US20230287287A1

US20230287287A1 - Catalytic Biogas Combined Heat and Power Generator

Info

Publication number: US20230287287A1
Application number: US18/123,517
Authority: US
Inventors: Herng Shinn Hwang
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-11-16
Filing date: 2023-03-20
Publication date: 2023-09-14
Also published as: WO2019099060A1; US10626790B2; US20190145310A1; US11293343B2; US20220260009A1; US20200123969A9; US20190383212A1

Abstract

An apparatus and method to desulfurize a biogas containing sulfur. Since biogas is produced by an anaerobic digester from human, animal, kitchen and agriculture's wastes, it is a short term recycled product from the photosynthesis of CO₂, and has a net zero carbon emission. The sulfur compounds in the biogas can be removed by the following steps: (1) converting ail sulfur compounds into H₂S by the hydrogen produced from the biogas over Pt group metal catalysts; (2) adsorbing the H₂S at high temperature by the regenerable Pt group metal catalyst and adsorbents. The desulfurized biogas is further converted by an ATR/CPO reformer or a steam generating reformer to produce various reformates.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No. 17/684,484 filed Mar. 2, 2022, which is a continuation of U.S. application Ser. No. 16/557,190 filed Aug. 30, 2019 which is a divisional of U.S. application Ser. No. 15/813,914, filed Nov. 15, 2017, which claims priority to U.S. provisional application No. 62/422,756, filed Nov. 16, 2016, the entire contents of which application(s) are incorporated herein by reference.

BACKGROUND OF THE INVENTION

The CO₂in the atmosphere is constantly captured and converted through photosynthesis by various types of plants to produce human or animals' foods, such as sugar, starch, rice, wheat, potato, yam, grass, algae, vegetable, tree leaves, fruits et. al. After these foods are digested by human or animals, their excreta or the excess kitchen and agriculture's wastes can be used to produce biogas by an anaerobic digester, and the subsequent use of this biogas as a fuel for a combined heat and power (CHP) generator is realistically just returning the captured CO₂back into the atmosphere. In other words, the biogas is actually a short term recycled product of converting CO₂from one type of energy material into various other types of energy material and/or biomass, and the net carbon emission from a biogas CHP generator is zero. Therefore, using biogas as a fuel for a heat and power generator can reduce worldwide net carbon emission.
Anaerobic Digester:
By using the fermentation process in the absence of oxygen at about 38° C. (i.e. about 100° F.), an anaerobic digester can be used to produce biogas, odorless organic water, and odorless solid fertilizer from the waste materials. The biogas produced from the digester consists of 55-60% methane, 40-45% CO₂, 0.4-1.2% N₂, 0.0-0.4% O₂and 0.02-0.4% H₂S (americanbiogascouncil.org).
Combustible Reformed Gas and IC Engine (i.e. Reformate Engine):
A lot of Internet videos and documents have showed that a reformate gas containing hydrogen and CO can successfully be used as the sole fuel for an internal combustion engine. For example, the reformate gas produced from the partial combustion of woods had been used for several years in Germany during World War II (https://www.youtube.com/watch?v=bIWVB-JpdEk). Also, a small California company, All Power Laboratory, has designed a small gasifier to generate combustible H₂and CO gas from waste woods and husk, and has used this gas as the only fuel for a commercial IC engine. It has been reported that the combination of their gasifier, an IC engine and an electrical generator can generated enough electricity for their own facility from the waste biomass.
U.S. Pat. Nos. 7,028,644 and 7,225,787, herein incorporated by references, had used an on-board Plasmatron converter to produce the H₂and CO reformate from hydrocarbons (HC) and bio-fuels. This reformate gas could then be mixed with extra air and fuel to become a lean burn fuel mixture as the engine's sole fuel, and the engine can then be operated under higher compression ratio. As the results, this on-board Plasmatron reformer could increase gasoline engine's thermal efficiency by 20-25%, could reduce gasoline engine's NO_xemission up to 90% and could reduce diesel engine's emission by 90% (Diamond and Cohn, Office of Transportation Technologies, press release December 2001).
Flexible-Fuel Hydrogen Generator for IC Engines and Gas Turbines:
U.S. Pat. No. 9,440,851, herein incorporated by reference, describes the use of an on-board catalytic reformer to produce H₂and CO reformate gas from various vaporized hydrocarbons and/or bio-fuels and, thus, it can be used to replace the Plasmatron reformer to generate H₂for the IC engine. Since this reformer uses the Pt group metal catalysts to accelerate the reactions, and it also includes the necessary devices and the control software for automatic operation of the generator, this catalytic reformer is fundamentally very different in equipment design and the operating procedures from those of the homogeneous (i.e. non catalytic) partial oxidation gasifier or Plasmatron.
The reformed gas so produced can be cooled, dried and compressed to 1-100 atmospheres, and can be stored in one or several high pressure vessels. This stored combustible reformate can then be used as a sole fuel for a reformate IC engine/gas turbine, which will drive a generator to produce electricity, or it can be combined with extra air and extra fuel to become a lean burn fuel mixture for the IC engine/gas turbine. By utilizing this lean combustion process at a higher compression ratio, complete combustion reactions inside the engine cylinder can successfully increase the engine/gas turbine's thermal efficiency and can also reduce its pollution emission.
Removing Hydrogen Sulfide from Biogas and the Common Industrial Desulfurization Process:
The biogas from the anaerobic digester contains 0.02-0.4% hydrogen sulfide (H₂S). After complete combustion inside an engine cylinder, the H₂S will be converted into SOx, which will combine with moisture/steam and produce acid in the exhaust gas. Therefore, to avoid corrosion to the downstream IC engine and other equipment, this H₂S biogas must be removed before using it as the direct IC engine/gas turbine's fuel.
Currently, the common low temperature sulfur removal processes for biogas are water wash, caustic soda solution wash (solutions such as sodium hydroxide, potassium hydroxide, calcium hydroxide, mono ethanolamine etc.), iron oxides, iron sponge, activated carbon, molecular sieve, silica gel, activated alumina, bio-bacteria sulfur removal technology, pressure swing adsorption process etc. However, if the above adsorbents are used, they either are non-regenerable or cannot be regenerated repeatedly for long term application. Therefore, they have waste disposal problem once they reach their saturation capacity (Allegue and Hinge, Danish Technological Institute, December 2014).
One common commercial industrial sulfur removal technology is to use the catalytic hydro-desulfurization process, which can convert any organic sulfur compounds catalytically with the recycled hydrogen to produce H₂S over a Co—Mo/Al₂O₃catalyst at 500° C. and 100 atmospheres and, then, the process will use ZnO adsorbent to remove the H₂S from the gas stream. In 1985, U.S. Pat. No. 4,522,894, herein incorporated by reference, had described a new catalytic autothermal reforming (ATR) process to produce hydrogen and CO over a monolithic Pt/Pd/Al₂O₃catalyst from a diesel oil, air and steam fuel mixture at O₂/C ratio=0.378, H₂O/C ratio=2.57, 1 atmosphere and a temperature <1000° C. Under this operating condition, all organic sulfur compounds (about 0.12% sulfur) in the commercial diesel oil were converted into hydrogen sulfide at about one atmosphere, and the produced H₂S in the reformate was then removed by a downstream high temperature ZnO adsorbent bed. In addition, U.S. Pat. No. 7,128,768, herein incorporated by reference, has described the use of a mini catalytic reformer or other H₂generator to produce dry hydrogen to convert all sulfur compounds in the hydrocarbons into H₂S, and then removed the H₂S by a downstream ZnO bed. However, the ZnO adsorbent needs to be replaced once it reaches its saturation capacity as shown in US 2004/0178124 A1, herein incorporated as reference.
U.S. Pat. No. 7,074,375, herein incorporated by reference, describes a catalytic oxidation process of converting all sulfur compounds into SOx (i.e. SO₂and SO₃) with an oxidation catalyst at a O₂/C ratio between 0.01 to 0.04, and at a preferred temperature between 250 to 400° C. The SOx produced can be removed by the downstream adsorbents such as alkali metal oxides, alkali earth metal oxides and/or base metal oxides (i.e. oxides of Ni, Fe, Cu, Zn supported on porous SiO₂or Al₂O₃). Subsequent U.S. Pat. Nos. 9,034,527, 9,640,822 and 9,515,338, herein incorporated by references, have advanced this catalytic oxidation process to remove the organic sulfur compounds from various hydrocarbons. Briefly, this patented sulfur removing process is to control the O₂/C ratio below 0.04 over an oxidation catalyst to produce selectively SOx, but not to hydrogenate the sulfur compounds into H₂S over a Pt group metal hydrogenation catalyst. As shown in the patent, H₂S will be produced if O₂/C ratio of the feed gas is greater than 0.04, especially above 0.08.
U.S. Pat. Nos. 7,820,037, 8,236,262, 8,308,848 and 9,421,516, herein incorporated as references, describe the preparation methods for Cu—Zn—Al—Ni/Fe, Ni—Cu—Al—Na—Zn, Ni/AI and Al/Ni/Zn oxide catalysts, which are used as adsorbents for removing sulfur compounds from various hydrocarbon fuels.
U.S. Pat. Nos. 4,552,733, 4,780,447, 4,939,113, 5,024,985, 5,196,390 and 7,871,459, herein incorporated as references, have shown that all sulfur compounds in the gasoline are converted into SO₂after the engine combustion, and the SO₂is stored by the downstream catalytic converter's oxygen storage component, which is mainly cerium oxide, as sulfate, sulfide and/or sulfur radicals. The stored sulfur is released as H₂S later by the next engine's rich operating mode. Therefore, it has been demonstrated that the Pt group catalyst, which also contains one or more oxides of Ni, Fe, Cu, Mn, Ce, Ce/Zr and mixture thereof, is able to remove H₂S from the exhaust gas by adsorption/reaction during the engine's rich operating mode and, then, be regenerated by converting the stored sulfur into SO₂with the exhaust gas during the next engine's lean operation mode, which contains a small % of excess O₂.
U.S. Pat. No. 7,901,566, herein incorporated as reference, describes the use of a catalyst in a pre-reformer to remove sulfur compounds from the hydrocarbon (HC) fuels with steam. The catalyst is a Pt/Rh supported on a non-sulfating SiO₂—ZrO₂oxide, which also consists at least one member of Ni, NiO, Mn, MnO, Fe, FeO and Fe₂O₃. The deactivated catalyst can then be regenerated either with O₂or with a gas mixture consisting of O₂, steam and HC to remove the adsorbed sulfur on the catalyst surface as SO₂.

BRIEF SUMMARY OF THE INVENTION

This distributed combined heat and power generator is to utilize the biogas from an anaerobic digester to provide heat and electricity to the local residents for their daily living. It can also avoid about 10% electricity transmission loss and/or any transmission power loss due to bad weather. Furthermore, since this catalytic reformer can produce H₂and CO from other fuels, any vaporized hydrocarbons or bio-fuels can be used to replace the biogas for generating heat and power with the same equipment. Therefore, this catalytic biogas CHP generator is actually a multi-fuel CHP generator.
To avoid severe corrosion to the downstream equipment, and to increase the H₂S adsorption capacity by the adsorbents, a new desulfurization system, which comprises one catalytic partial oxidation (CPO) sulfur converter and one high temperature regenerable adsorbent bed, is specifically designed to remove the H₂S and other sulfur compounds from the biogas, and this new desulfurization system is installed between the biogas storage tank and the main reformers as shown by #8 in FIG. 2 .
As shown in FIG. 2 , if the biogas contains high % sulfur compounds and/or other various containments, one low temperature pre-desulfurizer bed at a temperature between −25° to 50° C. can be installed between the biogas storage tank and this new desulfurization system. Briefly, this low temperature pre-desulfurizer bed utilizes one or more methods selected from the group consisting of liquid wash, filter, oxide adsorbents and/or the regenerable supported Pt group metal catalysts to remove moisture, sulfur and other containments from the biogas. However, the regenerable Pt group metal catalysts is preferred to be used in this bed, and its preparation method will be discussed in the following sections. Subsequently, the partially purified biogas can enter into the CPO sulfur converter of this new desulfurization system for further sulfur removal from the biogas.
For the CPO sulfur converter in this new desulfurization system, all sulfur compounds are converted into H₂S over Pt group catalysts by the hydrogen produced from the CPO reactions of biogas under the O₂/C ratio of 0.05 to 0.25 and a temperature between 200° to 800° C. The produced H₂S can then be removed from the reformate at a temperature between 300° to 900° C. by the supported regenerable Pt group metal catalysts, which also contain the H₂S adsorbent oxides. Here, the Pt group metal catalysts, which comprise one or more metals of Pt, Pd, Rh, Ir, Ru, Os and mixture thereof, are supported on a stabilized Al₂O₃. The Al₂O₃power has surface area between 50 to 600 m2/g, and also contains high temperature oxide stabilizer such as one or more oxides selected from the group of lanthanum, cerium, praseodymium, rhenium, zinc, tin, calcium, potassium, zirconium, yttrium, barium, strontium, neodymium, magnesium and the mixture thereof. Furthermore, one or more oxides, which are selected from the group of Ni, Cu, Fe, Co, Mo, Zn, Cu/Zn, Ce, Ce/Zr, Al, Mn and the mixture thereof, can be added to the above Pt metal group catalysts as the H₂S adsorbents, and these H₂S adsorbents are either unsupported oxides or oxides supported on the above stabilized Al₂O₃.
Subsequently, the desulfurized biogas can mix with additional O₂/air and water to adjust the inlet fuel mixture's O₂/CH₄and H₂O/CH₄ratios, and this fuel mixture can then be injected into: (1). a Flex-Fuel Autothermal (ATR) reformer to convert the remaining bio-methane to increase the % H₂in the reformate for fuel cell devices, and/or for the energy (i.e. excess electricity) storage as H₂gas; (2) a CPO reformer to adjust the produced reformate's H₂/CH₄ratio as a fuel for a reformate IC engine/gas turbine, which can perform H₂assisted lean combustion at a high compression ratio; or (3). a catalytic steam generating reformer to produce high pressure steam reformate, which can drive a steam turbine/steam engine and an electrical generator for generating electricity.
Three chemical processes can satisfactorily be used to produce H₂and CO from biogas, and these chemical reactions are as followings:

- (1). Steam Reforming Reformer (SR, Endothermic reaction):

CH₄+H₂O→CO+3H₂

- (2). Catalytic Partial Oxidation Reformer (CPO, Exothermic reaction):

CH₄+½O₂→CO+2H₂

- (3). Autothermal Reformer (ATR, Adiabatic reaction):

CPO+SR
2CH₄+½O₂+H₂O→2CO+5H₂
Another catalytic reaction is very useful to generate high pressure steam from biogas over the Pt group metal catalysts:

- (4). Complete Catalytic Combustion—steam generating reformer (Exothermic Reaction):

CH₄+2O₂→CO₂+2H₂O
In the last several decades, numerous patents and technical papers have published the results of the above reactions over the supported and unsupported Pt group catalysts with excellent activity and selectively. However, by analyzing the experimental facts, the results can be explained and summarized as: (A). reaction (2) is the dominant reaction when O₂/CH₄ratio of the inlet fuel mixture is less than 0.60; (B). reaction (1) is the only possible reaction without O₂in the fuel mixture; (C). reaction (4) is the dominant reaction when O₂/CH₄is over 1.00; (D). rate of reaction (2) is much faster than rate of reaction (1), i.e. partial oxidation reaction is the dominant reaction when both O₂and water are present in the inlet fuel mixture, and (E). reaction (3) is the combination of CPO reaction section followed by SR reaction section in an adiabatic reactor. Therefore, it can further be recognized and concluded from these studies that the reaction path and the reformate gas composition can be determined by simply controlling the O₂/CH₄ratio of the reformer's inlet fuel mixture. In other words, by simply controlling the O₂/CH₄ratio of the reformer's inlet fuel mixture and the operating conditions, the same flex-fuel catalytic reformer can be used to produce various reformate composition products, which can be utilized by various different power producing devices to produce heat and electricity for general applications.
U.S. Pat. No. 8,397,509, herein incorporated by reference, describes a “Catalytic Engine” process for generating a high pressure reformate, which contains high % steam, over the Pt group metal catalysts from hydrocarbons and bio-fuels by a catalytic reformer. This high pressure steam reformate is then used directly to drive a turbine, turbocharger and/or any type of gas turbine, and also to drive together an electric generator to generate electricity. Therefore, this “Catalytic Engine” process uses a catalytic reformer to replace a traditional shell and tube boiler for high pressure steam generation, and it can be used by a distributed stationary or mobile power station.
To extend the catalyst's life and to maintain high methane conversion for producing the H₂and CO reformate from bio-methane, the reaction temperature must be controlled below 1200° C. Since biogas contains a large amount of CO₂, and the CO₂has a high heat capacity, it can be used to replace portion of the feed water. Therefore, for the ATR reformer of this biogas CHP generator, the O₂/CH₄ratio of the inlet fuel mixture is controlled at a value between 0.05 to 0.80, and the (CO₂+H₂O)/CH₄ratio between 0.05 to 10.0.
U.S. Pat. Nos. 4,522,894, 9,440,851 and also the paper by Giroux et. al. (Applied Catalysis B. vol. 55, 185-200 (2005), herein incorporated by references, have demonstrated that the monolithic Pt metal group catalysts can effectively convert the hydrocarbons or bio-fuels into H₂and CO combustible gas by catalytic partial oxidation reactions, or by autothermal reactions. Therefore, this biogas CHP generator will continue to use the same monolithic Pt group metal catalysts prepared, described and used by U.S. Pat. Nos. 4,522,894 and 9,440,851 patents.
After the reformer, the dry reformate produced by either the ATR or the CPO reformer can be cooled, compressed and stored in high pressure vessels between 1 to 100 atmospheres. The stored reformate can then be used as fuel for the downstream IC engine/gas turbine to drive a generator, and to produce electricity for the system's control computer and instruments. Simultaneously, the electricity produced by wind turbine, solar panel and/or the electricity from battery can also be used to operate the controllers, and the excess electricity can be utilized to do electrolysis of DI water to produce H₂and O₂. Under the normal operating conditions, the H₂so produced can be used as portion of the lean fuel mixture for an IC engine/gas turbine to increase its combustion efficiency; The O₂so produced can be used to replace air as reformer's reactant to perform autothermal reactions and to produce the H₂from the biogas. Furthermore, the produced H₂can be compressed to a high pressure tank and, thus, the excess electricity can be stored as H₂. When necessary, the stored H₂can later be used by fuel cell devices and/or IC engines to produce electricity.
Based on thermodynamic equilibrium calculations, if pure O₂and pure CH₄are used in the inlet fuel mixture without the N2 dilution from air, the % (H₂+CO) concentration in the reformed gas generated by the CPO reformer can be increased from about 40% to about 60%. However, using the identical inlet fuel mixture, the % (H₂+CO) concentration generated by an ATR reformer can be increased from about 51% to about 72%. Therefore, using pure O₂to replace air as ATR/CPO reformer's reactant can improve the % (H₂+CO) in the reformate to the concentration close to that produced by the steam reforming reactions. In this case, the ATR reformer, which can produce higher % (H₂+CO) reformate from the same fuel mixture, will have the same SR reformer's advantage over the CPO reformer.
To reduce the sulfur content of the purified biogas below 10 ppbv for the fuel cell devices, a polishing desulfurizer bed, which comprises both the regenerable Pt group metal catalysts and the oxide sulfur adsorbents, is controlled at a temperature between −25° to 600° C. This polishing desulfurizer bed can be installed between the high temperature regenerable adsorbent bed and the subsequent ATR/CPO reformers as shown in FIG. 1 .
Finally, the hot reformate from the reformers and the hot exhaust gas from the IC engine/gas turbine can passed through heat exchangers to provide hot water and/or hot air for the local residents.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 : Flow Chart for a Catalytic Biogas Combined Heat and Power Generator.

FIG. 2 : Flow Chart for a Regenerable Desulfurization System (identified by #8).

FIG. 3 : Automatic Control Hardware Devices Consisting of One computer, One Programmable Logic Controller (PLC) and Several Input/output Interface Modules.

FIG. 4 : A Control Curve for Reactants' Flow Rates as a Function of Reformate Pressure in the Storage Vessels.

DETAILED DESCRIPTION OF THE INVENTION

Description of the Preferred Embodiments

Because of the global warming and the abnormal worldwide weather pattern in recent years, it is wise to combine the renewable energy resources such as biogas, solar, wind and geothermal energies to cut down the carbon emission and to provide heat and electricity from biogas for daily living.
For this invention, a Catalytic Biogas Combined Heat and Power (CHP) Generator and method of operating this CHP generator comprises:

- (1). one biogas storage tank at 1 to 100 atmospheres;
- (2). one regenerable desulfurization system comprising:
- a) one CPO sulfur converter for converting all sulfur compounds in the biogas over the supported Pt group metal catalyst into H₂S at a temperature between 200° to 800° C., wherein the O₂/C ratio of the inlet fuel mixture is between 0.05 to 0.25, and the % (H₂+Steam) in the gas mixture is between 0% to 20%, and
- b) one high temperature regenerable adsorbent bed at a temperature between 300° to 900° C., wherein the supported Pt group metal catalyst containing one or more oxides selected from the group of Ni, Cu, Fe, Co, Mo, Zn, Cu/Zn, Ce, Ce/Zr, Al, Mn and the mixture thereof are used to react/adsorb the H₂S on the catalyst,
- c) one engine exhaust gas with <2% excess O₂or a hot gas containing <5% O₂and <2% CH₄for catalyst regeneration, wherein the reacted/adsorbed sulfur on said supported Pt metal group catalyst is converted into odorless SO₂at a temperature between 300° to 900° C.;
- (3). one or more catalytic biogas reformers for producing various type of reformate gas over the Pt group metal catalysts by controlling the O₂/CH₄ratio of the reformer's inlet fuel mixture selected from:
- a) one flex-fuel catalytic ATR reformer to produce H₂reformate as a fuel for the IC engine/gas turbine, fuel cell electric generator or H₂storage, wherein the reformer's inlet fuel mixture contains O₂/CH₄<0.80 and (H₂O+CO₂)/CH₄<10.0;
- b) one steam generating reformer to produce high pressure steam for a steam turbine/steam engine, wherein the inlet fuel mixture of the generator is operated at O₂/CH₄ratio >1.0, H₂O/CH₄ratio >3.0 and at a temperature below 1000° C. and a pressure between 5 to 50 atmospheres, and
- c) one CPO reformer to adjust the reformate's H₂/CH₄ratio as a fuel for the reformate engine/gas turbine, wherein the O₂/C ratio of the biogas inlet fuel mixture is <0.80, and the (CO₂+H₂O)/CH₄is <5.0,
- (4). one or more power devices selected from the group of reformate engine, gas/steam turbine, steam engine, IC engine and fuel cell device for utilizing the proper reformate produced from the reformers described in (3) to produce power, wherein they are used to drive one or more electric generators to generate electricity;
- (5). several heat exchangers for recovering heat from the reformate and/or from the engine/gas turbine's exhaust gas, wherein the produced hot air and/or hot water from the heat exchangers are available for local residents and/or for general applications;
- (6). one electrolyzer for dissociating DI water to produce H₂and O₂, wherein the generator's self-generated electricity, and/or the electricity generated from a solar panel, a wind turbine, or an electric grid are used for the electrolysis of water;
- (7). several storage tanks for storing the reformate, H₂and O₂gases at 1 to 100 atmospheres, wherein each stored gas is used for general application; and
- (8). an automatic control system consisting of a control computer/micro processor, valves, flow controllers, thermocouples, sensors, pumps and control software, wherein the controlling system is used to deliver the specific inlet fuel mixture to each reformers at the specific O₂/CH₄, H₂O/CH₄, (H₂O+CO₂)/CH₄ratios, and also to control the reactions at the specific temperature and pressure.

Producing Hydrogen from Hydrocarbons and Bio-Fuels:
In the 1980s, U.S. Pat. No. 4,522,894 first introduced the monolithic Pt/Pd/Al₂O₃catalyst to produce H₂and CO by the catalytic partial oxidation reactions of the sulfur containing commercial diesel fuel, and also to provide heat for the following Ni/Al₂O₃or Pt/Rh/Al₂O₃pellet catalyst to produce more H₂and CO by catalytic steam reforming (SR) reactions. Because of its extremely rapid reaction rate and an excellent selectivity, the O₂in the reformer's inlet fuel mixture can be converted completely in less than 36 milliseconds (space velocity >100,000/hr @STP), and it is also found that the reacted diesel oil was mostly converted selectively into the main H₂and CO products, but not the unwanted full combustion products of H₂O and CO₂. Therefore, it was concluded that the monolithic Pt/Pd/Al₂O₃catalyst is an excellent partial oxidation catalyst. Later, in the 2000s, further additional developments worldwide had found that the unsupported or the supported monolithic or pellet Pt group metal catalysts were all excellent partial oxidation catalysts for producing H₂and CO from fuels such as natural gas, LPG, vaporized hydrocarbons and bio-fuels.
According to U.S. Pat. Nos. 4,522,894 and 9,440,851, the Pt group metal catalysts could be prepared by impregnating one or more of Pt group metal solutions at a given concentration into an Al₂O₃power, and obtain a catalyzed washcoat powder at 0.01 to 10.0% metal content. The Al₂O₃power has surface area between 50 to 600 m2/g, and also contains high temperature oxide stabilizer such as one or more oxides selected from the group of lanthanum, cerium, praseodymium, rhenium, zinc, tin, calcium, potassium, zirconium, yttrium, barium, strontium, neodymium, magnesium and the mixture thereof. Furthermore, one or more oxide powders, which are selected from the group of Ni, Cu, Fe, Co, Mo, Zn, Cu/Zn, Ce, Ce/Zr, Al, Mn and the mixture thereof, can be added and mixed with the above catalyzed Pt group washcoat powder as the H₂S adsorbents, and these H₂S adsorbents are either unsupported oxides or oxides supported on the above stabilized Al₂O₃. Then, the combined washcoat powders are coated on the surface of an high temperature inert carrier such as the ceramic monolithic support to obtain the total Pt group metal loading between 0.1 to 2500 g/ft3.
The inert monolith support was a ceramic carrier which contains 10 to 1200 CPI. The other suitable inert catalyst support can be a ceramic monolith, metallic monolith, pellet, wire mesh, screen, foam, plate, silicon carbide, static mixer etc. For the mobile devices/equipments, monolithic catalyst supports are preferred. But the monolith, pellet, gauze, wire mesh, screen, foam, plate, static mixer, heat exchanger or other shapes of catalyst's supports can satisfactory be used for stationary devices/equipments.
To be used as the catalyzed washcoat support, the inert materials must be capable of sustaining a temperature between 500° C. to 1200° C. in a rich or lean atmosphere without losing its surface area, strength and shape. For example, The inert ceramic substrate can be made of alumina, alumina-silica, alumina-silica-titania, mullite, cordierite, zirconia, zirconia-ceria, zirconia spinel, zirconia-mullite or silicon carbide, and the metallic substrate can be made of Fecralloy, Kanthal, stainless steel and other high temperature alloys.
Biogas ATR Reformer:
Due to the fact that the biogas contains large amount of CO₂, and CO₂has high heat capacity, CO₂can be used to replace water in the inlet fuel mixture for controlling the reformer's temperature below 1200° C. In other words, the composition of the inlet reformer's biogas fuel mixture should be modified, and the H₂O/CH₄ratio in the inlet fuel mixture can be decreased, and the CO₂/CH₄ratio can be increased from those described in U.S. Pat. No. 9,440,851. For this Biogas CHP Generator, the O₂/CH₄of the inlet reformer fuel mixture should be maintained <0.80, and the (H₂O+CO₂)/CH₄ratio between <10.0. In general, the reformer's temperature should be controlled below 1200° C. to maintain high methane conversion activity, and also to extend catalysts' service life without thermal deactivation and coke formation.
Additionally, the preferred operating condition without coke formation for this biogas CHP generator is to perform the reforming reactions, and to generate electricity under a steady (stationary) condition. Therefore, the reactants' flow rates. the inlet O₂/CH₄ratio, the inlet (CO₂+H₂O)/CH₄ratio and the reactor temperature are mostly controlled under a given steady state operating condition, and avoid any sudden abrupt change of each reactant's flow rate.
According to U.S. Pat. No. 9,440,851, all hydrocarbons which can be vaporized such as natural gas, LPG, CNG, biogas, bio-ethanol, methanol, gasoline, diesel, bio-diesel and other hydrocarbons, can be converted in this reformer to produce H₂and CO reformate by the Pt group metal catalysts under a given temperature and pressure. Therefore, in emergency or any special occasions, any one of the above fuels and/or their fuel mixture can be used as fuel for this apparatus. In other words, in addition to biogas, this Biogas CHP Generator is a multiple fuel CHP generator.
Reformate IC Engine/Gas Turbine:
According to U.S. Pat. Nos. 4,522,894 and 9,440,851, if the O₂/C ratio of the inlet reformer's fuel mixture is below 0.50 at a space velocity >100,000/hr (@STP), all O₂in the mixture will completely be converted by the Pt group metal catalysts to become part of the reformed gas, while the conversion of the hydrocarbon fuel will be less than 100%. Therefore, the % biogas conversion can be controlled by adjusting the O₂/CH₄ratio of the inlet fuel mixture between 0.05 to 0.50. In other words, the % methane remaining in the reformed gas can be controlled by adjusting the O₂/CH₄ratio and, thus, can produce various H₂/CH₄ratios of the Hythane gas (i.e. methane and H₂mixture) for the downstream IC engine/gas turbine. As mentioned previously in U.S. Pat. No. 7,721,682, herein incorporated by reference, the Hythane gas mixture can improve the engine's thermal efficiency and can reduce the NOx pollution.
Catalytic High Pressure Steam Generating Reformer:
According to reaction (4), bio-methane can be combusted completely into CO₂and H₂O, and the total reaction heat produced by the reaction can then be used completely to vaporize water and to generate high pressure reformate containing high % steam. This reformate stream is then used via pressure difference to drive a steam turbine, a turbocharger or a steam engine, which in turn will drive an electric generator to generate electricity (U.S. Pat. No. 8,397,509). Therefore, this catalytic reformer can be used to replace a traditional power plant's shell and tube boiler for high pressure steam generation. In addition, complete catalytic combustion of bio-methane with excess oxygen at a temperature below 1000° C. will not produce CH₄and NOx pollutants, and the total reaction heat is used completely for steam generation. In other words, there are no waste heat loss through the flue gas, and the system's thermal efficiency is improved.
Flow Control Curves:
One or more flow control curves can be used to define each reformer's reactant flow rate and the total reformer's output flow capacity as a function of pressure in the reformate's storage vessels. In other words, a given flow control curve is used to regulate each reactant's flow rate, to define the O₂/CH₄and (CO₂+H₂O)/CH₄ratios of the inlet fuel mixture, to define the dry reformate composition, to decide the reformer's start-up and shutdown, to regulate the reformer's operating temperature and pressure, and to determine the total reformer's reformate flow output. Briefly, according to the location on a given control curve, every single point on a given control curve can supply a group of pre-calibrated set points for all flow meters/controllers, the operating temperature and pressure, and these set points are down loaded from the control computer and/or the microprocessors to the programmable Logic Controller (PLC) for the purpose of controlling each reactant's flow rate, and the reformer's temperature and pressure; Once each reactant's flow rate is fixed according to the pre-calibrated set point, the O₂/CH₄and the (H₂O+CO₂)/CH₄ratios of the inlet fuel mixture are fixed, and the total flow rate of the inlet fuel mixture is fixed. Subsequently, after complete conversion of the inlet CH₄and O₂by the Pt group metal catalysts in the biogas reformer at a given reaction temperature and pressure, the total reformate flow output produced and the dry gas composition are determined.
In addition, if several multiple points on the same control curve are pre-calibrated at the same the O₂/CH₄and the (H₂O+CO₂)/CH₄ratios, but at different flow rates, these points are capable of producing a series of different reformate flow outputs with the same dry gas composition. Furthermore, multiple pre-calibrated control curves for other fuels are used to provide different reformer's inlet fuel mixtures and, thus, would produce by the same reformer the dry reformate from various hydrocarbon fuels and/or bio-fuels with different gas composition. In other words, by selecting the proper control curve, this reformer can operate effectively and efficiently with all potential fuels, and the biogas CHP generator can be a multiple fuel CHP generator. Therefore, it can be very useful in an emergency situation when biogas is not available or in short supply.
Catalytic De-Sulfurization Process:
If the biogas contains high % sulfur compounds and/or other various containments, one low temperature pre-desulfurizer at a temperature between −25° to 50° C. can be installed between the biogas storage tank and the CPO sulfur converter. The regenerable supported Pt group metal catalysts is preferred to be used in this pre-desulfurizer, and it comprises: (1). one or more regenerable Pt group metal catalysts, which comprise one or more metals of Pt, Pd, Rh, Ir, Ru, Os and mixture thereof, are supported on the stabilized Al₂O₃, and (2). one or more oxides selected from the group consisting of Zn, Ni, Ce, Ce/Zr, Fe, Co, Mo, Cu, Cu/Zn, zeolite, Mn, La, Ba, Sr, Al, Si and mixture thereof, wherein these oxides can be unsupported or supported on the stabilized Al₂O₃.
As described previously in U.S. Pat. No. 4,522,894, all organic sulfur compounds can be converted into H₂S by the hydrogen produced inside the ATR reformer, and the produced H₂S can be adsorbed and removed from the reformate by the downstream ZnO bed at a temperature between 300° to 400° C. However, under the influence of high % water/steam, the capacity of adsorbing H₂S by ZnO will be decreased rapidly from 10-20 gS/100 g to 0.1 gS/100 g, and lost its efficiency to remove H₂S from the stream (Farrauto, R. et al., Annu. Rev. Mater. Res. 2003, Vol. 33, Page 1-27). Therefore, in order to improve the H₂S adsorption capacity, the O₂/CH₄ratio of the inlet fuel mixture to the CPO sulfur converter in this regenerable desulfurization system is controlled at a value between 0.05 to 0.25, and the % (H₂+Steam) between 0 to 20%.
At a value of the O₂/CH₄ratio between 0.05 and 0.25, enough amount of O₂is provided to convert all the sulfur compounds in the inlet fuel mixture into H₂S by the hydrogen produced from the CPO reactions of biogas. Then, the produced H₂S is removed effectively in the following adsorption bed at a temperature between 200° to 800° C. It is known that sulfur compounds can be adsorbed strongly on the oxide surface of Ni, Cu, Fe, Co, Mo, Zn, Cu/Zn, Ce, Ce/Zr, Al, Mn and the mixture thereof, and that the Pt group metal catalyst can convert the adsorbed/reacted sulfur into SO₂. Therefore, as discussed previously, this high temperature regenerable adsorbent bed comprises one or more regenerable supported Pt group metal catalysts, which also contains one or more oxides as H₂S adsorbents. However, the catalyst must be kept below 900° C. to avoid thermal deactivation of the Pt group catalyst and the H₂S adsorbents.
Subsequently, the de-sulfurized biogas is then used by one or more CPO, ATR and steam generating reformers to produce various reformate composition according to the demand of the desired applications, as shown in FIG. 1 .
The adsorbed/reacted sulfur on the catalyst's washcoat (i.e. oxide) can be regenerated by passing either an exhaust gas with <2% excess O₂, or a hot gas containing <5% O₂and <2% CH₄over the Pt group metal catalysts, and can be released as SO₂at a temperature between 300° to 900° C. If the engine's exhaust gas is below 300° C., it is necessary to inject both air/O₂and CH₄simultaneously, and uses the CPO reaction heat to maintain the temperature during the regeneration. However, most of the time, the engine's exhaust gas temperature is high enough to do the regeneration and, in this case, only O₂/air is required to be injected into the exhaust gas.
During regeneration, the adsorbed/reacted sulfur will be converted into SO₂, which can either be vented into atmosphere, or be removed/absorbed by the traditional lime/limestone, water, or caustic soda wash techniques.
Due to the fact that every adsorbent has its own unique adsorbing capacity (i.e. limitation) for removing a specific contaminant compound, a combination of several different adsorbents operated at different temperatures is frequently required to remove completely the contaminants from a given fuel mixture, and the adsorbents are most likely required to be changed when a new fuel with different sulfur compounds is admitted into the inlet fuel mixture. However, if all organic sulfur compounds in the inlet fuel mixture are converted catalytically into H₂S, the removal of all sulfur compounds becomes a simpler task of removing H₂S from the reformate stream. Furthermore, since the supported Pt group catalysts used here can be regenerated for continuous application, this new sulfur removal technology becomes very convenient, and the catalyst/adsorbent can have a longer service life without being replaced and/or being land filled. Therefore, it has advantages over the current biogas non-regenerable H₂S removal techniques described previously.
To avoid deactivation of the electrodes for the fuel cell electric generators, such as PEMFC and SOFC, the sulfur level of the purified biogas must be maintained below 10 ppbv, while it is satisfactory to maintain below 25 ppmv for an IC engine/gas turbines. In other words, the degree of desulfurization of the biogas will depend on the intended application.
To insure the sulfur content of the purified biogas is constantly maintained below 10 ppbv, a polishing desulfurizer bed, which is controlled at a temperature between −25° to 600° C., can be installed between the high temperature regenerable adsorbent bed and the ATR/CPO reformer. This polishing desulfurizer bed comprises: (1). one or more regenerable Pt group metal catalysts supported on the stabilized Al₂O₃, and (2). one or more oxides selected from the group consisting of Zn, Ni, Ce, Ce/Zr, Fe, Co, Mo, Cu, Cu/Zn, zeolite, Mn, La, Ba, Sr, Al, Si and mixture thereof. The main purpose of this polishing desulfurizer is to clean up the residual sulfur compounds before the reformers with oxide adsorbents at a lower space velocity (i.e. larger adsorbent reactor volume).
Other fuels, such as natural gas, LPG, bio-ethanol, methanol, gasoline, diesel, bio-diesel, and other vaporized organic compounds, can utilize this sulfur removal methods and this Catalytic Biogas CHP Generator to remove all sulfur compounds from the fuel mixture. In other words, if the O₂/C ratio in the inlet fuel mixture of this CPO reformer is controlled at a value between 0.05 to 0.25 (i.e. C is the fuel carbon, does not include C in CO₂), and the % (H₂+H₂O) is between 0% to 20%, all organic sulfur compounds in any fuels mentioned previously will be converted into H₂S by the H₂produced by the CPO reaction, and the H₂S can be removed by the subsequent high temperature regenerable adsorbent bed and, if necessary, by the additional polishing desulfurizer bed.

Exemplary Embodiments Described

FIG. 1 is the flow chart for the Catalytic Biogas CHP Generator of this invention. As shown in FIG. 1 . the biogas which is generated by an anaerobic digester can be stored in tank #10, and the excess water, H₂S and other contaminants in the biogas will first be treated in the desulfurization system #8. As shown in FIG. 2 , the desulfurization system #8 comprises: (a). one low temperature pre-desulurizer (#19); (b). one CPO sulfur converter (#20); (c). two parallel high temperature H₂S adsorbent beds (#21A &21B); (d). one polishing desulfurizer (#21C). Here, the low temperature pre-sulfurizer (#19) is used to partially remove the H₂S, moisture and other contaminants from the biogas; CPO converter #20 is used to convert all remaining sulfur compounds into H₂S; the two parallel high temperature adsorbent bed #21A/21B are used to remove the H₂S from the biogas down to about 25 ppm level for the IC reformate engines, and the polishing desulfurizer (#21C) is used to remove the H₂S in the reformate from about 25 ppm down to 10 ppbv level for the fuel cell devices. Briefly, the CPO sulfur converter #20 and the adsorbent bed #21A and #21B are the main units for removing the sulfur compounds from the biogas in this desulfurization system #8. But the pre-desulfurizer #19 and the polishing desulfurier #21C are optional units, which are used only when the system requires additional treatments to either remove extra containments from the biogas, or to meet the more demanding sulfur requirement of the downstream fuel cell devices.
As shown in FIG. 2 , the dry desulfurized biogas from the desufurization system #8 is compressed and is stored in tank #24A at a pressure between 1 to 100 atmospheres. It can then be injected directly with additional amount of water and air/02 into the following CPO reformer (#22) to provide a fuel mixture at a given O₂/CH₄and H₂O/CH₄ratio. This CPO reformer #22 in the system can adjust the H₂/CH₄ratio to provide a given Hythane gas for the downstream reformate engine #6. In addition, the desulfurized biogas can be injected with additional amount of air/O₂and water at a specified O₂/CH₄and H₂O/CH₄ratio to the following ATR or steam generating reformer (#9), and the reformers will produce the reformate according the fuel mixture's O₂/CH₄ratio for the downstream power generating devices, such as IC engine, gas turbine, steam turbine/engine, fuel cell electric generators et. al.
Also, shown in FIG. 2 , the exhaust gas from the reformate engine #6 can be used to the regenerate the Pt group metal catalysts which are used in the pre-desulfurizer #19, the high temperature H₂S adsorbent bed #21A and #21 B, and the polishing desulfurizer #210 at a temperature between 300° and 900° C. In this case, the exhaust gas with air injection to <2% O₂is required to convert the adsorbed/reacted sulfur on the catalyst adsorbents into SO₂. However, if the temperature of the exhaust gas is not high enough, it is necessary to inject both biogas and air to obtain <5% CH₄and <2% O₂concentration, and to produce reaction heats over the Pt group metal catalyst for maintaining the regeneration temperature. Furthermore, any hot gas containing <5% CH₄and <2% O₂can also be used to replace the exhaust gas for the catalyst regeneration.
As shown in FIG. 1 , in addition to provide electricity to the CHP generator's PLC controller unit #3, the excess electricity from reformate engine and electric generator #6 can be combined with wind power/solar power #1, and/or the electricity from the general distribution grid #2 to perform electrolysis of DI water in vessel #5. The H₂and O₂so produced can be stored separately in tanks #4 and #7 respectively. The H₂in tank #4 can be used to assist the lean fuel combustion at high compression ratio inside the reformate engine's cylinder, which can improve its thermal efficiency; The O₂in tank #7 can be used to replace air as the reformer's oxidant in the ATR reformer's inlet fuel mixture, which can improve the % (H₂+CO) concentration in the reformate to be close to that produced by a steam reformer, and can make the separation of H₂from other gases easier.
When the reformer is first started, the biogas and the O_hfuel mixture must reach a minimum temperature (i.e. light-off temperature) between 200 to 350° C. to initiate and to accelerate the catalytic partial oxidation reactions of bio-methane. Therefore, the biogas fuel mixture must be preheated by one of the following three methods: (1). utilize the exhaust gas from engine #6; (2). utilize the H₂and O₂gases in tanks #4 and #7 to generate the oxidation reaction heat by passing them through the Pt group catalyst bed, and (3). utilize an igniter to ignite the biogas and air/O₂flame. Because H₂and O₂can react with each other to produce the reaction heat over the Pt group metal catalyst at the room temperature, using the produced reformate or the engine's exhaust gas is an excellent method to preheat the reformer. After the CPO reaction is initialized, the CPO reaction of bio-methane can generate enough reaction heat to keep the catalyst itself above its minimum reaction temperature (i.e. light-off temperature), and the reactions can be performed in an adiabatic condition.
After the ATR and water gas shift reformer #9, the reformate can pass through heat exchanger #11, and the cooled dry gas is stored in tank #14. The IC engine/gas turbine #15 can then use the stored reformate to drive an electric generator #16 to generate electricity. Finally, the exhaust gas from #15 can passed through #17 heat exchanger to generate hot water or hot air to provide heat for local residents. However, if a steam generating reformer is used to replace the ATR reformer in #9, the high pressure reformate containing high % steam can be used to drive a steam turbine/engine, and an electric generator to generate electricity. After the heat exchanger #11, the condensed water can be recycle back to #9 for reuse according to U.S. Pat. No. 8,397,509, and hot water and hot air are also generated from heat exchanger #11.
FIG. 3 is the brain of the control system, and it is shown as FIG. 3A in FIG. 1 . Here, a programmable logic controller (PLC) can communicate with a PC laptop computer via a RS-232 or an Ethernet cable, and the PLC can communicate with the input/output modules which connect directly to the automatic controlled devices. A control software is stored in the PC. As a group of the pre-calibrated set points is down loaded from the PC to the CPU inside the PLC, the CPU will then transmit the control signals to the respective control channels of the output module and, then, to the flow controllers to perform the actual flow rate and/or temperature control. In other words, when a given output module receives the set points, it will give the set point signals to each controlling device such as flow controllers, solenoid valves, oxygen sensor/regulator, temperature PID loops, and other instrument and devices, and the controlling devices would control flow rate and temperature according to the set points received. Similarly, each device can transmits its current status and any update information from the input modules to the PC computer via the reverse signal transmission loops.
FIG. 4 is an actual control curve, which indicates the % reformate flow output as a function of the pressure in the storage vessel. Briefly, every point on a given control curve includes a group of pre-calibrated set points for each flow controller and for the operating temperature and pressure. Therefore, each point will provide the fuel mixture with a given pre-calibrated O₂/CH₄and (H₂O+CO₂)/CH₄ratios, the pre-calibrated reactants' flow rate and the total reformate flow output flow. In other words, a given group of set points will be down loaded from the control PC to the PLC, these pre-calibrated flow set points will be transmitted individually to each flow controller and the flow controller in the system will adjust each reactant's flow rate. By combining and mixing each reactant's flow rate together at the reformer's inlet, a fuel mixture with the specified pre-calibrated O₂/CH₄and (H₂O+CO₂)/CH₄ratios can be obtained. If every point in the same control curve is pre-calibrated to give the fuel mixture with the same O₂/CH₄and (H₂O+CO₂)/CH₄ratios, but with different flow rates, every point on the same control curve will provide the same reformate composition but with different flow output. Similarly, different pre-calibrated control curve can provide a biogas fuel mixture with different O₂/CH₄and (H₂O+CO₂)/CH₄ratios and, thus, different reformate composition and flow output.
For other hydrocarbons and bio-fuels, similar pre-calibrated control curve can provide a fuel mixture with a given O₂/CH₄and (H₂O+CO₂)/CH₄ratio and, thus, a given reformate composition and flow output can be obtained.
For a small system, the combination of a PC and a PLC can be replaced with a powerful microprocessor, or by a PC which is equipped with the necessary input/output modules to accomplish the same control strategy.

Claims

1-20. (canceled)

21. A method for operating a catalytic partial oxidation (CPO) desulfurization system, comprising:

providing a biogas;

providing a catalytic partial oxidation (CPO) reformer;

creating an inlet fuel mixture by mixing the biogas with O₂to adjust the inlet fuel mixture's O₂/CH₄ratio and H₂O/CH₄ratio;

delivering the biogas to the CPO reformer; and

reacting the biogas in the CPO reformer to create a reformate having a H₂/CH₄ratio, wherein the O₂/CH₄ratio of the inlet fuel mixture is adjusted to control the H₂/CH₄ratio in the reformate.

22. The method of claim 21, comprising treating the biogas with a desulfurizer prior to creating the inlet fuel mixture.

23. The method of claim 22, wherein the desulfurizer comprises one or more of a liquid wash, a filter, oxide adsorbents and regenerable supported Pt group metal catalysts.

24. The method of claim 21, comprising producing the biogas using a fermentation process in the absence of oxygen.

25. The method of claim 21, wherein the CPO reformer comprises Pt group catalysts.

26. The method of claim 21, wherein reacting the biogas in the CPO reformer comprises converting sulfur in the biogas to H₂S in the reformate.

27. The method of claim 26, comprising removing the H₂S from the reformate.

28. The method of claim 27, wherein the H₂S is removed using supported regenerable Pt group metal catalysts.

29. The method of claim 28, wherein the H₂S is removed at a temperature between 300° to 900° C.

30. The method of claim 28, wherein the Pt group metal catalysts comprise one or more metals in the group of Pt, Pd, Rh, Ir, Ru, Os, and mixtures thereof, and are supported on stabilized Al₂O₃.

31. The method of claim 21, wherein the reacting the biogas in the CPO reformer is done at an O₂/C ratio of 0.05 to 0.25.

32. The method of claim 31, wherein the reacting the biogas in the CPO reformer is done at a temperature between 200° to 800° C.

33. The method of claim 21, comprising providing to an inlet of the CPO reformer a reactant mixture containing air or pure oxygen, water, and one or more fuels selected from the group consisting of a natural gas, a hydrocarbon and a biofuel for the purpose of controlling the H₂/CH₄ratio in the reformate by the O₂/CH₄ratio in the inlet feed mixture.

34. The method of claim 21, comprising using the produced reformate from the reformer with a given H₂/CH₄ratio as a fuel to perform hydrogen assisted combustion by a downstream internal combustion engine/gas turbine.

35. The method of claim 34, wherein the engine/gas turbine is connected to an electric generator to produce power as a distributed power station.