0.1 1 2 0.190 0.038 0.019 0.190 0.380 61880-53 1 0.2 0.1 1 1 0.184 0.037 0.018 0.184 0.184 61880-55 1 0.2 0.1 1 0 0.229 0.046 0.023 0.229 0.000 61880-70- 1 0.2 0.1 1 2 0.324 0.065 0.032 0.324 0.647 61880-70 725 C.

(88) TABLE-US-00010 TABLE 10 BET surface area and pore size of prepared NiCuMgCeCeAlO composite catalyst Surface Pore Pore Size, area Volume A Catalyst # m2/g cc/g Ad/De 61880-35 238.5 0.46 60/40 61880-49 163.0 0.43 65/50 61880-53 91.5 0.33 95/65 61880-55 39.8 0.17 200/100 61880-70- 140.1 0.25 65/50 61880-70 725 C. 76.1 0.2 95/80

Example VIIII. Preparation of Composite Reforming Catalysts in Monolith Structures

(89) The same TiO.sub.2 monolith as used in the previous sorbent loading was used to make the monolithic reforming catalyst by impregnation. Table 11 lists the four solutions used for impregnation. The impregnation solution was prepared using the same metal precursors as used in the above example. The preparation procedure is described in the following. The 2-cm TiO.sub.2 monolith was fully immersed in the solution at room temperature (20 C.) and soaked a few minutes under vacuum until no gas bubbles emerged out of the solution. The monolith was taken out of the solution. The excessive solution was drained first and then spins out by centrifugation. The wet sample was left in the fume hood to dry overnight and further dried in an oven at 120 C. The dried sample was calcined at 500 C. for 6 h with 1 C./min ramp rate in air. The impregnation was repeated to increase the catalyst loading.

(90) After the calcination, the monolith body was cut open to expose the interior channels. All the channels looked uniform in color and were of any slid deposit on the channel wall. Thus, the metal oxide reforming catalyst was deposited into the TiO.sub.2 support pores. The monolith was crushed into particles for BET surface area and pore volume measurements. The BET surface area and pore volume decreased with increasing the catalyst loading. This is explained by increased occupancy of the pores on the monolith channel by the catalyst.

(91) TABLE-US-00011 TABLE 11 Preparation of monolith reforming catalysts by impregnation solution concentration, Weight Catalyst metal mmol/g Time of gain Catalyst ID name ratio Ni Cu Mg Ce impregnation wt % 61880-20-1 Ni/TiO2 5 2.66 1 14 61880-25-1 Ni/TiO2 5 2.66 2 17 61880-25-2 NiCu/TiO2 5:1 2.27 0.47 2 19 61880-34 NiCuCe/TiO2 5:1:5 0.97 0.194 0.96 2 19 61880-25-3 NiCuMgCe/ 5:1:1.75:1 1.31 0.26 0.25 0.45 4 26 TiO2
With the above success, impregnating TiO2 monoliths was tried with more complex solutions. Different from the above procedure, the impregnation was conducted with hot solution and monolith to increase the catalyst loading. One impregnation solution was prepared by mixing the Ni(NO3)2.6H2O, Cu(NO3)2.2.5H2O, Mg(NO3)2.6H2O, Ce(NO3)3.6H2O, and Al(NO3)3.9H2O salts with an atomic ratio of Ni:Cu:Mg:Ce:Al=1:0.2:0.1:1:2. The weight concentration is shown in table 12. A minimal amount of water was added into the salt mixture, heated, and stirred at 60 C. until complete dissolution. A clear, green solution was obtained and denoted Sol 61880-72. Another solution was prepared by adding KNO3 salt in the above mixture with an atomic ratio of K/M (M=Ni+Cu+Mg+Ce+Al)=0.08, which is denoted as Sol 61880-72-K.

(92) TABLE-US-00012 TABLE 12 Solution concentrations used for impregnating NiCuMgCeA composite catalyst Solution # Ni(NO3)26H2O Cu(NO3)22.5H2O Mg(NO3)26H2O Ce(NO3)36H2O Al(NO3)39H2O KNO3 61880-72 18.5% 3.0% 1.7% 28.0% 48.8% 0% 61880-72-K 17.7% 2.9% 1.6% 26.7% 46.6% 4.6%
Bare TiO2 monoliths were placed in 75 C. oven to warm up prior to impregnation. The impregnation was conducted by immersing the warm monolith in the 70 C.-solution and degassing under vacuum for 5-10 min until no major gas bubbles emerged. Then, the monolith was taken out of the solution. The excessive solution inside the channel was drained first and then, removed on a centrifuge at 3000 rpm for 2-5 minutes. The wet monolith was left in the fume hood to dry at room temperature, and dried inside an oven at 120 C. overnight. After drying, two monoliths were impregnated second time with respective solution. All the dried monoliths were calcined in a tubular furnace in air at 500 C. for 6 h. Table 13 lists the four monolith catalyst samples prepared.

(93) TABLE-US-00013 TABLE 13 TiO2 monoliths impregnated with NiCuMgCeAl oxide composite catalysts Sol density, Monolith Bare # of Weight gain after Monolith ID Solution # g/cc length, cm weight, g impregnation calcination, wt % 60195-138-1 61880-72-K 1.62 5.05 6.2899 2 NA 60195-138-2 61880-72-K 1.62 5.20 6.932 1 16.6 60195-138-3 61880-72 1.58 5.19 6.5406 1 18.9 60195-138-4 61880-72 1.58 5.00 6.467 2 27.8
One-time impregnation resulted in the 16.6 and 18.9% catalyst weight gains with the 61880-72-K and 61880-72 solutions, respectively. Upon autopsy, the channels appeared uniform.
The elemental compositions and uniformity of the monolith catalysts were analyzed by SEM/EDS. Two SEM samples were prepared for each of the first three monoliths in Table 13. First sample has clean, fractured channel walls, while second sample has the flat channel wall being exposed. Three spots along the channel wall thickness were analyzed: two close to the wall surface, one in middle of the wall thickness. The elemental compositions of interior channel walls are compared to the exterior channel wall in Table 14. Presence of all the metallic elements inside the channel wall is confirmed. There are some variations in relative metal element loading at different spots at micrometer-scale. But, co-presence of targeted elements throughout the channel wall is confirmed.

(94) TABLE-US-00014 TABLE 14 Atomic compositions of the monoliths impregnated with NiCuMgCeAl oxide composite Total M to No Ti Individual M to Ni 60195 Location M/Ti K Ni Cu Ce La Mg Al -138-1 Thickness left 0.13 1.52 1.00 0.34 2.34 0.00 0.00 4.47 Thickness middle 0.15 1.71 1.00 0.55 1.65 0.00 0.03 5.55 Thickness right 0.20 2.30 1.00 0.33 1.45 0.00 0.71 8.17 Channel surface 0.19 2.84 1.00 1.32 4.74 0.00 0.73 7.25 Average 0.17 2.09 1.00 0.63 2.54 0.00 0.37 6.36 138-2 Thickness left 0.15 1.49 1.00 0.08 2.16 0.00 0.00 4.00 Thickness middle 0.18 1.66 1.00 0.08 1.80 0.00 0.13 5.19 Thickness right 0.20 1.83 1.00 0.21 2.25 0.00 0.28 6.03 Channel surface 0.17 1.63 1.00 0.47 1.68 0.00 0.08 4.55 Average 0.18 1.65 1.00 0.21 1.97 0.00 0.12 4.94 138-4 Thickness left 0.56 0.01 1.00 0.05 0.33 0.00 0.00 0.77 Thickness middle 0.86 0.00 1.00 0.26 0.17 0.00 0.14 1.47 Thickness right 0.74 0.00 1.00 0.23 0.20 0.00 0.02 1.51 Channel surface 0.16 0.02 1.00 0.63 1.28 0.00 0.30 3.77 Average 0.58 0.01 1.00 0.29 0.49 0.00 0.12 1.88 138-3 Thickness left 0.20 0.01 1.00 0.10 1.34 0.00 0.17 1.73 Thickness middle 0.17 0.00 1.00 0.14 1.13 0.00 0.11 0.98 Thickness right 0.24 0.00 1.00 0.14 1.25 0.00 0.57 2.55 Average 0.20 0.01 1.00 0.13 1.24 0.00 0.28 1.75
A new group of monolith catalysts listed in Table 15 were prepared using the NiCuMgCeAl solutions and procedures same as used above. With the repeated procedures, the resulting catalysts showed consistent weight gains. First impregnation resulted in catalyst weight gain 13.2-14.5 wt % among six samples. Different from the above trial with NiCuMgCeAl composite solution, second time impregnation was conducted on the calcined monolith rather than the dried. The second impregnation resulted in final catalyst weight gain of 25.5-30.0 wt % among the four samples.

(95) TABLE-US-00015 TABLE 15 TiO2 monoliths impregnated with NiCuCeMgLaAl oxide composite catalysts Second First impregnation impregnation Monolith Monolith support weight gain, wt % weight gain, wt % Final weight ID Length, After After After After gain 60195- Solution ID cm Weight, g drying calcination drying calcination wt % 145-1 61880-72-K 15.2 20.3503 42.5 13.9 30.3 10.2 25.5 145-2 61880-72-K 13.9 19.4530 45.9 14.5 32.7 13.8 30.3 145-3 61880-72-K 11.3 17.0141 46.2 14.3 NA NA 14.3 145-4 61880-72 10.8 15.6685 42.2 13.4 NA NA 13.4 145-5 61880-72 9.6 14.4469 42.2 13.2 37.6 13.9 29.0 145-6 61880-72 9.4 13.8092 45.9 14.0 30.7 11.0 26.5
Preparation of the monolith catalyst by coating was tried with coating slurry made of NiCuMgCeAlO composite particle, which was prepared using the previous particle preparation procedure. The coating slurry was introduced into the bare TiO2 monolith channel and drained. The excessive solution was further removed from the channel by centrifugation. Resulting coating looked uniform for the three samples. The coated samples were dried in fume hood overnight and then, dried in an oven at 120 C. for 5 days. The dried monolith was calcined at 500 C. for 6 h in air in a tubular furnace. Table 16 lists the weight gains. The catalyst loading was only a few percentage, which is fairly low. More problematically, the coating layer did not have any adhesion on the channel wall, and existed as a loose layer. This example shows that impregnation is a more effective method to load the metal oxide composite catalyst into monoliths.

(96) TABLE-US-00016 TABLE 16 TiO2 monoliths coated with NiCuMgCeAlO composite oxide slurry Weight gain Weight gain afer afer drying calcination Monolith ID Bare mass (g) wt % wt % 60195-140-1 7.2531 7.4 4.4 60195-140-2 6.7767 4.5 2.3 60195-140-3 6.5095 5.6 3.2

Example IX. Steam Reforming Reaction Testing of Bio-Oils in a Particle-Packed Bed

(97) Bio-oil feed used in this testing was an oak pyrolysis oil (TCPDU) received from NREL on Oct. 29, 2010. The oil remains fluidic at room temperature but was very viscous. Its composition was reported as 44.94% C, 7.29% H, 47.66% 0, 0.01% S, and <0.05% ash. The molecular formula is CH.sub.1.95O.sub.0.80.

(98) 2.0 g of catalyst particles were packed into a reactor tube with a bed packing height about 3.2 cm. The catalyst names and testing results of five reactor runs are summarized in Table 17. NiCuMgCeAl oxide composite was prepared in the catalyst particle form (Cat ID 61880-35 in Table 10). NiCuCe/TiO2 (as-received), Ni/TiO2 (700 C.-calcined), and Ni/TiO2 (H.sub.2O-washed and 700 C.-calcined) were prepared in the monolith form (Cat #61880-34, 61880-25-1 in Table 11). The Ni/TiO2 (700 C.-calcined) and Ni/TiO2 (H.sub.2O-washed and 700 C.-calcined) were prepared using the same procedure as Ni/TiO2 (61880-25-1 in Table 11) except for using of different TiO2 monolith. The 700 C.-calcined and H2O-washed monolith supports were used to remove potential harmful components in the as-received monolith. The monolith was crushed and sieved into 20-100 mesh, same sizes as the catalyst particle.

(99) For first two runs, top of the catalyst bed was packaged with a layer of quartz wool and a monolith spacer. In 3.sup.rd run, the monolith spacer was removed. In runs 4 and 5, nothing was packed on top of the catalyst bed. The reactor was heated to a mid-bed temperature of 400 C. Steam was introduced first and followed with bio-oil delivered by a syringe pump. The reactor effluent was cooled, and the steam and oil were condensed into a gas/liquid separator. The off-gas flow rate was measured by a flow meter and the gas composition was analyzed by a Mass Spec using argon as an internal standard. The gas production rate is calculated based on the off-gas flow rate and composition. All the runs were conducted near atmospheric pressure at GHSV=100,000. After the reaction was held for 10 to 40 min, the reactor was heated to either 450 C. or 500 C. Since the gas production varied with time, initial gas production rates are used for comparison of different reactor runs in Table 17.

(100) TABLE-US-00017 TABLE 17 Bio-oil steam reforming reaction testing results of particle catalyst beds Run # 1 2 3 4 5 Catalyst NiCuMgCeAl Oxide NiCuCe/TiO.sub.2 Ni/TiO.sub.2 Ni/TiO.sub.2 NiCuMgCeAl 61880-35 (as-received) (700 C.- (H.sub.2O-washed Oxide 61880-34 calcined) and 700 C.- 61880-35 calcined) Reactor Monolith guide Monolith guide Quartz Free space Free space packing bed/quartz wool bed/quartz wool above wool catalyst Bed temperature Top, C. 380 430 475 400 465 362 385 420 490 350 395 442 Mid, C. 400 450 510 450 500 400 410 460 520 387 440 490 Gas production rate H.sub.2, sccm 10 13 22.5 3.3 11.8 1.5 1.0 2.0 7.0 74 10 15 CO.sub.2, sccm 12 7.5 11 4.4 7.4 1.7 1.2 1.2 3.2 23 6 8 CO, sccm NA NA NA 4 6 2.2 2.5 3.6 5.8 6 3 5
Compared to the TiO2 monolith-supported catalysts, the NiCuMgCeAl oxide composite catalyst showed a significant reforming activity at 400 C. Thus, this catalyst formulation was used to prepare monolith catalysts.

Example X. Elemental Compositions of Metal Oxide Composite Catalyst

(101) The NiCuMgCeAl oxide composite catalyst before and after the bio-oil reforming test was analyzed by SEM. The elemental compositions are listed in Table 18. The micro-structures and EDS analytical spots are shown in FIG. 25. Even for the catalyst particle, there is significant variation in the elemental composition at different spots of a catalyst particle at micrometer scale. Co-existence of the metal elements in all the spots is confirmed. The composite catalyst of present invention is characterized by co-existence of these different metal elements at the same spot at micrometer scale.

(102) TABLE-US-00018 TABLE 18 Elemental compositions of NiCuMgCeAl oxide composite catalyst particle Ni Cu Ce Mg La Al Na Fresh Spot 1 1.00 0.35 0.15 0.57 0.00 2.02 0.00 Spot 2 1.00 0.36 0.10 0.43 0.00 1.61 0.00 Spot 3 1.00 3.20 0.99 0.38 0.01 21.37 0.00 Spot 4 1.00 0.31 0.07 0.48 0.00 1.76 0.00 Avg 1.00 0.46 0.14 0.48 0.00 2.60 0.00 STDEV 0.00 1.43 0.44 0.08 0.00 9.79 0.00 Spent Spot 1 1.00 0.38 0.29 0.68 0.01 2.79 0.11 Spot 2 1.00 0.33 0.12 0.48 0.00 2.19 0.06 Spot 3 1.00 0.43 0.27 0.61 0.01 2.65 0.00 Spot 4 1.00 0.46 0.63 0.90 0.01 2.73 0.00 Avg 1.00 0.40 0.32 0.66 0.01 2.57 0.09 STDEV 0.00 0.05 0.21 0.17 0.00 0.27 0.05

Example XI. Bio-Oil Reforming Testing of Monolithic Reforming Catalyst Module

(103) The TiO2 monolith impregnated with the KNiCuCeMgAl composite catalyst (Cat 60195-145-3 in table 15) was tested for steam reforming of bio-oil. To mitigate the small flow rate problems with the reacting testing apparatus, quartz tube of 6.2 mm OD4.2 mm ID was mounted onto top of the monolith by cement. The monolith module was housed inside a steel reactor tube of 20 mm ID, and steam/bio-oil line was connected to the quartz tube. In this way, the steam/bio-oil feed was directly delivered to the four reaction channels of the monolith module. The as-received bio-oil was a viscous, dark fluid. The bio-oil was pumped into the reactor at room temperature, while water was vaporized to abut 110 C. into steam. The steam combined with the bio-oil flowed downwards into the monolith channel via the quartz tube. The steel reactor tube was heated by a two-stage furnace with the top and bottom bed temperature being monitored and controlled.
The reactor temperature was raised to about 560 C. in 200 sccm of air. When the reactor temperature stabilized, 200 sccm of Ar purge gas was introduced into the reactor with 0.2 cc/min water and 0.2 cc/min of bio-oil. The reactor pressure was controlled at about 5 psig. The reactor effluent was cooled to about 6 C. The liquid was condensed and collected, while the gas was sampled for composition analysis by Mass Spec. After the steam reforming reaction was carried out about 20 min, the bio-oil and water feeds were stopped and 200 sccm air flow was introduced to conduct the catalyst regeneration. The regeneration was carried out about 20 min. FIG. 26 shows gas production profiles in 12 of consecutive reforming/regeneration cycles. The ability to activate the catalyst by heating in air was confirmed. The effectiveness to conduct bio-oil steam reforming in the monolith catalyst channel is demonstrated.

(104) The liquid products collected from all the reforming runs looked clear. These products are a mixture of water and un-converted (or reformed) bio-oil. A clear solution is very beneficial to re-processing of the remaining hydrocarbon species, and preferred embodiments of the invention can be characterized by the recovery of a clear liquid phase as the primary or only recovered liquid phase and, optionally, recycle of all or part of the liquid phase.