Patent Application
20190169506
The present invention is generally directed to systems and methods for synthetic fuels and chemical products generation with in-situ CO2 capture. A reduction-oxidation (redox) system using one or more chemical intermediates is generally utilized in conjunction with liquid fuel generation via indirect CO2 hydrogenation, direct hydrogenation, or pyrolysis.
Fossil fuels including crude oil, natural gas, and coal provide more than 85% of today's energy supply. These fossil fuels are usually transformed to carriers such as electricity and liquid transportation fuels prior to utilization by end consumers. Electricity is mainly produced by relatively abundant energy sources such as coal, natural gas, and nuclear. In contrast, liquid transportation fuel is almost exclusively obtained from crude oil, whose supply is relatively insecure with volatile prices. With an increasing energy demand and concomitant concerns over carbon emissions from fossil fuel usage, affordable synthetic transportation fuels from more abundant resources such as coal, biomass, and oil shale are desirable. To address the environmental concerns, the next generation synthetic fuel production processes need to be able to capture pollutants generated in the process. These pollutants include CO2, sulfur compounds, and mercury, among others.
Synthetic fuel is generated from gaseous fuels such as natural gas through reforming and the Fischer-Tropsch (“F-T”) scheme. Solid fuels such as coal, biomass, and pet coke can be converted to synthetic fuel through indirect liquefaction (gasification—water gas shift—Fischer-Tropsch), direct liquefaction, or pyrolysis. These systems are, however, more capital intensive than oil refining processes. Moreover, their energy conversion efficiencies are relatively low.
Synthetic fuel can also be generated from biomass via biochemical routes. However, a large amount of process water is utilized. Moreover, the biochemical approaches have stringent requirements on the feedstock.
All the aforementioned processes involve CO2 emissions. CO2 capture from these processes associates with notable energy losses and hence decreases in process efficiency.
Embodiments of the present invention provide alternatives to produce synthetic fuel from naturally occurring carbonaceous fuel sources with high efficiency and effective CO2 capture.
Embodiments of the present invention are generally directed to novel redox based systems for fuel and chemical production with in-situ CO2 capture. A redox system using one or more chemical intermediates is generally utilized in conjunction with liquid fuel generation via indirect Fischer-Tropsch synthesis, direct hydrogenation, or pyrolysis. The redox system is used to generate a hydrogen rich stream and/or CO2 and/or heat for liquid fuel and chemical production. A portion of the byproduct fuels and/or steam from liquid fuel and chemical synthesis is used as part of the feedstock for the redox system.
Additional features and advantages provided by embodiments of the present invention will be more fully understood in view of the following detailed description.
The following detailed description of the illustrative embodiments of the present invention can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:
Embodiment of the present invention are generally directed to systems and methods for converting carbonaceous fuels into synthetic fuels with minimal carbon emission and improved energy conversion efficiency. Such systems and methods generally include an indirect fuel reforming/gasification sub-system and a liquid fuel synthesis sub-system.
Based on the technique through which the synthetic fuel is produced, the various embodiments of the present invention can be generally grouped into three categories, i.e. indirect synthetic fuel generation integrated with an indirect fuel reforming/gasification sub-system, direct synthetic fuel generation integrated with an indirect reforming/gasification sub-system, and direct pyrolysis system integrated with an indirect fuel combustion sub-system. The following specification discusses the three categories respectively.
The indirect synthetic fuel generation system, which is strategically integrated with an indirect fuel reforming/gasification sub-system, is generally represented by
The indirect conversion of carbonaceous fuels such as coal and natural gas to synthetic liquid fuel through gasification/reforming followed by Fischer-Tropsch synthesis is well established. The processes, however, are inefficient due to the large irreversibility of the gasification/reforming step and the highly exothermic nature of the Fischer-Tropsch synthesis reactions and the inefficiency associated with the heat recovery and utilization. Further, significant energy losses will be incurred if the carbon generated in the process is captured. In addition, the indirect synthetic fuel generation systems are highly capital intensive.
The increasing concerns over energy security and CO2 emissions have cast serious doubt on both the environmental and economical acceptability of indirect synthetic fuel generation systems. To reduce the cost and carbon footprint of the indirect liquid fuel synthesis systems, drastic improvement in process energy conversion efficiencies coupled with CO2 capture are highly desirable. Embodiments of the present invention strategically integrate an indirect gasification/reforming sub-system with Fischer-Tropsch sub-system to achieve effects that: 1) reduce the irreversibility of the overall synthetic fuel product system; 2) improve the energy conversion efficiency; and 3) capture the CO2 generated in the process.
According to one aspect, carbonaceous fuel such as coal, biomass, pet coke, syngas, natural gas, extra heavy oil, wax, and oil shale, are first converted into separate streams of CO2 and H2 through the assistance of one or more chemical intermediates. The H2 and a portion of the CO2 are then reacted in a Fischer-Tropsch synthesis reactor to produce synthetic fuels and chemicals. The remaining CO2 is obtained in a concentrated form and can be readily sequestrated. The conversion of CO2 and H2, as opposed to CO and H2, in the Fischer-Tropsch reactor reduces the exothermicity of the F-T reaction. Moreover, this scheme potentially reduces the endothermicity of the gasification/reforming step. As a result, the overall process irreversibility can be reduced. Moreover, the steam produced from the exothermic F-T reactor is readily available for hydrogen generation in the gasification/reforming sub-system. While the use of CO2 and H2 for F-T synthesis was studied in the 1990s, the method for CO2 and H2 generation from carbonaceous fuels and the unique integration schemes between the CO2/H2 generation sub-system described herein are novel.
MeOx+CxHyOz→CO2+H2O+MeOy (Reactor 1)
MeOy+H2O→MeOz+H2 (Reactor 2, y<z≤x)
MeOz+O2→MeOx (Reactor 3,optional)
CO2+H2→—(CH2)—+H2O (CO2 hydrogenation)
Here CxHyOz refers to a carbonaceous fuel in general. Me is a metal or metal mixture that can be reduced by the carbonaceous fuel and subsequently oxidized by steam and air. Such metals include Fe, Co, In, Mn, Sn, Zn, Cu, W, and combinations thereof.
Reactor 1 is typically operated at 400-1200° C. and 1.01×105 Pa-8.10×106 Pa (1-80 atm). Reactor 2 is operated at a temperature of 0-300° C. lower than Reactor 1. Reactor 3, which is optional depending on the type of metal and the system configuration, is operated at a temperature 0-400° C. higher than Reactor 1. In preferred embodiments, Reactor 1 is operated at 600-900° C. The gasification/reforming sub-system is operated at 1.01×105 Pa-3.04×106 Pa (1-30 atm).
In certain embodiments, Reactor 1 is endothermic. A portion of the reduced solids from Reactor 1 is directly sent to Reactor 3 for oxidation with oxygen containing gas. The heat released in Reactor 3 is used to compensate for the heat required in Reactor 1. The extra heat generated in Reactor 3 is used for power generation to support the parasitic power usage. A small portion of the hydrogen from Reactor 2 can be used for fuel product upgrading.
As showing in
The F-T sub-system is operated at 200-500° C. and 1.01×106 Pa-8.10×107 Pa (10-100 atm). In some embodiments, compression of the CO2 rich gas and H2 rich gas from the gasification/reforming sub-system are compressed.
Sulfur may present in the carbonaceous fuel, contaminating the CO2 rich gas and H2 rich gas streams. One or more sulfur removal units may be used to clean up the product gas streams. In the case where an iron based catalyst is used for F-T synthesis, a high temperature sorbent bed using solid sorbents such as CaO, ZnO, etc. can be used to reduce the sulfur contaminants to levels of 100 ppm or less. When a less sulfur tolerant catalyst such as cobalt based F-T catalyst is used for F-T synthesis, additional sulfur removal steps such as that using MDEA, SELEXOL (trade name), or Rectisol (trade name) may be used. In the case when low sulfur fuel such as low sulfur biomass and sulfur free natural gas or syngas is used, the sulfur removal units are not necessary.
Fe2O3+Fuel→Fe/FeO+CO2+H2O(avg. valence of Fe is <1) (Reducer)
Fe/FeO+H2O→Fe3O4+H2 (Oxidizer)
Fe3O4+O2(Air)→Fe2O3 (Combustor)
In one embodiment, all of the hydrogen from the oxidizer and a portion of the CO2 from the reducer are introduced to the Fischer-Tropsch reactor to generate a mixture of hydrocarbons. The hydrocarbon mixture is then separated and refined. The fraction of the fuel mixture of lower economic value, e.g. unconverted syngas, light hydrocarbons, and naphtha, is sent to either the reducer or the gasifier/reformer to enhance carbon utilization. In essence, most of the carbon in the fuel is either fixed in the final synthetic fuel product or in the concentrated CO2 stream which is ready for sequestration after moderate compression. Hence, the net life cycle CO2 emissions of the system are comparable to petroleum based gasoline and diesel when coal is used as the fuel (with CO2 capture and sequestration). In the case when biomass and natural gas are used as the fuel, the net life cycle CO2 emission is much lower or even negative. In a carbon constrained scenario, a combination of feedstock such as coal/biomass, coal/natural gas can be used to reduce the CO2 emissions while taking advantage of abundantly available coal.
The F-T reactor generates a large amount of steam for F-T cooling purposes, and a portion of the steam is used in the oxidizer for hydrogen generation. The rest of the steam, after supplemental firing or superheating with a small portion of byproduct fuel and heat exchanging with high temperature exhaust gas streams in the process, is used for power generation to meet the parasitic energy needs.
The oxygen carrier comprises a plurality of ceramic composite particles having at least one metal oxide disposed on a support. Ceramic composite particles are described in Thomas U.S. Pat. No. 7,767,191; Fan, published PCT Application No. WO 2007082089; and Fan, PCT Application No. WO 2010037011. In addition to the particles and particle formula and synthesis methods described in Thomas, applicants, in a further embodiment, have developed novel methods and supporting materials to improve the performance and strength of the ceramic composite particles used in the present system.
The novel methods include the step of mixing a metal oxide with at least one ceramic support material in slurry form followed by drying, granulation, and pelletization. Ceramic support materials in addition to those described in the prior publications include magnesium oxide, bentonite, olivine, kaoline, and sepiolite. Olivine is also used as a promoter for hydrocarbon conversion.
Referring now to the reduction reaction in the first reactor of
FeOx+Fuel→FeOy+CO2+H2O
Fuel+CO2→CO+H2
Fuel+H2O→CO+H2
FeOx+CO/H2→FeOy+CO2/H2O
The preferred overall reaction is:
Fe2O3+Fuel→Fe/FeO+CO2+H2O
Specifically, metallic iron (Fe) is formed in the reducer. Simultaneously, an exhaust stream that contains at least 80% CO2 (dry basis) is produced from the reducer. In preferred embodiments, the CO2 concentration exceeds 95% and is directly sequestrable.
The preferred designs of the reducer include a moving bed reactor with one or more stages, a multistage fluidized bed reactor, a step reactor, a rotary kiln, or any suitable reactors or vessels known to one of ordinary skill in the art that provide a countercurrent gas-solid contacting pattern. The counter-current flow pattern between solid and gas is used to enhance the gas and solid conversion. The counter-current flow pattern minimizes the back-mixing of both solid and gas. Moreover, this flow pattern keeps the solid outlet of the reactor at a more reductive environment while the gas outlet of the reactor in maintained in a more oxidative environment. As a result, the gas and solid conversion are both enhanced.
Referring back to the oxidation reaction in the second reactor in
Fe+H2O→FeO+CO/H2
3FeO+H2O→Fe3O4+CO/H2
The preferred designs of the oxidizer also include a moving bed reactor and other reactor designs that provided a countercurrent gas-solid contacting pattern. A countercurrent flow pattern is preferred so that high steam to hydrogen and CO2 to CO conversion are achieved.
Referring back to the oxidation reaction in the third reactor in
Fe/FeO/Fe3O4+O2→Fe2O3
Alternatively, all the reducer oxygen carrier product will be introduced to the oxidizer to react with a sub-stoichiometric amount of steam. Substantially all of the partially regenerated oxygen carrier from the oxidizer will then be introduced to the combustor. By doing this, no by-pass solids stream is needed.
The preferred reactor designs for the combustor include a fast fluidized bed reactor, an entrained bed reactor, a transport bed reactor, or a mechanical conveying system. The functions of the combustor include: oxidation of the oxygen carrier to a higher oxidation state; and re-circulation of the oxygen carrier to the inlet of the reducer for another redox cycle.
The combustor is highly exothermic. The heat generated in the combustor can be used to compensate for the heat required in the reducer. This heat can also be used to preheat the feed streams and to generate power for parasitic energy consumptions. The high pressure gaseous streams discharged from the system can be used to drive expanders for gas compression.
Table 1 illustrates the mass flow of the major streams in a process when Illinois #6 coal and switchgrass are used as the feedstock and synthetic diesel is the product. Table 2 illustrates the energy balance of the system.
Table 3 illustrates the mass and energy flow of the major streams in a process when switchgrass is used as the feedstock and synthetic diesel is the product.
Although the cases exemplified by Tables 1-3 are specific to the type of feedstock, product, reforming/gasification sub-system, and liquid fuel production system, the choices for the aforementioned parameters have a large degree of freedom. For instance, multiple types of solids fuels can be used as the feed and various synthetic fuel products can be produced.
CaO+Fuel+H2O→CaCO3+H2
The spent sorbent is then regenerated at high temperatures using the waste heat from the system in the calciner:
CaCO3→CaO+CO2
A portion of the byproduct from the liquid fuel synthesis sub-system is combusted to provide the heat for calcination reaction. A hydration step is optionally added to reactivate the sorbent. The concentrated CO2 from the calciner is then compressed and sequestered.
The hydrogen and a portion of CO2 produced from the sorbent enhanced reforming scheme are then used to generate synthetic fuel. Compression of the CO2 stream is required prior to fuel synthesis.
The metal oxide is used as the carrier for both oxygen and heat. In the first unit, the reducer, high temperature metal oxide (600-1400° C.) is reduced by the residue char and light fractions from the pyrolyzer and refining block:
MeOx+unwanted fuel from pyrolyzer and refining block→MeOy+CO2
This step is mostly endothermic, the hot MeOy exiting the reducer is at a temperature ranging between 400-750° C.
The MeOy from the reducer enters into the prolyzer where it provides heat to the biomass feedstock for fast pyrolysis. The MeOy may become further reduced in the pyrolyzer to MeOz. The temperature of the MeOz exiting the pyrolyzer ranges between 300-650° C. The reducer and pyrolyzer can be either a moving bed or a fluidized bed. A fluidized bed is preferred for the pyrolyzer.
The MeOz from the pyrolyzer is then introduced to the oxidizer, which is similar to the combustor unit described with respect to
MeOz+O2→MeOx
The outlet temperature of the oxidizer ranges from 600-1400° C. The preferred reactor designs for the oxidizer include a fast fluidized bed reactor, an entrained bed reactor, a transport bed reactor, or a mechanical conveying system. The preferred metal for the redox operation include but are not limited to Co, Fe, Cu, Ni, Mn, and W. The support material and the metal are selected such that the metal oxide composite is not very catalytically active for tar cracking.
MeOx+unwanted fuel from pyrolyzer and refining block→MeOy+CO2
This step is often endothermic, the hot MeOy exiting the reducer at a temperature ranging between 400-750° C.
The reduced MeOy then enters the oxidizer which is preferably an entrained bed, transport bed, or a fast fluidized bed reactor. The oxidizer is designed similar to a shell and tube heat exchanger with metal oxide composite and air flowing in the shell side. Air oxidizes MeOy back to MeOx.
MeOy+O2→MeOx
Significant heat is generated in this step. Meanwhile, high temperature exhaust air is also generated. The reducer can be either a moving bed or a fluidized bed.
The N2 rich exhaust air, with a small amount of residual oxygen, can be directly used for biomass feeding and conveying in the fast pyrolyzer to provide the heat. In certain embodiments, an additional combustion step with excess amounts of byproduct fuel from the fast pyrolysis stage can be used to remove the residual oxygen prior to using the high temperature N2 rich gas for biomass feeding and conveying.
Pulverized biomass is introduced into the pyrolyzer which is installed inside the oxidizer. The pulverized biomass, carried by the high temperature gas, is injected in a tangential direction into the pyrolyzer and is conveyed upwards by the high temperature gas in a swirling manner. The centrifugal force causes the biomass to be close to the pyrolyzer/oxidizer wall through which heat can be transferred to the biomass for pyrolysis. The pyrolyzer is a fast fluidized bed, entrained bed, or a dilute transport bed.
Alternatively, the reducer can be integrated with the pyrolyzer to provide the heat to the pyrolyzer from its outer wall. In both cases, the pyrolyzer is operated at between 300-650° C., the reducer is operated at between 400-1300° C., and the oxidizer is operated at between 450-1350° C.
The performance of the reducer in the redox based reforming/gasification sub-system is important to the success of the integrated embodiments as shown in
This is a continuation of U.S. patent application Ser. No. 15/376,590, filed on Dec. 12, 2016, which is a divisional of U.S. patent application Ser. No. 13/394,396, filed on Mar. 6, 2012, now U.S. Pat. No. 9,518,236, issued on Dec. 13, 2016, which is a U.S. national stage entry of International Patent Application No. PCT/US2010/048121, filed on Sep. 8, 2010, which claims priority to U.S. Provisional Patent Application No. 61/240,446, filed on Sep. 8, 2009, the entire contents of each of which are fully incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 61240446 | Sep 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13394396 | Mar 2012 | US |
| Child | 15376590 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15376590 | Dec 2016 | US |
| Child | 16216911 | US |
