OA20694A - Waste to energy conversion without C02 emissions. - Google Patents

Abstract

The invention provides a method for energy extraction from municipal and mixed waste streams. The method employs a three-stage pyrolysis to produce a hydrogen-rich pyrolysis gas, which maximizes energy extraction without releasing carbon dioxide into the atmosphere. Optionally, the energy in high-pressure C02 from the process is recovered in stages by expansion through gas turbines.

Description

WASTE TO ENERGY CONVERSION WITHOUT CO2 EMISSIONS

FIELD OF THE INVENTION

[0001] The présent invention generally relates to the oxidative processing of carboncontaining waste in order to extract the available Chemical energy, with capture of the carbon dioxide produced.

BACKGROUND

[0002] Biomass (matter derived from plants and animais) contains a vast number of organic compounds in which reduced forms of carbon and hydrogen are the basic éléments. Oxidation of these éléments to water and carbon dioxide releases energy, which makes biomass a potential a source of energy.

[0003] Although the direct combustion of biomass as a source of energy (e.g., by burning wood for heat production) has largely been abandoned in the developed world, an analogous process is emerging in the form of energy crops dedicated to the production of fuels such as biogas, biodiesel and bioethanol. Also under development are methods for conversion of cellulosic waste into éthanol by fermentation. The conversion of biomass to fuel is regarded as carbon neutral, in that atmospheric carbon dioxide, fixed by photosynthesis, is the source of the reduced carbon in the fuels.

[0004] A largely untapped source of energy is the biomass found in municipal waste (chiefly garbage and sewage sludge) and agricultural waste (stover and bagasse.) At the présent time, three processes see lîmited use in extracting energy from these waste streams; the heat produced by combustion in incinerators can be used to energize steam-drîven turbines for electricity production; anaérobie digestion or fermentation of some types of waste can be used to produce biogas (largely methane); and thermolytic methods (gasificatîon and pyrolysis) can be used to generate hydrogen and oils from poorly-fermentable (chiefly lignocellulosic) waste.

[0005] Lignocellulosic biomass (cellulose, hemi-eellulose and lignin) is the most abundant organic material in the biosphère. It is abundant in waste streams from the forest industry and agriculture, and represents 40-60% of municipal solid waste. The thermolytic process for processing lignocellulosic material consists of a succession of treatments. An initial thermolysis between températures of 300 to 600°C is carried out in the absence of oxygen, — 2 followed by high température gasification at 900-1300°C in the presence of water vapor and oxygen, with net production of carbon monoxide and hydrogen (i.e., synthesis gas). This is an endothermie transformation, and the required energy can be obtained by oxidatîon of a fraction of the input materiai to carbon dioxide and water; alternative^, an external source of supplémentai energy can be provided.

[0006] Additional hydrogen (and energy) can be obtained from synthesis gas via an exothermic gas shift reaction, CO + H₂0 CO₂ + H₂, but the prior art practice has been to direct the synthesis gas to a Fischer-Tropsch unît for conversion to liquid hydrocarbons, or to methanol. The gas shîft reaction is employed not to produce hydrogen per se, but to optimize the H2/CO ratio for conversion to liquid fuel or feedstock, with a net loss of energy content.

[0007] The drawbacks of incinération (combustion) include the difficulties of meeting increasingly stringent air pollution émission standards, and community résistance to the presence of incinerators în general. Chlorine-, nitrogen-, and sulfur-containing substances in the feed give rise to acidîc products that must be captured and neutralized. The treatment of large volumes of exhaust gases requires a capital investment in large-scaie equipment. The high moisture content of typical municipal waste is vaponzed during incinération, at an energy cost of approximately 1,000 Btu/lb of water.

[0008] Pyrolyzers generate gas and oils by heating organic waste materials to high températures, ca. 400-500°C., but with poor energy efficiency and iittle control over the composition of the resulting materials. As with an incinerator, a pyrolyzer needsto boil off the water présent in the feed, which is energetically demanding. Pyrolysis chambers need to be 20 |_arge |_{n orc}|_{er t0} process waste on a useful scale, which leads to uneven heating of the waste, poor control over the chemistry, and poor quality of the end products.

[0009] Gasifiers operate with partial combustion of waste products. Air, oxygen, or steam is passed over the waste products in an amount that is sufficîent to oxidize only a fraction of the combustible material. Gaseous products such as CO₂, H₂O, CO, H₂ and light hydrocarbons are produced, and the generated beat thermolyzes the remaining waste products into oils, gases, and carbonaceous material. Again, vaporization of the water in the input stream présents an energy cost. The gases produced are too voluminous to be stored and must be used in situ, or piped to a location where they can be used as a feedstock. Gasifiers also sufferfrom energyconsuming water-containing feeds.

[0010] Pyrolysis and gasification methods also hâve problems with sulfur- and chlonnecontaining materials, which are transformed to mercaptans and organic chlorides.

[0011] Examples of prior art processes are found in U .5. Pat, Nos. 5,269,947, 5,360,553, and 5,543,061, which disclose a two-stage waste gasification process. In a first stage, the waste is heated to ca. 2OO-25O”C at up to 120 atmosphères pressure. Under these conditions the water content of the waste hydrolyses biopolymers such as fats and proteins to form a mixture of oils. In a second stage, the pressure is released, causing about half of the water to flash off as steam. The mixture is then heated further to drive off the remaîning water, as the mixture breaks down into gaseous products, oils, and carbon, which are coliected and separated.

[0012] U.S. Patent No. 8,003,833 describes a similar process, carried out in a multi-stage manner with carefui management, recovery, and use of beat energy. Soluble organics (sugars, glycerin, amino acids, etc.) are removed after the initial hydrolysis, in the form of a solution that can be used as fertilizer. Subséquent thermal processing yields marketable gases and oils, along with a carbon-rich biochar that can be combusted to provide energy needed to operate the plant.

[0013] The exploitation of biomass and municipal waste streams for the production of organic feedstocks, fuels, and energy, while thermodynamically viable, remains inefficient in practice, and the prior art processes release significant amounts of carbon dioxide to the atmosphère. There remains a need for a highly efficient process for waste-to-energy conversion, and a need for reduced carbon dioxide émissions from such processes.

BRIEF DESCRIPTION OFTHE INVENTION

[0014] The invention provides a combination of processes which, taken together, can accept a variety of inputs, such as mixed municipal waste, sewage, used tires and oils, and agricultural and food-processing wastes, and produce energy with high efficîency and minimal émissions. The recyding of recoverable materials can be carried out in an easy and economica! manner. [0015] The invention relies on a combination of éléments to achieve low émissions and high efficîency. One element is the use of induction heating of the reactors, which is rapid, efficient, and enables high températures with accurate control. A second element is the use of co-generated electricity, produced in a fuel cell using hydrogen gas generated by the process, to power the induction heaters.

[0016] Another element is the use of the Boudouard reaction (Equation 1) C(s)+C0j(g)^2C0(g) (Eqn. 1) coupled with the water-gas shift reaction (Equation 2)

CO + H₂O 2 CO2 + H₂ (Eqn. 2) to effect the conversion of a large fraction of the Chemical energy contained in the biomass into the Chemical energy contained in elemental hydrogen. Through reliance on the oxidation 5 of hydrogen, rather than carbon, the inefficiencies and environmental disadvantages of prior art carbon combustion methods can be avoided.

[0017] The hydrogen-rich gas thus produced enables the fuel cell to produce a considérable amount of electricity. The exhaust from the fuel cell is high-temperature steam, which may be used to generate additional electricity via a steam turbine.

[0018] In an alternative embodiment, rather than employing a fuel cell, the hydrogen is separated from the carbon monoxide and burned to generate high-pressure steam, from 10 which electricity is generated, with the CO being returned as an input to the water-gas shift réaction.

[0019] Ail of the CO₂ produced by the process is contained, so that no energy-consuming absorption process is required, and as a resuit the process has essentially zéro atmospheric émissions. A fraction of the captured CO2 is used as input to the Boudouard reaction; the remainder is suitable for use as a feedstock or fertilizer, or for séquestration by deep well injection.

BRIÈF DESCRIPTION OFTHE DRAWINGS

[5 [0020] Figure 1 is a diagram showing the initial shredding and drying of the incoming waste stream.

[0021] Figure 2 is a diagram showing the low-température pyrolysis stage of the process. [0022] Figure 3 is a diagram showing the medium- and high-temperature pyrolysis stages of the process.

[0023] Figure 4 is a diagram showing the fuel cell, steam turbine, and gas separator stages of the process.

[0024] Figure 5 is a diagram showing the low- and medium-temperature pyrolysis stages of an alternative embodiment of the process.

[0025] Figure 6 is a diagram showing the iow-temperature pyroiysis stage of an alternative embodiment of the process.

[0026] Figure 7 is a diagram showing the fuel cell, gas turbine, and gas separator stages of an alternative embodiment of the process.

[0027] Figure 8 is a diagram showing the initial shredding and drying of the incoming waste an alternative embodiment.

DETAILED DESCRIPTION OF THE INVENTION

[0028] The invention provides a number of related processes for extracting energy from biomass and municipal waste streams. These are as follows:

[0029] A process for obtaining energy from waste comprising:

(a) drying the waste;

(b) anaérobie pyroiysis of the waste at 300°C to 600°C to produce syngas, char, and bio-oil;

(c) anaérobie pyroiysis of the syngas in the presence of a portion of the bio-oil, a portion of the char, additional carbon dioxide, and added water, at 600’C to 900°C, to increase the hydrogen content of the syngas;

(d) anaérobie pyroiysis of the gas and oil produced at (c), in the presence of additional water and additional carbon monoxide, at 800°C to 1200°C and about 20 atmosphères pressure, tofurther increase the hydrogen content of the gas;

(e) separating hydrogen, carbon dioxide and carbon monoxide from the gas produced at (d);

(f) using the separated carbon monoxide as the additional carbon monoxide in step (d); and (g) using the separated carbon dioxide as the additional carbon dioxide in step (c).

[0030] The above process may further comprise fuelling a steam generator by combustîng the hydrogen separated at step (e).

[0031] In another embodimemt, the process comprises:

(a) drying the waste;

(b) anaérobie pyroiysis of the waste at 300T to 600’C to produce syngas, char, and bio-oil;

A (c) anaérobie pyrolysis of the syngas in the presence of a portion of the bio-oil, a portion of the char, additional carbon dioxide, and added water, at 600⁼C to 900°C, to increase the hydrogen content of the syngas;

(d) anaérobie pyrolysis of the gas and oil produced at (c), in the presence of additional water and additional carbon monoxide, at 800“C to 1200’C and about 20 5 atmosphères pressure, to further increase the hydrogen content of the gas;

(e) fuelling a fuel cell with the gas produced at (d), (f) driving a steam generator with steam produced by the fuel cell;

(g) separating carbon dioxide and carbon monoxide from the effluent gases of the fuel cell;

(h) using the carbon monoxide as the additional carbon monoxide in step (c); and (i) using a portion of the carbon dioxide as the additional carbon dioxide in step (b) .

[0032] in another embodiment, the process comprises:

(a) dryîng the waste;

(b) anaérobie pyrolysis of the waste at 300°C to 600°C to produce syngas, char, and bio-oil;

(c) anaérobie pyrolysis of the syngas in the presence of a portion of the bio-oil, a portion of the char, additional carbon dioxide, and added water, at 600‘C to 900 C, to increase the hydrogen content of the syngas;

(d) anaérobie pyrolysis of the gas and oil produced at (c), in the presence of additional water and additional carbon monoxide, at 800°C to 1200’C and about 20 atmosphères pressure, to further increase the hydrogen content of the gas, । (e)chillingthegas produced at(d) sufficiently toliquefytheCO2, andseparating the liquid C02 from the hydrogen and carbon monoxide;

(f) fuelling a fuel cell with the hydrogen and carbon monoxide produced at (e), {g) using the carbon monoxide exiting the fuel cell as the additional carbon monoxide in step (c);

(h) heating the liquid carbon dioxide separated at (e) so as to produce high pressure CO2 gas;

(i) generating electricity by expanding the high pressure CO2 gas produced at (h) through a gas turbine, thereby cooling the CO2;

(j) using the cooled CO2 generated at (i) to effect the Chiliing of gas at (e); and (k) using a portion ofthe carbon dioxide as the addîtional carbon dioxide in step (b).

[0033) In ail of the above processes, the fuel cell is preferably a solid oxide fuel cell (SOFC). An SOFC and steam generatortogether may comprise an integrated SOFC/turbine System. [0034] A key element of the présent invention is the use of the Boudouard reaction (Equation 1), the conversion of carbon dioxide and solid carbon into carbon monoxide:

C(s) + COz (g) 2 CO(g) (Eqn. 1)

[0035] The Boudouard equilibrium favors the formation of CO at high températures, shifting to the right at températures above ca. 700°C. In the process of the invention, the Boudouard equilibrium is coupled wîth the water-gas shift reaction (Equation 2) at to 600900°C, which converts the CO to CO₂ and hydrogen:

CO + H₂O ?» CO2 + H2 (Eqn. 2)

[0036] The net resuit is shown in Equation 3:

C(s) + CO2 (g) + 2H₂O ?» 2CO2 + 2H2 (Eqn. 3) [0037] The overall process transfers the potential Chemical energy présent in elemental carbon to the potential Chemical energy found in hydrogen. This is accomplished by carrying out an initial low-tempe rature anaérobie pyrolysis, to produce syngas, bio-oil, and carbon char, and then recycling COz, carbon biochar, and water (end products ofthe overall process) back into the System prior to high-temperature pyrolysis and reforming. The bio-oil and syngas, and recycled char and CO₂, are fed to a medium-temperature pyrolysis unit operating at 600-900°C, at which température the gas mixture becomes enriched in CO via the operation of Eqn. 1. A portion ofthe bio-oil can be removed at this point for use as liquid fuel.

[DD38] The CO-enriched gas is then compressed and fed, together with the bio-oil and additional water, toa high-pressure (20 atm), high-temperature (up to 1200 C) reforming unit, where cracking of liquid hydrocarbons takes place, and any remaining methane is oxidized by water to CO and H₂ (Equation 4):

CH4 + H2O CO + 3H₂ (Eqn. 4)

A ⁸

[0039] The composition of the gas is further shifted toward COz and Hz via the water-gas shîft reaction (Eqn. 2.) Through the above three-stage process, a large fraction ofthe Chemical energy contained in the biomass is converted into the Chemical energy contained în elementai hydrogen.

[0040] The hydrogen-rich gas is then fed to a fuel cell, along with oxygen or air, for génération of electricity. The exhaustfrom the fuel cell is high-temperature steam, which can be used to generate additional electricity via a steam turbine. In an alternative embodiment, the steam turbine may be powered by combustion of the hydrogen. This is a less efficient process, but it avoids the capital investirent and maintenance costs of the fuel cell. [0041] The unburned gas from the fuel cell, consisting of CO and C02, is compressed to 40 atm and fed to a separator, where it is cooled to liquefy the COz. Gaseous CO is separated and returned to the high température reforming unit, while the liquid COz is sent to expansion (évaporation) units. Part of the now-gaseous COz îs returned to the medium-temperature pyrolysis unit, and the remainder, still at about 20 atm, constitutes the COz effluent of the overall process. The expansion units serve as heat sinks for the coolant used to cool the separator.

] 5 [0042] The invention will now be described in greater detail. Turning to Fig. 1, mixed solid waste (municipal garbage, dried sludge, agricultural bagasse, etc.), preferably freed of ferrons metals and aluminium, is fed to a shredder 1. Liquid waste (sewage, concentrated sludge, etc.) is piped in at intake 2, and combined with the output ofthe shredder at mixer 3, which may be for example an auger for both mixing and propelling the waste stream. A heater 4 jq raises the température of the waste stream to about 140°C în order to dry the waste.

Pressurized steam is preferably used to energize the heater, and în the embodiment shown the steam enters at 5, with the condensate exiting at 6, where it joins the flow of condensate exiting from the steam turbine (Fig. 4, described below). The steam is preferably provided by the hot exhaust from the fuel cell, as described below. Steam produced by the drying waste 5 collects in chamber 7, where it serves to pressurize the waste and ensure that it flows in the proper direction. The pressure is controlled by valve8; steam released through 8 is condensed, combined with the heater and turbine condensâtes at 9, and exits at 10 for use elsewhere în the System. The dried waste 11 exits through transport pipe 12 and proceeds to the pyrolyzer units (Fig. 2.)

[0043] Referring now to Figure 2, waste 11 arrives at the distal end of transport pipe 12, and flows upward to the induction-heated low-temperature pyrolyzer unit 13. The dry waste is suspended, throughout the System, in bio-oil 14, which serves as the heat transfer fluid and reaction medium for the pyrolysis reactions. The pyrolyzer 13 is operated anaerobically, at 5 300T to 600’C, preferably at about 500°C. At this température, as is known in the art, organic materials thermally break down into char, gases and oils, yîeldîng bio-oil 14 which flows into réservoir 15. Bio-oil is removed at 16 at the same rate it isformed, so as to maintain the waste 11 within the heated zone of the pyrolyzer. A portion of the carbon in the waste is reduced to biochar, or coke, which is carried over with the bio-oil into réservoir 15. A solîds separator θ 17 collects the bio-char, along with inorganic solids (ash, silica, glass and meta! fragments, etc.) that are présent in or generated from the waste. The solid wastes are collected at 18. Carbon char is separated from the collected solids, and is returned to the medium température pyrolyzer (Fig. 3.) The syngas 19 produced by the reaction is largely H₂ and CO, with lesser amounts of CO₂ and CH4. It is removed via valve 20 and also passes on to the mediumtemperature pyrolyzer.

[0044j The above description is intended to be an outline of one embodiment of a portion of the invention. Those skilled in the art will appreciate that other methods of processing, drying, transporting, and anaerobically pyrolyzing biomass and organic waste to produce biooil, bio-char, and bio-gas are known in the art (see M.l. Jahirul et al., Biofuels Production through Biomass Pyrolysis—A Technological Review. Energies 2012, 5:4952-5001, 20 doi:lO.339O/en5124952), and any of the known methods are contemplated to be adaptable for use at this stage of the presently-described process. Précisé operating details, such as operating température, résidence time, and throughput, will be adjusted for optimum performance as the composition of the waste stream varies over time. Agricultural wastes, in particular, are tikeiy to vary with the seasons.

[0045] Turning to Figure 3, the medium- and high-temperature pyrolysis units are illustrated.

Bio-gas exiting from valve 20 (Fig. 2) enfers the medium-temperature pyrolyzer 21 via port 22.

Bio-oil 14 exiting the réservoir at 16 (Fig. 2) enters the bottom of the medium-temperature pyrolyzer at 23. Water enters via tube 24, and bio-char (carbon) recovered from the lowtemperature pyrolyzer is introduced at port 25. A separate feed of waste oil (from fryers, auto maintenance, etc.) may be separately fed into the System at 26, and carbon dioxide from the CO 2 separator (Fig. 4) is introduced at 27.

[0046] The pyrolyzer 21 is operated at a pressure of 1-5 atm, between 600° C and 900’C. Under these conditions, the Boudouard réaction (Eqn. 1) oxidizes the added carbon to carbon monoxide, with concomitant réduction of the added CO₂ to additional CO. Due to the presence of water, a water-gas shift reaction (Eqn. 2) then takes place, with the net production of additional hydrogen gas. The hydrogen-rich syngas 28 is then compressed by compresser 29 to about 20 atm before being fed to the high-temperature pyrolyzer 30. Bio-oil is removed at 31, pressurized to about 20 atm at 32, and also fed to the high-pressure pyrolyzer 30. Excess bio-oil is drawn off at 33, for use as a fuel or feedstock. Water is introduced to the hightemperature pyrolyzer via 24, and recycled CO from the CO2 separator (Fig. 4) is introduced at 34.

[0047] The high-temperature pyrolzyer is operated at a pressure of about 20 atm, at 800°C to 1200^oC, preferably at a température of about 900°C. Under these conditions, hydrocarbon cracking and steam reforming (Equation 4) take place, further enriching the gas phase in hydrogen, and the water-gas shift reaction converts the CO thus produced to yet more hydrogen. The net resuit of these processes is Equation 5:

[0048] CH4 + 2H2O S CO2 + 4H2 (Eqn. 5)

[0049] The gases 35, which are at this point prindpally hydrogen and CO2, are drawn away through outlet 36, and delivered to the fuel cell (Figure 4).

[0050] Turning now to Fig. 4, the pyrolyzer gas outlet 36 leads to valve 37, which in normal operation passes the gases tofuel cell 38. Fuel cell 38 is preferably a solid oxide fuel cell (SOFC) designed for high-pressure and high-temperature operation; such units are known in the art and are commercially available. Arr or oxygen is fed to the cell via inlet 39. Hot steam issues at 40, and is used to drive turbine 41 for génération of additional electricity. A portion of the steam is diverted at 42 to the heater 4 (Fig. 1) that dries the incoming waste stream, and the steam may be used as a thermal energy source elsewhere in the installation as needed.

[0051] Hybrid Systems combining SOFC fuel cells and turbines powered by the SOFC exit gases are known in the art; see U. Damo et al., Solid oxide fuel cell hybrid System: A detailed review of an environmentally clean and efficient source of energy. Energy 168:235-246 (2019) doi:10.1016/j.energy,2018.11.091. Integrated SOFC/turbine Systems hâve become commercially available; an example is the MEGAMIE™ sériés of integrated Systems manufactured by Mitsubishi Hitachi Power Systems, Ltd. of Yokohama, Japan. It is contemplated that commercial integrated Systems can be readily adapted for use in the process of the présent invention.

10052] A mixture of carbon dioxide and carbon monoxide remains after the hydrogen is oxîdized in the fuel cell, and these gases are compressed at 43 to about 40 atm and passed to the gas separator 44. The CO₂, still under 40 atm pressure, is cooled to about 4°C, at which point it liquéfiés, permitting the gaseous CO to be drawn away at 45 and returned to the hightemperature pyrolyzer at 34 (Fîg. 3). The liquid CO₂ 46 is sent on to expanders 47 and 48. Expander 47 discharges CO₂ at a pressure of about 1 atm; this gas is recyded to the medtumpressure pyrolyzer 21 (Fig. 3). Expander 48 discharges CO₂ at a pressure of about 20 atm. This gas is pipeline-ready, and can be used as a feedstock for chemical processes, for fertilizer production, or for enhanced oil recovery or underground séquestration. The costs and ineffîciencies of CO₂ capture are entirely avoided, due to the closed nature of the System of the invention.

[0053] The expansion of the CO₂ in expanders 47 and 48 îs accompanied by considérable cooling. This is captured by heat exchangers 49 and 50, respectively, which serve to cool and liquefy the compressed CO₂. A third heat exchanger 51, immersed în coolant 52, provides cooling for reactors, condensers, and other equipment as desired.

[0054] Of the energy supplied by hydrogen, only about 35% is used by the chemical processes of the invention, and the addition to the pyrolyzers of additional water makes it possible to improve upon this balance. The remainder is available for electricity production. [0055] The C0₂ produced is easily transmitted to agriculture in liquefied form, for dissolution in irrigation water. The use of carbonated water for irrigation is known to increase yields, particularly in greenhouse environments, but the method has not been widely employed to date. The avaîlability of piped-in CO₂ from installations of the System of this invention will make the technology readily available.

[0056] The présent invention is sufficientîy clean and efficient to make mining of landfills for their energy content a viable enterprise, and could make it possible to reclaim land currently gîven over to the storage of trash.

A 12

[0057] An alternative embodiment is shown in Figures 5-8, where the energy contained in the high-pressure CO2 is more efficiently recovered.

[0058] Turning to Fig. 8, as in the embodiment described above a carbon-containing municipal waste feedstock, preferably freed of glass and métal components, is reduced to a granular stage, kneaded, and fed into the System by mechanical means, such as augur 80. Sufficient water (up to 50%) may be added to assist in movement of the waste through input tube 81 to the low-temperature pyrolizer 55 (see Fig. 5.)

[0059] Turning to Fig. 5, the first step is the thermal treatment of the feedstock, sheltered from oxygen, in an induction powered pyrolizer 55 at températures ranging from 450 to 650 °C, and at pressures that can vary from a few bars to 20 bars. At températures above about 500°C, there is a danger of explosion from the self-combustion of hydrogen and carbon [0 monoxîde, most acutely at concentrations of about 4% for hydrogen and 14% for carbon monoxide. This danger is elimînated by injecting gaseous CO2 directiy into the reaction chamber of the reactor at 58.

[0060] At the end of this first stage of thermal treatment, the feedstock has been reduced into three different fractions, whose relative proportions will vary according to the feedstock, the température and the time of exposure to heat:

. Biochar, a high carbon product close to pure carbon, on the order of 5 to 25%;

• Bio-oiI, a hydrocarbon product similar to crude oil, from 30 to 65%; and •Syngas, composed mainly of carbon monoxide and hydrogen.

[0061] Each of the above fractions produced from the pyrolizer is directed separately:

• The biochar is decanted by gravîty to an intermédiare storage vessel 56, and a portion of the stored biochar is introduced at 57 as a carbonaceous additive and réaction catalyzer during the next (gasification) stage;

• The bio-oil is intermediately stored at 60 (Fig. 6) before being reintroduced to the gasification stage; and • The syngas is fed directiy in gaseous form to the gasification process.

[0062] As described above, biochar, syngas, and bio-oil are fed to a medium-temperature pyrolyzer 59 along with water and CO2, where the Boudouard reaction and water-gas shift 25 reaction take place, with the net production of hydrogen gas and carbon monoxide. The

A ¹³ produced gases and oils are fed at high pressure, as described above, to the high-tempe rature pyrolyzer 61 (Fig, 6) forgasification, resulting in a hydrogen-rich syngas product,

[0063] In this embodiment, CO2 gas produced by the process is captured and used as a working fluid, codant, and heat transfer fluid at low and medium pressures. The process, in this embodiment, liquéfiés the CO2 gas at about -20’C and about 20 bars pressure, the minimum pressure of the syngas at the exit of the gasification process. Liquid CO2 is stored at 70 (Fig. 7.)

[0064] Turning to Fig. 7, the liquid CO2 is fed to a virtua! compressor 71, where it is heated by hot bîo-oil from the pyrolizers. The abrupt, adiabatic rise in température of the CO2 within a constant volume produces an increase in the pressure of the gas, resulting in a high-pressure, ¹⁰ high-energy gas. The gas is further heated at 72 by heat exchange with hot syngas from the pyrolizers, and/or by heat exchange with steam at 78, before being used as the working gas in gas turbine 73, generating electricity. The Virtual compresser also supplies medium-pressure CO2, which is expanded through turbines 64 and 65 for additional electricity génération. The resulting low-pressure, cool CO2 is circulated through the outermost annular space of the ¹⁵ concentric piping System shown in Figs. 5*7. The chi11ed gas exiting the turbine 73 is used at heat exchanger77 to chill the syngas exiting pyrolyzer 61, condensingthe CO2 to a liquid which is separated and piped to storage vessel 70.

[0065] The syngas exiting heat exchanger 77 is introduced to a fuel cell 74 as described above, where the hydrogen is oxidized and the residuai CO and any CO2 are recyded into the feedstock at 75. Steam produced by the fuel cell is stored at 76, from where it is supplied to pyrolyzer 59 as an input to the water-gas shift reaction.

₂₀ [0066] A preferred feature of this embodiment is the use of concentric piping, wherein the high-pressure (ca. 20 bar) CO2 pipes are enclosed within the interiorof the medium-pressure CO2 piping. This reduces the required thickness of the high-pressure piping, making it feasible to transport gas at very high pressure wrthout long runs of excessively massive pipe. Optionally, as shown in the drawings, the medium-pressure CO2 piping may in turn be enclosed within low-pressure CO2 piping, which may provide further savings in weight and materials.

Claims (5)

1. We claim:

   1. A process for obtaining energy from waste, which comprises:

   (a) drying the waste;

   (b) anaérobie pyrolysis of the waste at 300’Cto 600°C to produce syngas, char, and biooil;

   (c) anaerobic pyrolysis of the syngas in the presence of a portion of the bio-oil, a portion of the char, additional carbon dioxide, and added water, at 600°C to 900’C, to increase the hydrogen content of the syngas;

   5 (d) anaérobie pyrolysis of the gas and oil produced at (c), in the presence of additional water and additional carbon monoxide, at 800’C to 1200°C and about 20 atmosphères pressure, to further increase the hydrogen content of the gas;

   (e) separating hydrogen, carbon dioxide and carbon monoxide from the gas produced at (d);

   (f) using the separated carbon monoxide as the additional carbon monoxide in step (d); and (g) using the separated carbon dioxide as the additional carbon dioxide in step (c).
2. 2. The process of claim 1, further comprising:

   10 (h) fuelling a steam generator by combusting the hydrogen separated at (e).
3. 3. A process for obtaining energy from waste, comprising:

   (a) drying the waste;

   (b) anaerobic pyrolysis of the waste at 300“C to 600°Cto produce syngas, char, and biooil;

   (c) anaerobic pyrolysis of the syngas in the presence of a portion of the bio-oil, a portion of the char, additional carbon dioxide, and added water, at 600 C to 900 C, to increase the hydrogen content of the syngas;

   (d) anaerobic pyrolysis of the gas and oil produced at (c), in the presence of additional

   15 water and additional carbon monoxide, at 800°C to 1200°C and about 20 atmosphères pressure, to further increase the hydrogen content of the gas;

   • (e) fuelling a fuel cell with the gas produced at (d), (f) driving a steam generator with steam produced by the fuel cell;

   (g) separating carbon dioxide and carbon monoxide from the effluent gases of the fuel cell;

   (h) using the carbon monoxide as the additional carbon monoxide in step (c); and (i) using a portion of the carbon dioxide as the additional carbon dioxide in step (b).

   5 4. The process of daim 3, wherein the fuel cell is a solid oxide fuel cell (SOFC).

   5 The process of claim 4, wherein the SOFC and steam generator are an integrated SOFC/turbîne System.
4. 7 . A process for obtainîng energy from waste, comprising:

   (a) drying the waste;

   (b) anaérobie pyrolysis of the waste at 300°C to 600°C to produce syngas, char, and biooil;

   (c) anaérobie pyrolysis of the syngas in the presence of a portion of the bio-oil, a portion of the char, additional carbon dioxide, and added water, at 600°C to 900’C, to increase the hydrogen content of the syngas;

   10 (d) anaérobie pyrolysis of the gas and oil produced at (c), in the presence of additional water and additional carbon monoxide, at 800°C to 1200°C and about 20 atmosphères pressure, to further increase the hydrogen content of the gas;

   (e) chilling the gas produced at (d) sufficiently to liquefy the CO2, and separating the liquid CO2 from the hydrogen and carbon monoxide;

   (f) fuelling a fuel cell with the hydrogen and carbon monoxide produced at (e), (g) using the carbon monoxide exiting the fuel cell as the additional carbon monoxide in step (c);

   15 (h) heating the liquid carbon dioxide separated at (e) so as to produce high pressure CO2 gas;

   (i) generating electricity by expandîng the high pressure CO2 gas produced at (h) through a gas turbine, thereby cooling the CO2;

   (j) using the cooled C02 generated at (i) to effect the chiHing of gas at (e); and (k) using a portion of the carbon dioxide as the additional carbon dioxide in step (b).
5. 8 . The process of claim 7, wherein the fuel cell is a solid oxide fuel cell (SOFC).

   9 The process of claim 8, wherein the SOFC and steam generator are an integrated SOFC/turbine System.